WO2021193720A1 - Adhesive optical film - Google Patents

Adhesive optical film Download PDF

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Publication number
WO2021193720A1
WO2021193720A1 PCT/JP2021/012257 JP2021012257W WO2021193720A1 WO 2021193720 A1 WO2021193720 A1 WO 2021193720A1 JP 2021012257 W JP2021012257 W JP 2021012257W WO 2021193720 A1 WO2021193720 A1 WO 2021193720A1
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WO
WIPO (PCT)
Prior art keywords
pressure
weight
monomer
less
sensitive adhesive
Prior art date
Application number
PCT/JP2021/012257
Other languages
French (fr)
Japanese (ja)
Inventor
普史 形見
賢一 片岡
智哉 西野
祐輔 山本
慎太郎 野依
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2021049060A external-priority patent/JP2022008014A/en
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020227036353A priority Critical patent/KR20220156594A/en
Priority to CN202180024191.3A priority patent/CN115315647A/en
Publication of WO2021193720A1 publication Critical patent/WO2021193720A1/en

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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00Adhesives based on unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • C09J7/381Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385Acrylic polymers
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to an adhesive optical film, and more particularly to an adhesive optical film including a light transmitting member and an adhesive layer bonded to the light transmitting member.
  • an adhesive also referred to as a pressure-sensitive adhesive; the same applies hereinafter
  • adhesives are widely used for the purpose of joining, fixing, protecting, etc. in various industrial fields such as home appliances, automobiles, various machines, electric devices, and electronic devices.
  • a display device such as a liquid crystal display device or an organic EL display device
  • a polarizing film, a retardation film, a cover window member, and various other light-transmitting members are joined to another member. Uses to be mentioned.
  • Patent Documents 1 and 2 are listed as technical documents relating to adhesives for optical members.
  • Patent Documents 1 and 2 describe a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester polymer containing a monomer having a plurality of aromatic rings as a monomer unit as a main component, and a pressure-sensitive adhesive obtained by cross-linking the pressure-sensitive adhesive composition.
  • a specific pressure-sensitive adhesive having a refractive index exceeding 1.570 there is also known a technique of blending particles made of an inorganic material having a high refractive index (for example, inorganic particles such as zirconium oxide particles and titanium oxide particles) into a resin to increase the refractive index, but inorganic particles are blended.
  • the refractive index and the adhesive properties (for example, peel strength, flexibility, etc.) of the adhesive have a trade-off relationship, it is difficult to apply the adhesive to the field of the adhesive.
  • an adhesive optical film including a light transmitting member and an adhesive layer laminated on the light transmitting member.
  • the adhesive optical film has an adhesive surface composed of the adhesive layer.
  • the pressure-sensitive adhesive layer has a refractive index of more than 1.570, a total light transmittance of 86% or more, and a haze value of 3.0% or less.
  • the light transmissive member and the adhesive layer are integrated. Therefore, by using the adhesive optical film, the light transmissive member and the adherend are formed through the adhesive layer. It is possible to efficiently and accurately form a structure in which and is laminated.
  • the thickness of the pressure-sensitive adhesive layer is 5 ⁇ m or more. According to the pressure-sensitive adhesive layer having such a thickness, good pressure-sensitive adhesive properties can be easily obtained. Further, since the pressure-sensitive adhesive layer having such a thickness absorbs irregularities that may exist on the surface of the adherend and is easily bonded to the adherend with good adhesion, adhesion having a high refractive index on the adherend.
  • the agent layer can be appropriately provided.
  • the peel strength (adhesive strength) of the adhesive optical film with respect to the glass plate is 3N / 25 mm or more. Having such adhesive strength is preferable from the viewpoint of bonding reliability with the adherend.
  • the adhesive surface has an arithmetic mean roughness Ra of 100 nm or less. Having such a highly smooth adhesive surface is preferable from the viewpoint of optical homogeneity. For example, in a usage mode in which light is extracted through the pressure-sensitive adhesive surface (a mode in which the pressure-sensitive adhesive layer is arranged on the viewpoint side of the self-luminous element in a light emitting device, etc.), uneven brightness occurs due to the surface state of the pressure-sensitive adhesive layer. Can be suppressed.
  • the water absorption rate of the pressure-sensitive adhesive layer is 1.0% or less. According to the pressure-sensitive adhesive layer having a low water absorption rate, it is possible to suppress a dimensional change of the pressure-sensitive adhesive layer due to a fluctuation in the amount of water in the pressure-sensitive adhesive layer. Thereby, the warp of the adhesive type optical film or the laminated body containing the adhesive type optical film can be suppressed.
  • the pressure-sensitive optical film is configured as a laminate containing the pressure-sensitive adhesive layer and the resin film as a light-transmitting member.
  • an adhesive optical film with a release liner which comprises any of the adhesive optical films disclosed herein and a release liner arranged on the adhesive surface of the adhesive optical film. Will be done.
  • the adhesive optical film disclosed herein is manufactured, stored, distributed, processed, etc. in the form of an adhesive optical film with a release liner in which a release liner is arranged on the adhesive surface in this way, and is applied to an adherend. It can be preferably used in a mode in which the release liner is peeled off from the adhesive surface before sticking.
  • the self-luminous element means a light emitting element capable of controlling the emission brightness by the flowing current value.
  • the self-luminous element may be composed of a single body or an aggregate.
  • Specific examples of the self-luminous element include, but are not limited to, a light emitting diode (LED) and an organic EL.
  • the light emitting device may include such a self-luminous element as a component.
  • Examples of the light emitting device include, but are not limited to, a light source module device used as lighting (for example, a planar light emitting body module) and a display device having pixels formed therein.
  • FIG. 1 An example of the configuration of the adhesive optical film disclosed by this specification is shown in FIG.
  • this adhesive type optical film 1 the light laminated on the pressure-sensitive adhesive layer 10 in which the first surface 10A is the surface to be attached to the adherend (adhesive surface) and the second surface 10B of the pressure-sensitive adhesive layer 10. It is configured as a single-sided adhesive adhesive optical film (single-sided adhesive sheet) including a transparent member 20.
  • the second surface 10B of the pressure-sensitive adhesive layer 10 is bonded to the first surface (non-peelable surface) 20A of the light-transmitting member 20.
  • the light transmissive member 20 can be, for example, a resin film for optics.
  • the light transmissive member 20 may be an optical film such as a polarizing plate.
  • the adhesive surface 10A is peeled off so that at least the adhesive layer side is a peelable surface (peeling surface). It may be in the form of an adhesive optical film 50 with a release liner protected by a liner 30.
  • the second surface 20B of the light transmissive member 20 (the surface opposite to the first surface 20A, also referred to as the back surface) is a peeling surface, and the adhesive surface 10A hits the second surface 20B.
  • the adhesive surface 10A may be protected by being wound or laminated so as to be in contact with each other.
  • the pressure-sensitive adhesive layer 10 may have a single-layer structure, and is a laminated structure in which two or more sub- pressure-sensitive adhesive layers having different compositions are directly in contact with each other (that is, without being separated by a layer of a non-adhesive material). You may.
  • the adhesive optical film disclosed herein can be a component of an optical laminate in which an optical member is bonded to at least one surface of an adhesive layer.
  • the adhesive optical film 1 shown in FIG. 1 can be a component of the optical laminate 100 in which the optical member 70 is bonded to the first surface 10A of the adhesive layer 10, as shown in FIG.
  • the optical member may be, for example, a glass plate, a resin film, a metal plate, or the like.
  • the adhesive type optical film 1 shown in FIG. 1 when the light transmitting member 20 is an optical member such as an optical film, the adhesive type optical film 1 is formed on the second surface 10B of the adhesive layer 10 by the optical member. Can be grasped as a bonded optical laminate.
  • the adhesive optical film disclosed herein includes a light-transmitting member having a non-peelable first surface and a second surface, and a first adhesive layer is fixed to the first surface. It may be in the form of a double-sided adhesive adhesive optical film in which the second pressure-sensitive adhesive layer is fixedly laminated on the second surface.
  • a double-sided adhesive adhesive optical film hereinafter, also referred to as a double-sided adhesive optical film
  • the second surface 20B is a non-peelable surface, a second pressure-sensitive adhesive layer is provided on the second surface 20B, and the second surface of the second pressure-sensitive adhesive layer is the second surface of the light-transmitting member 20.
  • Examples thereof include a form in which the first surface (the surface opposite to the second surface) of the second pressure-sensitive adhesive layer is bonded to 20B and is the second pressure-sensitive surface of the double-sided pressure-sensitive optical film.
  • the composition of the pressure-sensitive adhesive constituting the second pressure-sensitive adhesive layer may be the same as or different from the composition of the pressure-sensitive adhesive constituting the first pressure-sensitive adhesive layer.
  • the double-sided adhesive optical film before use may be in a form in which the first adhesive surface and the second adhesive surface are protected by a release liner.
  • the adhesive optical film disclosed herein may be in the form of a roll or in the form of a single leaf. Alternatively, it may be an adhesive optical film in a form further processed into various shapes.
  • the pressure-sensitive optical film disclosed herein has a pressure-sensitive adhesive layer having a refractive index of more than 1.570.
  • Such an adhesive layer can be realized by forming at least one surface (adhesive surface) of the adhesive layer with an adhesive having a refractive index of more than 1.570.
  • a pressure-sensitive adhesive having a refractive index of more than 1.570, a pressure-sensitive adhesive composition capable of forming the pressure-sensitive adhesive, and a pressure-sensitive optical film containing the pressure-sensitive adhesive can be provided.
  • the refractive index of the pressure-sensitive adhesive means the refractive index of the surface (adhesive surface) of the pressure-sensitive adhesive.
  • the refractive index of the pressure-sensitive adhesive can be measured using a commercially available refractive index measuring device (Abbe refractive index meter) under the conditions of a measurement wavelength of 589 nm and a measurement temperature of 25 ° C.
  • Abbe refractive index meter for example, a model "DR-M4" manufactured by ATAGO or an equivalent product thereof is used.
  • a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive to be evaluated can be used.
  • the refractive index of the pressure-sensitive adhesive can be measured by the method described in Examples described later.
  • the refractive index of the pressure-sensitive adhesive can be adjusted, for example, by the composition of the pressure-sensitive adhesive (for example, the composition of the monomer components constituting the base polymer, additives that can be used if necessary, etc.).
  • the refractive index of the pressure-sensitive adhesive may be preferably 1.580 or higher, more preferably 1.585 or higher, and even more preferably 1.590 or higher (eg 1.595 or higher). ..
  • the index of refraction of the pressure-sensitive adhesive is, for example, 1.600 or greater or greater than 1.600, 1.605 or greater or greater than 1.605, or 1.610 or greater or 1 It can be over 610.
  • the preferable upper limit of the refractive index of the pressure-sensitive adhesive is not limited to a specific range because it may differ depending on the refractive index of the adherend and the like.
  • the refractive index of the pressure-sensitive adhesive may be, for example, 1.700 or less, 1.670 or less, or 1.650 or less in consideration of the balance with the adhesive properties and transparency.
  • the adhesive optical film disclosed herein is in the form of a double-sided adhesive optical film in which one surface is a first adhesive surface and the other surface is a second adhesive surface, at least the first.
  • the refractive index of the first adhesive surface may satisfy any of the above-mentioned refractive coefficients, and the refractive index of the second adhesive surface is not particularly limited.
  • the refractive index n 2 of the second adhesive surface can be approximately comparable to the refractive index n 1 of the first adhesive surface. More specifically, the absolute value of the difference in refractive index between the two adhesive surfaces, that is,
  • , can be, for example, less than 0.05, less than 0.03, or less than 0.01.
  • may be 0.00 or greater than 0.00.
  • the difference between the refractive index n 1 of the first adhesive surface and the refractive index n 2 of the second adhesive surface of the double-sided adhesive optical film, that is, n 1 to n 2 is, for example, greater than 0.00. It may be large, 0.01 or more, 0.03 or more, 0.05 or more, 0.10 or more, 0.15 or more, 0.20 or more, 0. It may be 25 or more.
  • the magnitude relationship between n 1 and n 2 may be reversed.
  • the double-sided adhesive optical film having different refractive indexes between the first adhesive surface and the second adhesive surface is, for example, a first and second adhesive layers having different refractive indexes on the first surface and the second surface of the light transmissive member. Can be realized by laminating.
  • the pressure-sensitive optical film disclosed herein includes a pressure-sensitive adhesive layer having the above-mentioned high refractive index and a total light transmittance of 86% or more.
  • the total light transmittance of the pressure-sensitive adhesive layer is preferably 88% or more, more preferably 90% or more (for example, more than 90.0%), and even 90.5% or more. It may be 93% or more, or 95% or more.
  • the upper limit of the total light transmittance is a value obtained by subtracting the light loss (Frenel loss) due to reflection generated at the air interface from 100%, and practically, it may be about 98% or less, or even about 96% or less. Well, it may be about 95% or less.
  • the total light transmittance of the pressure-sensitive adhesive layer may be about 94% or less, about 93% or less, or about 92% or less in consideration of the refractive index and the adhesive property.
  • Total light transmittance is measured using a commercially available transmittance meter in accordance with JIS K 7136: 2000. As the transmittance meter, the trade name "HAZEMETER HM-150" manufactured by Murakami Color Technology Research Institute or its equivalent is used. More specifically, for example, the total light transmittance of the pressure-sensitive adhesive layer can be measured according to the examples described later.
  • the total light transmittance of the pressure-sensitive adhesive layer can be adjusted by selecting, for example, the composition and thickness of the pressure-sensitive adhesive layer.
  • the pressure-sensitive optical film disclosed herein is in the form of a double-sided pressure-sensitive optical film in which a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer are fixedly laminated on the first and second surfaces of a light-transmitting member.
  • at least the first pressure-sensitive adhesive layer may satisfy any of the above-mentioned total light transmission rates, and the total light transmission rate of the second pressure-sensitive adhesive layer is not particularly limited.
  • the total light transmittance of the second pressure-sensitive adhesive layer satisfies any of the total light transmittances of the first pressure-sensitive adhesive layer described above.
  • the pressure-sensitive optical film disclosed herein includes a pressure-sensitive adhesive layer having the above-mentioned high refractive index and a haze value of 3.0% or less.
  • the haze value of the pressure-sensitive adhesive layer is preferably 2.0% or less, more preferably 1.0% or less, still more preferably 0.9% or less. It may be 0.8% or less, 0.5% or less, or 0.3% or less.
  • the lower limit of the haze value of the pressure-sensitive adhesive layer is not particularly limited, and a smaller haze value is preferable from the viewpoint of improving transparency.
  • the haze value may be, for example, 0.05% or more, or 0.1% or more, in consideration of the refractive index and the adhesive property. It may be 0.2% or more, 0.3% or more, or 0.4% or more.
  • the "haze value” refers to the ratio of diffuse transmitted light to total transmitted light when the measurement target is irradiated with visible light. Also called cloudy value.
  • the haze value can be measured according to the method described in Examples described later.
  • the haze value of the pressure-sensitive adhesive layer can be adjusted by selecting, for example, the composition and thickness of the pressure-sensitive adhesive layer.
  • the pressure-sensitive optical film disclosed herein is in the form of a double-sided pressure-sensitive optical film in which a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer are fixedly laminated on the first and second surfaces of a light-transmitting member.
  • the first pressure-sensitive adhesive layer may satisfy any of the above-mentioned haze values
  • the haze value of the second pressure-sensitive adhesive layer is not particularly limited.
  • the haze value of the second pressure-sensitive adhesive layer satisfies any of the haze values of the first pressure-sensitive adhesive layer described above.
  • the adhesive surface of the adhesive optical film preferably has high surface smoothness.
  • the arithmetic average roughness Ra of the adhesive surface is limited to a predetermined value or less.
  • a configuration having an adhesive surface designed to have a low arithmetic mean roughness Ra is preferable from the viewpoint of optical homogeneity.
  • the arithmetic mean roughness Ra for example, in a usage mode in which light is extracted through the pressure-sensitive adhesive surface (such as a mode in which the pressure-sensitive adhesive layer is arranged on the viewpoint side of the self-luminous element in a light emitting device), the pressure-sensitive adhesive layer. It is possible to exert the effect of suppressing the occurrence of brightness unevenness due to the surface condition of the above.
  • the low arithmetic mean roughness Ra of the adhesive surface is also advantageous for suppressing optical strain, and the suppression of optical strain also contributes to the improvement of optical homogeneity.
  • the arithmetic mean roughness Ra of the adhesive surface is preferably about 70 nm or less, more preferably about 65 nm or less, still more preferably about 55 nm or less, and may be less than 50 nm. It may be less than 45 nm or less than 40 nm. From the viewpoint of production efficiency and the like, in some embodiments, the arithmetic mean roughness Ra of the adhesive surface may be, for example, about 10 nm or more, about 20 nm or more, or about 30 nm or more (for example, about 40 nm or more).
  • the arithmetic average roughness Ra of the first adhesive surface and the arithmetic average roughness Ra of the second adhesive surface may be about the same. , May be different.
  • the maximum height Rz of the adhesive surface is limited to a predetermined value or less.
  • a configuration having an adhesive surface designed to have a low maximum height Rz is preferable from the viewpoint of optical homogeneity.
  • the low maximum height Rz of the adhesive surface is also advantageous for suppressing optical distortion.
  • the maximum height Rz of the first adhesive surface is limited to a predetermined value or less, and the maximum height Rz of both adhesive surfaces. Is more preferably limited to a predetermined value or less. Since each adhesive surface of the double-sided adhesive optical film has high surface smoothness, it is possible to preferably realize adhesion having excellent optical homogeneity.
  • the maximum height Rz of the adhesive surface is preferably about 600 nm or less, more preferably about 500 nm or less, still more preferably about 450 nm or less, and particularly preferably about 400 nm or less. It may be less than 350 nm, less than 300 nm, or less than 250 nm. From the viewpoint of production efficiency and the like, in some embodiments, the maximum height Rz of the adhesive surface may be, for example, about 10 nm or more, about 50 nm or more, about 100 nm or more, or about 200 nm or more. In the form of the adhesive type optical film having the first adhesive surface and the second adhesive surface, the maximum height Rz of the first adhesive surface and the maximum height Rz of the second adhesive surface may be the same or different. May be.
  • the arithmetic mean roughness Ra and the maximum height Rz of the adhesive surface are measured using a non-contact type surface roughness measuring device.
  • a non-contact type surface roughness measuring device a light interference type surface roughness measuring device is used, and for example, a three-dimensional optical profiler (trade name "NewView7300", manufactured by ZYGO) or an equivalent product thereof can be used. can.
  • the specific measurement operation and measurement conditions can be set according to the measurement conditions described in Examples described later, or to obtain results equivalent to or corresponding to those according to the measurement conditions.
  • the arithmetic mean roughness Ra and maximum height Rz of the adhesive surface are the composition and properties (viscosity, leveling property, etc.) of the adhesive composition used to form the adhesive layer, and the surface of the release liner that protects the adhesive surface (release surface). ) Can be adjusted according to the properties.
  • the pressure-sensitive adhesive layer constituting the pressure-sensitive optical film has a water absorption rate limited to a predetermined value or less.
  • a predetermined value or less it is preferable that the above-mentioned refractive index, total light transmittance and haze value are satisfied, and the water absorption rate is limited to a predetermined value or less.
  • the adhesive optical film or the adhesive optical film caused by the mismatch of the dimensional changes between the adhesive layer and the layer adjacent thereto (which may be a light transmitting member, a release liner, an adherend, etc.) It is possible to suppress the warp of the included optical laminate. It is preferable that the fluctuation of the water content in the pressure-sensitive adhesive layer can be suppressed from the viewpoint of maintaining the flatness, transparency, refractive index and the like of the pressure-sensitive adhesive layer constant. Further, since the pressure-sensitive adhesive layer having a low water absorption rate does not easily absorb water, it is suitable as an adhesive type optical film used for a member or product containing an element that dislikes water such as an organic EL element.
  • the water absorption of the pressure-sensitive adhesive layer is preferably about 1.0% or less, preferably 0.7% or less, and 0.5% or less (eg 0.5%). Less than), more preferably 0.4% or less, 0.3% or less, and 0.2% or less.
  • the lower limit of the water absorption rate of the pressure-sensitive adhesive layer is not particularly limited, but from a practical point of view such as compatibility with the pressure-sensitive adhesive properties, for example, it may be 0.01% or more, 0.05% or more, or 0.1%. It may be more than or equal to, 0.15% or more, and 0.25% or more.
  • the water absorption rate of at least the first pressure-sensitive adhesive layer is limited to a predetermined value or less. From the viewpoint of obtaining a higher effect, it is more preferable that the water absorption rates of the first and second pressure-sensitive adhesive layers are all limited to a predetermined value or less.
  • the water absorption rate (also referred to as water content) of the pressure-sensitive adhesive layer is measured by the following method. The same method is adopted in the examples described later. [Measurement of moisture content]
  • the pressure-sensitive adhesive layer to be evaluated is cut into a size of 4 cm ⁇ 5 cm (area: 20 cm 2 ) together with two release liners arranged on one surface and the other surface, and the release liner on one surface is removed. Then, it is attached to the aluminum foil that has been weighed in advance. Next, the release liner on the other surface of the pressure-sensitive adhesive layer is removed, placed in a constant temperature and humidity chamber having a temperature of 60 ° C. and a relative humidity of 90%, and taken out after 72 hours.
  • the gel fraction of the pressure-sensitive adhesive layer is appropriately set according to the purpose of use, the mode of use, and the like, and is not limited to a specific range.
  • the gel fraction is, for example, about 99% or less, and about 97% or less is appropriate. From the viewpoint of facilitating a good balance between high refractive index and adhesive properties, in some preferred embodiments, the gel fraction is about 95% or less, more preferably about 92% or less (for example, about 90% or less). obtain.
  • the fact that the gel fraction is not too high appropriately follows the unevenness that may exist on the surface of the adherend (for example, the uneven structure provided for the purpose of improving the light extraction efficiency in the light emitting device), and satisfactorily follows. It is also preferable from the viewpoint of close contact.
  • the gel fraction may be approximately 88% or less, approximately 75% or less, or approximately 65% or less.
  • the gel fraction of the pressure-sensitive adhesive layer is, for example, about 10% or more, and preferably about 20% or more, from the viewpoint of imparting appropriate cohesiveness to the pressure-sensitive adhesive and appropriately expressing the pressure-sensitive adhesive properties. Yes, it may be about 30% or more.
  • the gel fraction is preferably about 30% or more, more preferably about 40% or more, and is about 40% or more. It may be 45% or more, about 50% or more, about 65% or more, or about 75% or more.
  • the gel fraction can be adjusted by adjusting the molecular weight, molecular structure, concentration, degree of cross-linking, etc. of the base polymer. The gel fraction is measured by the following method.
  • a predetermined amount of the pressure-sensitive adhesive sample (weight Wg 1 ) is wrapped in a porous polytetrafluoroethylene film (weight Wg 2 ) having an average pore size of 0.2 ⁇ m in a purse-like shape, and the mouth is tied with an octopus thread (weight Wg 3 ).
  • a porous polytetrafluoroethylene (PTFE) film the trade name "Nitoflon (registered trademark) NTF1122" (average pore diameter 0.2 ⁇ m, porosity 75%, thickness 85 ⁇ m) available from Nitto Denko Co., Ltd. or its equivalent Use the item.
  • the gel fraction described above can be applied to at least the adhesive layer constituting the first adhesive surface, preferably the first adhesive surface. It is applied to both the constituent pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer constituting the second pressure-sensitive adhesive surface.
  • the gel fraction of the pressure-sensitive adhesive layer constituting the first adhesive surface and the gel fraction of the pressure-sensitive adhesive layer constituting the second adhesive surface may be about the same or different.
  • the storage elastic modulus G' (Storage modulus G')
  • the storage elastic modulus G'(25) of the pressure-sensitive adhesive can be, for example, about 700 kPa or less. In some embodiments, the storage elastic modulus G'(25) of the pressure-sensitive adhesive is preferably about 600 kPa or less, preferably 500 kPa or less, from the viewpoint of ease of attachment to the adherend.
  • the storage elastic modulus G'(25) of the pressure-sensitive adhesive is approximately 330 kPa or less, from the viewpoint of increasing the flexibility of the pressure-sensitive adhesive in the room temperature range (for example, 25 ° C.) and facilitating adhesion to the adherend. It is advantageous to have it, and it is preferably 300 kPa or less. In some embodiments where stickability and flexibility at room temperature are more important, the storage elastic modulus G'(25) of the pressure-sensitive adhesive may be, for example, less than 270 kPa or less than 250 kPa, and may be less than 200 kPa.
  • the storage modulus G'(25) of the pressure-sensitive adhesive may be less than 100 kPa or less than 90 kPa.
  • the lower limit of the storage elastic modulus G'(25) of the pressure-sensitive adhesive is not particularly limited, but may be, for example, 30 kPa or more, 50 kPa or more, or 70 kPa or more from the viewpoint of workability and handleability.
  • the storage elastic modulus G'(25) may be 100 kPa or higher, 150 kPa or higher, 200 kPa or higher, 250 kPa or higher, or 300 kPa or higher, in consideration of increasing the refractive index.
  • the storage elastic modulus G'(hereinafter, also referred to as "storage elastic modulus G'(50)") of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer at 50 ° C. is particularly limited. However, it can be less than 100 kPa, for example. In some embodiments, the storage modulus G'(50) is preferably less than 60 kPa, preferably less than 40 kPa, more preferably less than 38 kPa (eg, less than 36 kPa). As described above, the adhesive having a limited storage elastic modulus G'(50) can easily improve the adhesion to the adherend by appropriately heating it as necessary, whereby the adherend can be adhered to the adherend.
  • the lower limit of the storage elastic modulus G'(50) of the pressure-sensitive adhesive is not particularly limited.
  • the storage elastic modulus G'(50) may be, for example, 10 kPa or higher, 15 kPa or higher, 20 kPa or higher, or 23 kPa or higher, from the viewpoint of the heat resistant properties of the pressure-sensitive adhesive.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer has the following conditions: (A) The storage elastic modulus G'(25) at 25 ° C. is 350 kPa or less (preferably less than 200 kPa, for example 180 kPa or less); and (b) the storage elastic modulus G'(50) at 50 ° C. is less than 60 kPa (preferably less than 60 kPa). Is less than 50 kPa, more preferably less than 40 kPa, eg less than 38 kPa); It is preferable to satisfy at least one of the above.
  • a pressure-sensitive adhesive that satisfies at least the above condition (a) is preferable from the viewpoint of adhesion to an adherend in a room temperature range (for example, 25 ° C.).
  • a pressure-sensitive adhesive that satisfies at least the above condition (b) is preferable because the adhesion (adhesiveness) to the adherend can be easily improved by heating to a temperature slightly higher than room temperature.
  • the adhesive that does not satisfy the above condition (a) and satisfies the above (b) has good reworkability (reapplyability) at the initial stage of application in the room temperature range, and is heated to a temperature slightly higher than room temperature. It can be used as a heat-activated adhesive that can effectively increase the peel strength from the adherend.
  • the thermal activation may be performed by heating the pressure-sensitive adhesive to a temperature slightly higher than room temperature when it is attached to the adherend.
  • the temperature slightly higher than the room temperature is, for example, about 60 ° C. or lower, preferably about 55 ° C. or lower (for example, about 50 ° C. or lower).
  • the ratio of the storage elastic modulus G'(50) [kPa] to the storage elastic modulus G'(25) [kPa] of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is, for example, 70% or less, 40% or less, 30% or less, or 20% or less.
  • a pressure-sensitive adhesive having a small G'(50) / G'(25) is suitable for use as the above-mentioned heat-activated type pressure-sensitive adhesive.
  • the lower limit of G'(50) / G'(25) is not particularly limited.
  • G'(50) / G'(25) is, for example, 5% or more, preferably 10% or more from the viewpoint of heat resistance characteristics of the pressure-sensitive adhesive, and may be 12% or more, or 15% or more.
  • the storage elastic moduli G'(25) and G'(50) can be obtained by dynamic viscoelasticity measurement, and G'(50) / G'(25) can be calculated from the results.
  • Dynamic viscoelasticity measurement can be performed by a conventional method using a commercially available dynamic viscoelasticity measuring device, for example, using "Advanced Rheometric Expansion System (ARES)" manufactured by TA Instruments or an equivalent product thereof. It can be performed under the following measurement conditions.
  • As the sample for measurement a sample prepared to have a thickness of about 1.5 mm by laminating the pressure-sensitive adhesive layer to be evaluated as necessary is used. [Measurement condition]
  • Deformation mode Torsion measurement frequency: 1Hz
  • Temperature rise rate 5 ° C / min
  • Shape Parallel plate 7.9 mm ⁇
  • the storage modulus G'(25), G'(50) and storage modulus ratio of the pressure-sensitive adhesive layer are selected from the composition of the monomer components constituting the base polymer of the pressure-sensitive adhesive (for example, the type and content of the monomer (m1)). It can be adjusted by selecting the amount), the presence / absence of the cross-linking agent, the selection of the type and the amount used, the presence / absence of the refractive modulus improver and the thermoplastic material described later, the selection of the type and the amount used, and the like.
  • the monomer (m1) in addition to the first monomer which is the main component of the monomer (m1), a relatively small amount of a second monomer having a chemical structure different from that of the first monomer is used in the first monomer.
  • G'(50) when used in combination with a monomer, G'(50) can be reduced and G'(50) / G'(25) can be lowered in addition to the case where the first monomer is used alone as the monomer (m1). ..
  • the above-mentioned storage elasticity G'(25), G'(50) and storage elasticity ratio constitute at least the first adhesive surface. It is applied to the pressure-sensitive adhesive layer, preferably applied to both the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive surface and the pressure-sensitive adhesive layer constituting the second pressure-sensitive adhesive surface.
  • the storage elastic modulus G'of the pressure-sensitive adhesive layer constituting the first adhesive surface and the storage elastic modulus G'of the pressure-sensitive adhesive layer forming the second adhesive surface may be about the same or different.
  • the peak temperature of the tan ⁇ of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is preferably about ⁇ 50 ° C. or higher, and more preferably about 50 ° C. or lower. ..
  • the pressure-sensitive adhesive tan ⁇ has a measurement temperature range of -60 ° C while sandwiching a disk-shaped pressure-sensitive adhesive sample with a thickness of about 2 mm and a diameter of 7.9 mm between parallel plates and applying shear strain at a frequency of 1 Hz using a viscoelasticity tester.
  • Tpeak peak temperature of tan ⁇ of the pressure-sensitive adhesive
  • the Tpeak of the pressure-sensitive adhesive is preferably 45 ° C. or lower or 35 ° C. or lower, preferably 30 ° C. or lower (for example, 25 ° C. or lower), 20 ° C. or lower, and 15 ° C. or lower. It may be as follows. Adhesives with a lower Tpeak tend to provide good initial adhesiveness and adhesion in the room temperature range. On the other hand, it is preferable that the Tpeak of the pressure-sensitive adhesive is not too low from the viewpoint of imparting appropriate cohesiveness to the pressure-sensitive adhesive, and it tends to be suitable for both high refractive index and high refractive index.
  • the Tpeak of the pressure-sensitive adhesive may be, for example, ⁇ 40 ° C. or higher, ⁇ 30 ° C. or higher, ⁇ 20 ° C. or higher, ⁇ 5 ° C. or higher, 5 ° C. or higher. However, it may be 15 ° C. or higher, and further may be 25 ° C. or higher.
  • a pressure-sensitive adhesive having a relatively high Tpeak can be preferably used in an embodiment in which one or both of the pressure-sensitive adhesive and the adherend are heated to a temperature slightly higher than room temperature, if necessary, when the pressure-sensitive adhesive is attached to the adherend.
  • the Tpeak of the pressure-sensitive adhesive can be adjusted by selecting the composition of the pressure-sensitive adhesive (for example, the composition of the monomer components constituting the base polymer, the presence or absence of a refractive index improver or a thermoplastic material, the type and the amount used), and the like. ..
  • the Tpeak of the above-mentioned adhesive is preferably applied to at least the adhesive layer constituting the first adhesive surface, and more preferably. It is applied to both the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive surface and the pressure-sensitive adhesive layer constituting the second pressure-sensitive adhesive surface.
  • the Tpeak of the pressure-sensitive adhesive layer forming the first adhesive surface and the Tpeak of the pressure-sensitive adhesive layer forming the second adhesive surface may be the same or different.
  • the type of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited.
  • the pressure-sensitive adhesive may be an acrylic polymer, a rubber-based polymer (for example, natural rubber, synthetic rubber, a mixture thereof, etc.), a polyester-based polymer, a urethane-based polymer, a polyether polymer, or a silicone-based polymer that can be used in the field of pressure-sensitive adhesives.
  • One or more of various rubber-like polymers such as polyamide polymers and fluoropolymers are included as adhesive polymers (hereinafter, also referred to as "base polymers" in the sense of structural polymers forming adhesives). obtain.
  • a pressure-sensitive adhesive containing an acrylic polymer or a rubber-based polymer as a base polymer can be preferably adopted.
  • a pressure-sensitive adhesive (acrylic pressure-sensitive adhesive) using an acrylic polymer as a base polymer is preferable.
  • the technique disclosed herein is preferably carried out in an embodiment using an acrylic pressure-sensitive adhesive.
  • a pressure-sensitive adhesive layer composed of an acrylic pressure-sensitive adhesive that is, a pressure-sensitive adhesive film having an acrylic-based pressure-sensitive adhesive layer will be mainly described. It is not intended to be limited to those composed of agents.
  • the "base polymer” of the pressure-sensitive adhesive refers to the main component of the rubber-like polymer contained in the pressure-sensitive adhesive, and is not interpreted in any limitation other than this.
  • the rubber-like polymer refers to a polymer that exhibits rubber elasticity in a temperature range near room temperature.
  • the “main component” refers to a component contained in an amount of more than 50% by weight unless otherwise specified.
  • the "acrylic polymer” refers to a polymer containing a monomer unit derived from a monomer having at least one (meth) acryloyl group in one molecule as a monomer unit constituting the polymer.
  • a monomer having at least one (meth) acryloyl group in one molecule is also referred to as an “acrylic monomer”. Therefore, the acrylic polymer in this specification is defined as a polymer containing a monomer unit derived from an acrylic monomer.
  • a typical example of the acrylic polymer is a polymer in which the proportion of the acrylic monomer in the total monomers used in the synthesis of the acrylic polymer is more than 50% by weight (preferably more than 70% by weight, for example, more than 90% by weight). Be done.
  • "(meth) acryloyl” means a comprehensive reference to acryloyl and methacryloyl.
  • acrylic means acrylic and methacrylic, respectively. Therefore, the concept of the acrylic monomer here may include both a monomer having an acryloyl group (acrylic monomer) and a monomer having a methacryloyl group (methacryl monomer).
  • the adhesive optical film disclosed herein has a refractive index of more than 1.570, a total light transmittance of 86% or more, and a haze value of 3.0% or less (preferably 2.0% or less, More preferably, it can be carried out in an embodiment including an acrylic pressure-sensitive adhesive layer (1.0% or less).
  • an acrylic pressure-sensitive adhesive layer (1.0% or less).
  • the acrylic polymer that is the base polymer of the acrylic pressure-sensitive adhesive layer those containing an aromatic ring-containing monomer (m1) as a monomer component constituting the acrylic polymer are preferable. That is, an acrylic polymer containing an aromatic ring-containing monomer (m1) as a monomer unit is preferable.
  • the "monomer component constituting the acrylic polymer” is a monomer contained in the pressure-sensitive adhesive composition in the form of a preformed polymer (which may be an oligomer) or a non-polymerized monomer. Regardless of whether it is contained in the pressure-sensitive adhesive composition in its form, it means a monomer constituting a repeating unit of an acrylic polymer in a pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition. That is, the monomer component constituting the acrylic polymer may be contained in the pressure-sensitive adhesive composition in any form of a polymer, a non-polymer, or a partial polymer.
  • a pressure-sensitive adhesive composition containing substantially all of the monomer components for example, 95% by weight or more, preferably 99% by weight or more
  • a pressure-sensitive adhesive composition containing substantially all of the monomer components in the form of a polymer is preferable from the viewpoint of easily forming a pressure-sensitive optical film with less distortion and warpage.
  • a compound containing at least one aromatic ring and at least one ethylenically unsaturated group in one molecule is used.
  • the monomer (m1) one of the compounds may be used alone or in combination of two or more.
  • Examples of the ethylenically unsaturated group include (meth) acryloyl group, vinyl group, (meth) allyl group and the like.
  • a (meth) acryloyl group is preferable from the viewpoint of polymerization reactivity, and an acryloyl group is more preferable from the viewpoint of flexibility and adhesiveness.
  • a compound (that is, a monofunctional monomer) in which the number of ethylenically unsaturated groups contained in one molecule is 1 is preferably used as the monomer (m1).
  • the number of aromatic rings contained in one molecule of the compound used as the monomer (m1) may be 1 or 2 or more.
  • the upper limit of the number of aromatic rings contained in the monomer (m1) is not particularly limited, and may be 16 or less, for example.
  • the number of aromatic rings may be, for example, 12 or less, preferably 8 or less, from the viewpoint of ease of preparation of the acrylic polymer (A) and transparency of the pressure-sensitive adhesive. More preferably, it may be 5 or less, 4 or less, 3 or less, or 2 or less.
  • the aromatic ring of the compound used as the monomer (m1) is, for example, a benzene ring (which may be a benzene ring forming a part of a biphenyl structure or a fluorene structure); a naphthalene ring, an inden ring, an azulene ring, an anthracene ring, and a phenanthrene.
  • It may be a carbon ring such as a fused ring of a ring; for example, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, an isooxazole ring, and the like. It may be a heterocycle such as a thiazole ring or a thiophene ring.
  • the heteroatom contained as a ring-constituting atom in the heterocycle may be one or more selected from the group consisting of, for example, nitrogen, sulfur and oxygen.
  • the heteroatom constituting the heterocycle can be one or both of nitrogen and sulfur.
  • the monomer (m1) may have a structure in which one or more carbon rings and one or more heterocycles are condensed, for example, a dinaphthothiophene structure.
  • the aromatic ring may have one or more substituents on the ring-constituting atom, and may not have a substituent.
  • the substituent includes an alkyl group, an alkoxy group, an aryloxy group, a hydroxyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydroxyalkyl group, a hydroxyalkyloxy group, and a glycidyloxy group.
  • Etc. but are not limited thereto.
  • the number of carbon atoms contained in the substituent is preferably 1 to 4, more preferably 1 to 3, and may be, for example, 1 or 2.
  • the aromatic ring has one or more substituents that do not have a substituent on the ring-constituting atom or are selected from the group consisting of an alkyl group, an alkoxy group and a halogen atom (eg, a bromine atom). It can be an aromatic ring having.
  • the fact that the aromatic ring of the monomer (m1) has a substituent on its ring-constituting atom means that the aromatic ring has a substituent other than the substituent having an ethylenically unsaturated group.
  • the aromatic ring and the ethylenically unsaturated group may be directly bonded or may be bonded via a linking group.
  • the linking group is, for example, an alkylene group, an oxyalkylene group, a poly (oxyalkylene) group, a phenyl group, an alkylphenyl group, an alkoxyphenyl group, and a structure in which one or more hydrogen atoms are substituted with hydroxyl groups in these groups. It can be a group containing one or more structures selected from the group (eg, hydroxyalkylene group), oxy group (—O— group), thiooxy group (—S— group), and the like.
  • the aromatic ring and the ethylenically unsaturated group are directly bonded or bonded via a linking group selected from the group consisting of alkylene groups, oxyalkylene groups and poly (oxyalkylene) groups.
  • An aromatic ring-containing monomer having a structure having a structure can be preferably adopted.
  • the number of carbon atoms in the alkylene group and the oxyalkylene group is preferably 1 to 4, more preferably 1 to 3, and may be, for example, 1 or 2.
  • the number of repetitions of the oxyalkylene unit in the poly (oxyalkylene) group can be, for example, 2 to 3.
  • Examples of compounds that can be preferably used as the monomer (m1) include aromatic ring-containing (meth) acrylates and aromatic ring-containing vinyl compounds.
  • the aromatic ring-containing (meth) acrylate and the aromatic ring-containing vinyl compound can be used individually by 1 type or in combination of 2 or more types, respectively.
  • One or more aromatic ring-containing (meth) acrylates may be used in combination with one or more aromatic ring-containing vinyl compounds.
  • the content of the monomer (m1) in the monomer component constituting the acrylic polymer (A) is not particularly limited, and the desired refractive index and adhesive properties (for example, peel strength, flexibility, etc.) and / or optical properties (for example, all) are not particularly limited. It can be set so as to realize a pressure-sensitive adhesive layer that has both light transmittance, haze value, etc.).
  • the content of the monomer (m1) in the monomer component may be, for example, 30% by weight or more, preferably 50% by weight or more, 60% by weight or more, or 70% by weight or more. good.
  • the content of the monomer (m1) may be, for example, more than 70% by weight, 75% by weight or more, or 80% by weight or more. It may be 85% by weight or more, 90% by weight or more, or 95% by weight or more.
  • the upper limit of the content of the monomer (m1) in the above-mentioned monomer component is 100% by weight. From the viewpoint of achieving both high refractive index and adhesive properties and / or optical properties in a well-balanced manner, it is advantageous that the content of the monomer (m1) is less than 100% by weight, for example, about 99% by weight or less.
  • the content of the monomer (m1) may be 93% by weight or less, 90% by weight or less, 80% by weight or less, or 75% by weight or less. In some embodiments where more adhesive and / or optical properties are emphasized, the content of the monomer (m1) in the monomer component may be 70% by weight or less, 60% by weight or less, or 45% by weight or less. good.
  • the monomer (m1) has two or more aromatic rings (preferably carbon rings) in one molecule because a high refractive index increasing effect can be easily obtained.
  • Monomers can be preferably used.
  • a monomer having two or more aromatic rings in one molecule hereinafter, also referred to as “monomer containing a plurality of aromatic rings”
  • a monomer having a structure in which two or more non-condensed aromatic rings are bonded via a linking group a monomer having a structure in which two or more non-condensed aromatic rings are bonded via a linking group.
  • a monomer having a structure in which two or more non-condensed aromatic rings are chemically bonded directly that is, without interposing other atoms
  • a monomer having a condensed aromatic ring structure a monomer having a fluorene structure, and a monomer having a dinaphthothiophene structure.
  • the monomer containing a plurality of aromatic rings may be used alone or in combination of two or more.
  • the linking group is, for example, an oxy group (-O-), a thiooxy group (-S-), an oxyalkylene group (for example, -O- (CH 2 ) n- group, where n is 1 to 3, preferably 1).
  • oxyalkylene groups eg-S- (CH 2 ) n -groups, where n is 1-3, preferably 1)
  • linear alkylene groups ie-(CH 2 ) n -groups, where n is 1 to 6, preferably 1 to 3
  • the oxyalkylene group, the thiooxyalkylene group, and the group in which the alkylene group in the linear alkylene group is partially halogenated or completely halogenated, and the like can be used.
  • linking group examples include an oxy group, a thiooxy group, an oxyalkylene group and a linear alkylene group.
  • the monomer having a structure in which two or more non-condensed aromatic rings are bonded via a linking group include phenoxybenzyl (meth) acrylate (for example, m-phenoxybenzyl (meth) acrylate) and thiophenoxybenzyl (meth). Examples thereof include acrylate, benzylbenzyl (meth) acrylate, and the like.
  • the monomer having a structure in which the above two or more non-condensed aromatic rings are directly chemically bonded may be, for example, a biphenyl structure-containing (meth) acrylate, a triphenyl structure-containing (meth) acrylate, a vinyl group-containing biphenyl, or the like. Specific examples include o-phenylphenol (meth) acrylate and biphenylmethyl (meth) acrylate.
  • Examples of the monomer having a condensed aromatic ring structure include naphthalene ring-containing (meth) acrylate, anthracene ring-containing (meth) acrylate, vinyl group-containing naphthalene, and vinyl group-containing anthracene.
  • 1-naphthylmethyl (meth) acrylate also known as 1-naphthalenemethyl (meth) acrylate
  • hydroxyethylated ⁇ -naphthol acrylate 2-naphthoethyl (meth) acrylate
  • 2-naphthoxyethyl acrylate 2-naphthoxyethyl acrylate
  • 2 -(4-Methoxy-1-naphthoxy) ethyl (meth) acrylate etc.
  • the monomer having a fluorene structure examples include 9,9-bis (4-hydroxyphenyl) fluorene (meth) acrylate and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (meth) acrylate. And so on. Since the monomer having a fluorene structure contains a structural portion in which two benzene rings are directly chemically bonded, it is included in the concept of a monomer having a structure in which two or more non-condensed aromatic rings are directly chemically bonded.
  • Examples of the monomer having a dinaphthophene structure include (meth) acryloyl group-containing dinaphthophene, vinyl group-containing dinaphthophene, and (meth) allyl group-containing dinaphthothiophene.
  • R 1 is a hydrogen atom or a methyl group), (meth) acryloyloxyethyl dinaphthophene (eg, CH 2 CH (R 1 ) C (O) at the 5th or 6th position of the dinaphthophene ring.
  • R 1 is a hydrogen atom or a methyl group), vinyl dinaphthophene.
  • a compound having a structure in which a vinyl group is bonded to the 5- or 6-position of the naphthophene ring (meth) allyloxydinaphthophene, and the like.
  • the monomer having a dinaphthophene structure is included in the concept of a monomer having a condensed aromatic ring structure because it contains a naphthalene structure and also has a structure in which a thiophene ring and two naphthalene structures are condensed.
  • NS a compound having a structure in which a vinyl group is bonded to the 5- or 6-position of the naphthophene ring
  • Examples of the monomer having a dibenzothiophene structure include (meth) acryloyl group-containing dibenzothiophene, vinyl group-containing dibenzothiophene, and the like.
  • a monomer having a dibenzothiophene structure is included in the concept of a monomer having a condensed aromatic ring structure because it has a structure in which a thiophene ring and two benzene rings are condensed. Neither the dinaphthothiophene structure nor the dibenzothiophene structure corresponds to a structure in which two or more uncondensed aromatic rings are directly chemically bonded.
  • a monomer having one aromatic ring (preferably a carbon ring) in one molecule may be used as the monomer (m1) in the technique disclosed herein.
  • a monomer having one aromatic ring in one molecule can be useful for improving the flexibility of the pressure-sensitive adhesive, adjusting the pressure-sensitive adhesive properties, improving the transparency, and the like.
  • the monomer having one aromatic ring in one molecule is preferably used in combination with a monomer containing a plurality of aromatic rings from the viewpoint of improving the refractive index of the pressure-sensitive adhesive.
  • Examples of monomers having one aromatic ring in one molecule include benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, phenyl (meth) acrylate, ethoxylated phenol (meth) acrylate, and phenoxypropyl (meth) acrylate.
  • the monomer (m1) a monomer having a structure in which an oxyethylene chain is interposed between an ethylenically unsaturated group and an aromatic ring in various aromatic ring-containing monomers as described above may be used.
  • the number of repetitions of the oxyethylene unit (-CH 2 CH 2 O-) in the oxyethylene chain is typically 1 to 4, preferably 1 to 3, more preferably 1 to 2, and is, for example, 1.
  • ethoxylated aromatic ring-containing monomer examples include ethoxylated o-phenylphenol (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, ethoxylated cresol (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol.
  • Di (meth) acrylate and the like can be mentioned.
  • the content of the monomer containing a plurality of aromatic rings in the monomer (m1) is not particularly limited, and may be, for example, 5% by weight or more, 25% by weight or more, or 40% by weight or more.
  • the content of the aromatic ring plurality-containing monomer in the monomer (m1) may be, for example, 50% by weight or more, 70% by weight, from the viewpoint of facilitating the realization of a pressure-sensitive adhesive having a higher refractive index.
  • the above is preferable, and it may be 85% by weight or more, 90% by weight or more, or 95% by weight or more.
  • Substantially 100% by weight of the monomer (m1) may be a monomer containing a plurality of aromatic rings.
  • the content of the aromatic ring plurality-containing monomer in the monomer (m1) is less than 100% by weight, for example, in consideration of the balance between the high refractive index and the adhesive property and / or the optical property. It may be 98% by weight or less, 90% by weight or less, 80% by weight or less, or 65% by weight or less. In some embodiments, the content of the aromatic ring multiple-containing monomer in the monomer (m1) may be 70% by weight or less, 50% by weight or less, or 25% by weight in consideration of adhesive properties and / or optical properties.
  • the technique disclosed herein can also be carried out in an embodiment in which the content of the monomer containing a plurality of aromatic rings in the monomer (m1) is less than 5% by weight. It is not necessary to use a monomer containing a plurality of aromatic rings.
  • the content of the aromatic ring-containing monomer in the monomer component constituting the acrylic polymer is not particularly limited, and the desired refractive index and adhesive properties (for example, peel strength, flexibility, etc.) and / or optical properties (for example, total light transmission) are not particularly limited. It can be set so as to realize a pressure-sensitive adhesive layer that is compatible with (property, haze value, etc.).
  • the content of the monomer containing a plurality of aromatic rings in the above-mentioned monomer component may be, for example, 3% by weight or more, 10% by weight or more, or 25% by weight or more.
  • the content of the aromatic ring plurality-containing monomer in the above-mentioned monomer component may be, for example, more than 35% by weight, more than 50% by weight, from the viewpoint of facilitating the realization of a pressure-sensitive adhesive having a higher refractive index. It may be more than 70% by weight, 75% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more.
  • the content of the monomer containing a plurality of aromatic rings in the above-mentioned monomer component may be 100% by weight, but may be less than 100% by weight from the viewpoint of achieving both high refractive index and adhesive properties and / or optical properties in a well-balanced manner.
  • the content of the aromatic ring plurality-containing monomer in the above-mentioned monomer component may be 70% by weight or less, 50% by weight or less, and 25% by weight or less in consideration of adhesive properties and / or optical properties. However, it may be 15% by weight or less, or 5% by weight or less.
  • the technique disclosed herein can also be carried out in an embodiment in which the content of the monomer containing a plurality of aromatic rings in the above-mentioned monomer component is less than 3% by weight.
  • a high refractive index monomer may be preferably employed as at least a portion of the monomer (m1).
  • the "high refractive index monomer” refers to a monomer having a refractive index of, for example, about 1.510 or more, preferably about 1.530 or more, and more preferably about 1.550 or more.
  • the upper limit of the refractive index of the high-refractive index monomer is not particularly limited, but is, for example, 3.000 or less from the viewpoint of ease of preparation of the pressure-sensitive adhesive composition and ease of compatibility with flexibility suitable as a pressure-sensitive adhesive. It may be .500 or less, 2.000 or less, 1.900 or less, 1.800 or less, or 1.700 or less.
  • the high refractive index monomer may be used alone or in combination of two or more.
  • the refractive index of the monomer is measured using an Abbe refractive index meter under the conditions of a measurement wavelength of 589 nm and a measurement temperature of 25 ° C.
  • As the Abbe refractive index meter a model "DR-M4" manufactured by ATAGO or an equivalent product thereof can be used. If the manufacturer or the like provides a nominal value of the refractive index at 25 ° C., the nominal value can be adopted.
  • the high-refractive index monomer has a refractive index among the compounds included in the concept of the aromatic ring-containing monomer (m1) disclosed herein (for example, the compounds and compound groups exemplified above). Can be adopted as appropriate. Specific examples include m-phenoxybenzyl acrylate (refraction: 1.566, homopolymer Tg: ⁇ 35 ° C.), 1-naphthylmethyl acrylate (refraction: 1.595, homopolymer Tg: 31 ° C.), O-phenylphenol acrylate ethoxylated (number of repetitions of oxyethylene unit: 1, refraction: 1.578), benzyl acrylate (refraction (nD20): 1.519, homopolymer Tg: 6 ° C), phenoxyethyl acrylate (Refraction (nD20): 1.517, homopolymer Tg: 2 ° C.), phenoxydiethylene glycol acrylate (refraction: 1.510, homopolymer Tg:
  • the content of the high refractive index monomer (that is, the aromatic ring-containing monomer having a refractive index of about 1.510 or more, preferably about 1.530 or more, more preferably about 1.550 or more) in the monomer (m1) is particularly high. It is not limited, and may be, for example, 5% by weight or more, 25% by weight or more, 35% by weight or more, or 40% by weight or more. In some embodiments, the content of the high refractive index monomer in the monomer (m1) may be, for example, 50% by weight or more, preferably 70% by weight or more, from the viewpoint of facilitating the acquisition of a higher refractive index. , 85% by weight or more, 90% by weight or more, 95% by weight or more.
  • Substantially 100% by weight of the monomer (m1) may be a high refractive index monomer.
  • the content of the high refractive index monomer in the monomer (m1) is less than 100% by weight, for example, from the viewpoint of achieving both high refractive index and adhesive properties and / or optical properties in a well-balanced manner. It may be 98% by weight or less, 90% by weight or less, 80% by weight or less, or 65% by weight or less.
  • the content of the high refractive index monomer in the monomer (m1) may be 70% by weight or less, 50% by weight or less, and 25% by weight or less in consideration of adhesive properties and / or optical properties.
  • the technique disclosed herein can also be carried out in an embodiment in which the content of the high refractive index monomer in the monomer component (m1) is less than 5% by weight. It is not necessary to use a high refractive index monomer.
  • the content of the high refractive index monomer in the monomer component constituting the acrylic polymer is not particularly limited, and the desired refractive index and adhesive properties (for example, peel strength, flexibility, etc.) and / or optical properties (for example, total light transmittance) are not particularly limited. , Haze value, etc.) can be set so as to realize a pressure-sensitive adhesive layer.
  • the content of the high refractive index monomer in the monomer component may be, for example, 3% by weight or more, 10% by weight or more, or 25% by weight or more.
  • the content of the high refractive index monomer in the above-mentioned monomer component may be, for example, more than 35% by weight, and more than 50% by weight. It may be more than 70% by weight, 75% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more.
  • the content of the high refractive index monomer in the above-mentioned monomer component can be 100% by weight, but it is advantageous to make it less than 100% by weight from the viewpoint of achieving a good balance between the high refractive index and the adhesive property and / or the optical property.
  • the content of the high refractive index monomer in the monomer component may be 70% by weight or less, 50% by weight or less, or 25% by weight or less in consideration of adhesive properties and / or optical properties. It may be 15% by weight or less, or 5% by weight or less.
  • the technique disclosed herein can also be carried out in an embodiment in which the content of the high refractive index monomer in the monomer component is less than 3% by weight.
  • the Tg of the homopolymer as at least a portion of the monomer (m1) is 10 ° C. or lower (preferably 5 ° C. or lower or 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower). , More preferably ⁇ 20 ° C. or lower, for example ⁇ 25 ° C. or lower), an aromatic ring-containing monomer (hereinafter, may be referred to as “monomer L”) is adopted.
  • the content of the aromatic ring-containing monomer (m1) in the monomer component increases the content of the pressure-sensitive adhesive.
  • the storage elasticity G'geners generally tends to increase, the increase in the storage elasticity G'can be suppressed by adopting the monomer L as a part or all of the monomer (m1). This makes it possible to improve the refractive index while better maintaining the flexibility suitable as a pressure-sensitive adhesive.
  • the lower limit of Tg of the monomer L is not particularly limited.
  • the Tg of the monomer L may be, for example, ⁇ 70 ° C. or higher, ⁇ 55 ° C. or higher, or ⁇ 45 ° C. or higher.
  • the monomer L one type can be used alone or two or more types can be used in combination.
  • the monomer L among the compounds included in the concept of the aromatic ring-containing monomer (m1) disclosed herein (for example, the compounds and compound groups exemplified above), those having the corresponding Tg are appropriately adopted. be able to.
  • the aromatic ring-containing monomer that can be used as the monomer L m-phenoxybenzyl acrylate (Tg of homopolymer: ⁇ 35 ° C.) can be mentioned.
  • Another preferred example is phenoxydiethylene glycol acrylate (homopolymer Tg: ⁇ 35 ° C.).
  • the content of the monomer L in the monomer (m1) is not particularly limited, and may be, for example, 5% by weight or more, 25% by weight or more, or 40% by weight or more. In some embodiments, the content of the monomer L in the monomer (m1) may be, for example, 50% by weight or more, from the viewpoint of facilitating the acquisition of a pressure-sensitive adhesive having both high refractive index and flexibility at a higher level. , 60% by weight or more, 70% by weight or more, 75% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more. Substantially 100% by weight of the monomer (A1) may be the monomer L.
  • the content of the monomer L in the monomer (m1) may be less than 100% by weight from the viewpoint of achieving both flexibility suitable as a pressure-sensitive adhesive and high refractive index in a well-balanced manner. , 98% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 50% by weight or less, 25% by weight or less, or 10% by weight or less.
  • the technique disclosed herein can also be carried out in an embodiment in which the content of the monomer L in the monomer (m1) is less than 5% by weight. It is not necessary to use the monomer L.
  • the content of the monomer L in the monomer component constituting the acrylic polymer may be, for example, 3% by weight or more, 10% by weight or more, or 25% by weight or more. In some embodiments, the content of the monomer L in the monomer component may be, for example,> 35% by weight, 50 It is preferably more than 70% by weight, more than 70% by weight, more than 75% by weight, more than 85% by weight, more than 90% by weight, and more than 95% by weight.
  • the content of the monomer L in the above-mentioned monomer component can be 100% by weight, but it is advantageous that the content is less than 100% by weight in consideration of the balance between the high refractive index and the adhesive property and / or the optical property.
  • the content of the monomer L in the monomer component may be 70% by weight or less, 50% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less. good.
  • the technique disclosed herein can also be carried out in an embodiment in which the content of the monomer L in the monomer component is less than 3% by weight.
  • the glass transition temperature Tg m1 based on the composition of the monomer (m1) is preferably about 20 ° C. or lower, preferably 10 ° C. or lower (eg 5) from the viewpoint of adhesive flexibility. (° C. or lower), more preferably 0 ° C. or lower, still more preferably ⁇ 10 ° C. or lower, ⁇ 20 ° C. or lower, or ⁇ 25 ° C. or lower.
  • the lower limit of the glass transition temperature Tg m1 is not particularly limited. In consideration of the balance with the effect of improving the refractive index, the glass transition temperature Tg m1 may be, for example, ⁇ 70 ° C. or higher, ⁇ 55 ° C. or higher, or ⁇ 45 ° C.
  • the technique disclosed herein can also be preferably carried out in an embodiment in which the glass transition temperature Tg m1 is, for example, ⁇ 40 ° C. or higher, ⁇ 35 ° C. or higher, ⁇ 33 ° C. or higher, ⁇ 30 ° C. or higher, or ⁇ 25 ° C. or higher.
  • the glass transition temperature Tg m1 based on the composition of the monomer (m1) is a Tg obtained by the Fox formula described later based on the composition of only the monomer (m1) among the monomer components constituting the acrylic polymer.
  • the glass transition temperature Tg m1 is a homopolymer of each aromatic ring-containing monomer used as the monomer (m1) by applying the Fox formula described later for only the monomer (m1) among the monomer components constituting the acrylic polymer. It can be calculated from the glass transition temperature and the weight fraction of each aromatic ring-containing monomer in the total amount of the monomers (m1).
  • the Tg of the homopolymer of the monomer and the glass transition temperature Tg m1 are the same.
  • the aromatic ring-containing monomer (m1) includes monomer L (ie, homopolymer Tg of 10 ° C. or lower, preferably 5 ° C. or lower or 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower, even more preferably.
  • monomer L ie, homopolymer Tg of 10 ° C. or lower, preferably 5 ° C. or lower or 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower, even more preferably.
  • a monomer H having a Tg higher than 10 ° C. can be used in combination.
  • the Tg of the monomer H may be, for example, more than 10 ° C., more than 15 ° C., or more than 20 ° C.
  • the monomer L and the monomer H in combination, for example, in a configuration in which the content of the aromatic ring-containing monomer (m1) in the monomer component is relatively large, the high refractive index and flexibility of the pressure-sensitive adhesive are compatible at a higher level. Can be made to.
  • the usage amount ratio of the monomer L and the monomer H can be set so as to preferably exhibit such an effect, and is not particularly limited. For example, it is preferable to set the usage amount ratio of the monomer L and the monomer H so as to satisfy any of the above-mentioned glass transition temperatures Tg m1.
  • the aromatic ring-containing monomer (m1) can be preferably selected from compounds that do not contain a structure in which two or more uncondensed aromatic rings are directly chemically bonded (eg, a biphenyl structure).
  • a monomer component having a composition in which the content of the compound containing a structure in which two or more non-condensed aromatic rings are directly chemically bonded is less than 5% by weight (more preferably less than 3% by weight and may be 0% by weight).
  • the acrylic polymer composed of is preferable.
  • Limiting the amount of a compound containing a structure in which two or more non-condensed aromatic rings are directly chemically bonded in this way is a viewpoint of realizing a pressure-sensitive adhesive having a good balance of flexibility, tackiness and high refractive index. Can be advantageous from.
  • the monomer component constituting the acrylic polymer may further contain a monomer (m2) in addition to the above-mentioned monomer (m1).
  • the monomer (m2) is a monomer corresponding to at least one of a monomer having a hydroxyl group (hydroxyl group-containing monomer) and a monomer having a carboxy group (carboxy group-containing monomer).
  • the hydroxyl group-containing monomer is a compound having at least one hydroxyl group and at least one ethylenically unsaturated group in one molecule.
  • the carboxy group-containing monomer is a compound containing at least one carboxy group and at least one ethylenically unsaturated group in one molecule.
  • the monomer (m2) can be useful for introducing cross-linking points into the acrylic polymer and imparting appropriate cohesiveness to the pressure-sensitive adhesive.
  • the monomer (m2) may be used alone or in combination of two or more.
  • the monomer (m2) is typically a monomer that does not contain an aromatic ring.
  • Examples of the ethylenically unsaturated group contained in the monomer (m2) include a (meth) acryloyl group, a vinyl group, a (meth) allyl group and the like.
  • a (meth) acryloyl group is preferable from the viewpoint of polymerization reactivity, and an acryloyl group is more preferable from the viewpoint of flexibility and adhesiveness.
  • a compound (that is, a monofunctional monomer) in which the number of ethylenically unsaturated groups contained in one molecule is 1 is preferably used as the monomer (m2).
  • hydroxyl group-containing monomers examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and (meth).
  • Hydroxy (meth) acrylate such as 8-hydroxyoctyl acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate Alkyl includes, but is not limited to.
  • hydroxyl group-containing monomers examples include 4-hydroxybutyl acrylate (Tg: ⁇ 40 ° C.) and 2-hydroxyethyl acrylate (Tg: ⁇ 15 ° C.). From the viewpoint of improving flexibility in the room temperature range, 4-hydroxybutyl acrylate having a lower Tg is more preferable. In a preferred embodiment, more than 50% by weight (eg, more than 50% by weight, more than 70% by weight or more than 85% by weight) of the monomer (m2) can be 4-hydroxybutyl acrylate.
  • the hydroxyl group-containing monomer may be used alone or in combination of two or more.
  • the hydroxyl group-containing monomer may be one or more selected from compounds having no methacryloyl group.
  • the hydroxyl group-containing monomer having no methacryloyl group include the above-mentioned various hydroxyalkyl acrylates.
  • hydroxyalkyl acrylate By using hydroxyalkyl acrylate, hydroxy groups that help provide cross-linking points and impart appropriate cohesiveness can be introduced into the acrylic polymer, and the room temperature is higher than when only the corresponding hydroxyalkyl methacrylate is used. It is easy to obtain an adhesive with good flexibility and adhesiveness in the region.
  • carboxy group-containing monomers examples include acrylic monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate, as well as itaconic acid, maleic acid, fumaric acid, and crotonic acid. Examples thereof include, but are not limited to, isocrotonic acid. Examples of carboxy group-containing monomers that can be preferably used include acrylic acid and methacrylic acid. The carboxy group-containing monomer may be used alone or in combination of two or more. A hydroxyl group-containing monomer and a carboxy group-containing monomer may be used in combination.
  • the content of the monomer (m2) in the monomer component constituting the acrylic polymer is not particularly limited and can be set according to the purpose.
  • the content of the monomer (m2) can be, for example, 0.01% by weight or more, 0.1% by weight or more, or 0.5% by weight or more.
  • the content of the monomer (A2) is preferably 1% by weight or more, preferably 2% by weight or more, or 4% by weight or more. ..
  • the upper limit of the content of the monomer (m2) in the monomer component is set so that the total content with the content of other monomers does not exceed 100% by weight.
  • the content of the monomer (m2) is, for example, 30% by weight or less or 25% by weight or less, and the content of the monomer (m1) is relatively increased to achieve high refraction. From the viewpoint of facilitating rate, it is preferably 20% by weight or less, more preferably 15% by weight or less, less than 12% by weight, less than 10% by weight, or less than 7% by weight. ..
  • the content of the hydroxyl group-containing monomer in the monomer component is not particularly limited, and is, for example, 0.01% by weight or more (preferably 0.1% by weight or more, more preferably 0). It can be 5.5% by weight or more). In some embodiments, the content of the hydroxyl group-containing monomer is preferably 1% by weight or more, preferably 2% by weight or more, or 4% by weight or more of the monomer component.
  • the upper limit of the content of the hydroxyl group-containing monomer in the monomer component is set so that the total content with the content of other monomers does not exceed 100% by weight, and it is appropriate to set it to, for example, 30% by weight or less or 25% by weight or less. From the viewpoint of facilitating high refractive index by relatively increasing the content of the monomer (m1), it is preferably 20% by weight or less, more preferably 15% by weight or less, and 12% by weight. It may be less than 10% by weight, less than 7% by weight, or less than 7% by weight.
  • the content of the carboxy group-containing monomer in the monomer component is not particularly limited, and is, for example, 0.01% by weight or more (preferably 0.1% by weight or more, more preferably 0.1% by weight or more). Can be 0.3% by weight or more).
  • the content of the carboxy group-containing monomer may be 1% by weight or more, 2% by weight or more, or 4% by weight or more.
  • the upper limit of the content of the carboxy group-containing monomer in the monomer component is set so that the total with the amount of other monomers used does not exceed 100% by weight, and it is appropriate to set it to, for example, 30% by weight or less or 25% by weight or less.
  • the content is preferably 20% by weight or less, more preferably 15% by weight or less, and 12 It may be less than 10% by weight, or less than 10% by weight.
  • the content of the carboxy group-containing monomer is preferably less than 7% by weight, preferably less than 5% by weight, and 3% by weight. It may be less than%, less than 1% by weight, or less than 0.5% by weight.
  • the technique disclosed herein can be preferably carried out, for example, in a mode in which only a hydroxyl group-containing monomer is used as the monomer (m2), that is, a mode in which a carboxy group-containing monomer is not used.
  • the total content of the monomer (m1) and the monomer (m2) in the monomer component constituting the acrylic polymer may be, for example, 31% by weight or more, preferably 51% by weight or more, or 61% by weight or more. , 71% by weight or more.
  • the total content of the monomer (m1) and the monomer (m2) in the monomer component constituting the acrylic polymer is, for example, 76% by weight from the viewpoint of facilitating the effect of these monomers. It may be more than 81% by weight, preferably 86% by weight or more, 91% by weight or more, 96% by weight or more, 99% by weight or more, substantially 100% by weight. But it may be.
  • the monomer component constituting the acrylic polymer may contain a monomer other than the above-mentioned monomer (m1) and the above-mentioned monomer (m2), if necessary.
  • An example of such an optional component is an alkyl (meth) acrylate (hereinafter, also referred to as “monomer (m3)”).
  • the monomer (m3) can be useful for adjusting the flexibility of the pressure-sensitive adhesive and improving the compatibility in the pressure-sensitive adhesive.
  • an alkyl (meth) acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms (that is, C 1-20) at the ester terminal can be preferably used.
  • C 1-20 alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate.
  • alkyl (meth) acrylates having a homopolymer Tg of ⁇ 20 ° C. or lower are preferably employed as at least a portion of the monomer (m3). Can be done.
  • Such low Tg alkyl (meth) acrylates can help improve the flexibility of the adhesive.
  • the lower limit of Tg of the alkyl (meth) acrylate is not particularly limited, and may be, for example, ⁇ 85 ° C. or higher, ⁇ 75 ° C. or higher, ⁇ 65 ° C. or higher, or ⁇ 60 ° C. or higher.
  • Specific examples of the low Tg alkyl (meth) acrylate include n-butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), and isononyl acrylate (iNA).
  • the monomer (m3) it is preferable that at least a part of the monomer (m3) is an alkyl acrylate from the viewpoint of flexibility, adhesiveness and the like.
  • the content of the alkyl (meth) acrylate in the monomer component can be set so that the effect of use thereof is appropriately exhibited.
  • the content of the alkyl (meth) acrylate may be, for example, 1% by weight or more, 3% by weight or more, 5% by weight or more, or 8% by weight or more.
  • the content of the alkyl (meth) acrylate may be 15% by weight or more, 30% by weight or more, or 45% by weight or more.
  • the upper limit of the content of the monomer (m3) in the monomer component is set so that the total content with the content of other monomers does not exceed 100% by weight, and can be, for example, less than 50% by weight. In some embodiments, the content of the monomer (m3) can be, for example, less than 35% by weight.
  • the refractive index of alkyl (meth) acrylate is relatively low. Therefore, in order to increase the refractive index, the content of the monomer (m3) in the monomer component is limited, and the content of the monomer (m1) is relatively large. It is advantageous to do.
  • the content of the monomer (m3) is preferably 24% by weight or less, preferably less than 23% by weight, more preferably less than 20% by weight, 17% by weight of the monomer component. It may be less than% by weight, less than 12% by weight, less than 7% by weight, less than 3% by weight, or less than 1% by weight. It is not necessary to use the monomer (m3) substantially.
  • the monomer component constituting the acrylic polymer may contain a monomer other than the above-mentioned monomers (m1), (m2), and (m3) (hereinafter, referred to as "other monomer"), if necessary.
  • the above-mentioned other monomers can be used, for example, for the purpose of adjusting Tg of an acrylic polymer, adjusting the adhesive performance, improving the compatibility in the pressure-sensitive adhesive layer, and the like.
  • the above-mentioned other monomers may be used alone or in combination of two or more.
  • Examples of the above-mentioned other monomers include monomers having functional groups other than hydroxyl groups and carboxy groups (functional group-containing monomers).
  • other monomers that can improve the cohesive force and heat resistance of the pressure-sensitive adhesive include sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, and cyano group-containing monomers.
  • an amide group-containing monomer for example, (meth).
  • amino group-containing monomer for example, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, etc.
  • monomer having a nitrogen atom-containing ring for example, , N-vinyl-2-pyrrolidone, N- (meth) acryloy
  • the monomers having a nitrogen atom-containing ring there is also a monomer corresponding to an amide group-containing monomer such as N-vinyl-2-pyrrolidone.
  • an amide group-containing monomer such as N-vinyl-2-pyrrolidone.
  • vinyl ester-based monomers such as vinyl acetate; non-aromatic ring-containing (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; ethylene, Olefin-based monomers such as butadiene and isobutylene; Chlorine-containing monomers such as vinyl chloride; alkoxy group-containing monomers such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and ethoxyethoxyethyl (meth) acrylate; Vinyl ether such as methyl vinyl ether System monomers; and the like.
  • ethoxyethoxyethyl acrylate also known as ethyl carbitol acrylate, homopolymer Tg: ⁇ 67 ° C.
  • the amount used is not particularly limited, and can be appropriately set within a range in which the total amount of the monomer components does not exceed 100% by weight.
  • the content of the other monomer in the monomer component can be, for example, about 35% by weight or less, and is about 25, from the viewpoint of facilitating the effect of improving the refractive index by using the monomer (m1). It is appropriate to set it to about 20% by weight or less (for example, 0 to 25% by weight), and it may be about 20% by weight or less (for example, 0 to 20% by weight), about 10% by weight or less, or about 5% by weight or less. For example, it may be about 1% by weight or less.
  • the technique disclosed herein can be preferably carried out in a manner in which the monomer component is substantially free of the other monomers.
  • the monomer component constituting the acrylic polymer may have a composition in which the amount of the methacryloyl group-containing monomer used is suppressed to a predetermined value or less.
  • the amount of the methacryloyl group-containing monomer used in the monomer component may be, for example, less than 5% by weight, less than 3% by weight, less than 1% by weight, or less than 0.5% by weight. Limiting the amount of the methacryloyl group-containing monomer used in this way can be advantageous from the viewpoint of realizing a pressure-sensitive adhesive having both flexibility and adhesiveness and a high refractive index in a well-balanced manner.
  • the monomer component constituting the acrylic polymer may have a composition that does not contain a methacryloyl group-containing monomer (for example, a composition consisting of only an acryloyl group-containing monomer).
  • the monomer component constituting the base polymer (for example, an acrylic polymer) of the pressure-sensitive adhesive layer uses an amount of a carboxy group-containing monomer from the viewpoint of suppressing coloring or discoloration (for example, yellowing) of the pressure-sensitive adhesive. Is preferably restricted.
  • the amount of the carboxy group-containing monomer used in the monomer component may be, for example, less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.3% by weight, and 0.1. It may be less than% by weight or less than 0.05% by weight.
  • This limitation of the amount of carboxy group-containing monomer used means that metal materials that can be placed in contact with or in close proximity to the adhesives disclosed herein (eg, metal wiring that may be present on the adherend). It is also advantageous from the viewpoint of suppressing corrosion of metal films, etc.).
  • the technique disclosed herein can be preferably carried out in a manner in which the above-mentioned monomer component does not contain a carboxy group-containing monomer.
  • the monomer component constituting the base polymer of the pressure-sensitive adhesive layer is a monomer having an acidic functional group (including a sulfonic acid group, a phosphoric acid group, etc. in addition to a carboxy group). It is preferable that the amount used is limited.
  • the amount of the acidic functional group-containing monomer used in the monomer component of such an embodiment can be applied.
  • the technique disclosed herein can be preferably carried out in a mode in which the monomer component does not contain an acidic group-containing monomer (that is, a mode in which the base polymer of the pressure-sensitive adhesive layer is acid-free).
  • the base polymer of the pressure-sensitive adhesive layer preferably has a glass transition temperature Tg T based on the composition of the monomer components constituting the polymer, which is approximately 20 ° C. or lower. , Approximately 10 ° C or lower, more preferably 0 ° C or lower, -10 ° C or lower, -20 ° C or lower, -25 ° C or lower, ⁇ 28 ° C or lower, ⁇ 28 ° C or lower, ⁇ It may be 30 ° C. or lower.
  • a low glass transition temperature Tg T can be advantageous from the viewpoint of improving the flexibility of the pressure-sensitive adhesive.
  • the glass transition temperature Tg T may be, for example, ⁇ 60 ° C. or higher, preferably ⁇ 50 ° C. or higher, and more preferably ⁇ 45 ° C. or higher, from the viewpoint of facilitating high refractive index of the pressure-sensitive adhesive. Yes, it may be above -40 ° C, above -35 ° C, above -25 ° C, above -15 ° C, or above -5 ° C. good.
  • the glass transition temperature Tg T of the polymer means the glass transition temperature obtained by the Fox formula based on the composition of the monomer components constituting the polymer, unless otherwise specified.
  • Tg is the glass transition temperature (unit: K) of the copolymer
  • Wi the weight fraction of the monomer i in the copolymer (copolymerization ratio based on the weight)
  • Tgi is the homopolymer of the monomer i.
  • the glass transition temperature (unit: K) of Represents the glass transition temperature (unit: K) of.
  • the glass transition temperature of the homopolymer used for calculating Tg the values described in publicly known materials such as "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) shall be used.
  • the monomers whose multiple types of values are described in the Polymer Handbook the highest value is adopted.
  • the Tg of the homopolymer is not described in the publicly known material, the value obtained by the measuring method described in Japanese Patent Application Publication No. 2007-51271 shall be used.
  • the method for obtaining the base polymer of the pressure-sensitive adhesive layer is not particularly limited, and is a solution polymerization method or an emulsion polymerization method.
  • a known polymerization method such as a bulk polymerization method, a suspension polymerization method, and a photopolymerization method can be appropriately adopted.
  • the solution polymerization method may be preferably employed.
  • the polymerization temperature at the time of solution polymerization can be appropriately selected depending on the type of monomer and solvent used, the type of polymerization initiator, etc., and is, for example, about 20 ° C. to 170 ° C. (typically 40 ° C. to 140 ° C.). °C).
  • the solvent (polymerization solvent) used for solution polymerization can be appropriately selected from conventionally known organic solvents.
  • aromatic compounds such as toluene (typically aromatic hydrocarbons); acetate esters such as ethyl acetate; aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane; 1,2-dichloroethane and the like.
  • the initiator used for polymerization can be appropriately selected from conventionally known polymerization initiators according to the type of polymerization method.
  • one or more azo-based polymerization initiators such as 2,2'-azobisisobutyronitrile (AIBN) can be preferably used.
  • Other examples of polymerization initiators include persulfates such as potassium persulfate; peroxide-based initiators such as benzoyl peroxide and hydrogen peroxide; substituted ethane-based initiators such as phenyl-substituted ethane; aromatic carbonyl compounds. ; Etc. can be mentioned.
  • polymerization initiator is a redox-based initiator that is a combination of a peroxide and a reducing agent.
  • the polymerization initiator may be used alone or in combination of two or more.
  • the amount of the polymerization initiator used may be a normal amount, for example, about 0.005 to 1 part by weight (typically about 0.01 to 1 part by weight) with respect to 100 parts by weight of the monomer component. ) Can be selected.
  • chain transfer agents can be used for the above polymerization, if necessary.
  • mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid, and ⁇ -thioglycerol can be used.
  • a chain transfer agent containing no sulfur atom non-sulfur chain transfer agent may be used.
  • non-sulfur chain transfer agents examples include anilines such as N, N-dimethylaniline and N, N-diethylaniline; terpenoids such as ⁇ -pinene and turpinolene; ⁇ -methylstyrene, ⁇ -methylstyrene dimer and the like. Styrenes; etc.
  • the chain transfer agent may be used alone or in combination of two or more. When the chain transfer agent is used, the amount used can be, for example, about 0.01 to 1 part by weight with respect to 100 parts by weight of the monomer raw material.
  • the weight average molecular weight (Mw) of the base polymer is not particularly limited, and may be in the range of , for example, approximately 10 ⁇ 10 4 to 500 ⁇ 10 4. From the viewpoint of adhesive performance, the Mw of the base polymer is about 20 ⁇ 10 4 to 400 ⁇ 10 4 (more preferably about 30 ⁇ 10 4 to 150 ⁇ 10 4 , for example, about 50 ⁇ 10 4 to 130 ⁇ 10 4 ). It is preferably in the range.
  • the Mw of the polymer can be determined by gel permeation chromatography (GPC) in terms of polystyrene. Specifically, it can be obtained by measuring under the following conditions using the trade name "HLC-8220 GPC" (manufactured by Tosoh Corporation) as the GPC measuring device.
  • GPC gel permeation chromatography
  • the above-mentioned pressure-sensitive adhesive layer may contain a refractive index improver, if necessary, in addition to the base polymer.
  • the refractive index improving agent in the present specification means a material capable of increasing the refractive index of the pressure-sensitive adhesive layer by its use.
  • the refractive index improver a material having a refractive index higher than that of the pressure-sensitive adhesive layer containing the refractive index improver can be preferably used.
  • the refractive index improving agent a material having a higher refractive index than the base polymer (for example, the acrylic polymer (A)) of the pressure-sensitive adhesive layer containing the refractive index improving agent can be preferably used.
  • the refractive index improver is preferably an organic material.
  • the organic material used as the refractive index improver may be a polymer or a non-polymer. Further, it may or may not have a polymerizable functional group.
  • the refractive index improver may be used alone or in combination of two or more.
  • the refractive index of the refractive index improver (for example, the additive (H RO ) described later) can be set in an appropriate range in relation to the refractive index of the base polymer, and is not limited to a specific range.
  • the refractive index of the refractive index improver can be selected from, for example, more than 1.55, more than 1.56 or more than 1.57, and higher than the refractive index of the base polymer.
  • the refractive index of the refractive index improver is preferably 1.58 or more, preferably 1.60 or more. It is more preferably 63 or more, 1.65 or more, 1.70 or more, or 1.75 or more.
  • the desired refractive index can be achieved by using a smaller amount of the refractive index improver. This is preferable from the viewpoint of suppressing deterioration of adhesive properties and optical properties.
  • the upper limit of the refractive index of the refractive index improver is not particularly limited, but from the viewpoint of compatibility in the pressure-sensitive adhesive and the ease of compatibility between high refractive index and flexibility suitable as a pressure-sensitive adhesive, for example, 3.000 or less. It may be 2.500 or less, 2.000 or less, 1.950 or less, 1.900 or less, or 1.850 or less.
  • the refractive index improvers (e.g., later-described additives (H RO)) difference between the refractive index n a of the refractive index n b and the base polymer, i.e. n b -n a (hereinafter, " ⁇ n A ”) is set to be greater than 0.
  • ⁇ n A is, for example, 0.02 or greater, 0.05 or greater, 0.07 or higher, 0.10 or higher, 0.15 or higher, 0.20 or higher. Alternatively, it may be 0.25 or more.
  • ⁇ n A may be, for example, 0.70 or less, 0.60 or less, or 0 in some embodiments. It may be .50 or less, 0.40 or less, or 0.35 or less.
  • the difference between the refractive index n b of the refractive index improver (eg, additive (H RO ) described below) and the refractive index n T of the pressure-sensitive adhesive layer containing the refractive index improver, i.e. n b n T (hereinafter, also referred to as “ ⁇ n B ”) is set to be larger than 0.
  • ⁇ n B is, for example, 0.02 or greater, 0.05 or greater, 0.07 or higher, 0.10 or higher, 0.15 or higher, 0.20 or higher. Alternatively, it may be 0.25 or more.
  • ⁇ n B may be, for example, 0.70 or less, 0.60 or less, or 0 in some embodiments. It may be .50 or less, 0.40 or less, or 0.35 or less.
  • the amount of the refractive index improver used with respect to 100 parts by weight of the base polymer (when a plurality of types of refractive index improvers are used, the total amount thereof) is not particularly limited and can be set according to the purpose.
  • the amount of the refractive index improver used with respect to 100 parts by weight of the base polymer can be, for example, 1 part by weight or more, and it is advantageous to use 3 parts by weight or more. It is preferably 7 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more.
  • the amount of the refractive index improver used with respect to 100 parts by weight of the base polymer can be, for example, 80 parts by weight or less, so that the refractive index of the pressure-sensitive adhesive is increased and the deterioration of the pressure-sensitive adhesive properties and the optical properties is suppressed. From the viewpoint of achieving a good balance between the above and the like, it is advantageous to use 60 parts by weight or less, and preferably 45 parts by weight or less. In some embodiments where more adhesive properties and optical properties are emphasized, the amount of the refractive index improver used with respect to 100 parts by weight of the base polymer may be, for example, 30 parts by weight or less, 20 parts by weight or less, or 15 parts by weight.
  • the technique disclosed herein is preferably carried out even in an embodiment in which the amount of the refractive index improver used in 100 parts by weight of the base polymer in the pressure-sensitive adhesive layer is less than 1 part by weight, or the refractive index improver is substantially not used. be able to.
  • “not practically used” means that it is not used at least intentionally.
  • the refractive index improver may preferably be an organic material having a higher refractive index than the base polymer.
  • additive (HRO) represents an organic material having a high refractive index.
  • a base polymer for example, an acrylic polymer, preferably an acrylic polymer (A)
  • HRO additive
  • the refractive index and adhesive properties peeling strength, flexibility, etc.
  • the organic material used as an additive ( HRO ) may be a polymer or a non-polymer. Further, it may or may not have a polymerizable functional group.
  • the additive (H RO ) may be used alone or in combination of two or more.
  • the refractive index of the additive (H RO ) is measured using an Abbe refractive index meter under the conditions of a measurement wavelength of 589 nm and a measurement temperature of 25 ° C., similarly to the refractive index of the monomer. If the manufacturer or the like provides a nominal value of the refractive index at 25 ° C., the nominal value can be adopted.
  • the molecular weight of the organic material used as an additive ( HRO ) is not particularly limited and can be selected according to the intended purpose.
  • the molecular weight of the additive (HRO ) is balanced from the viewpoint of achieving a good balance between the effect of increasing the refractive index and other properties (for example, flexibility suitable for an adhesive and optical properties such as haze). Is more than about 10,000, preferably less than 5,000, more preferably less than 3,000 (eg, less than 1,000), less than 800, less than 600, less than 500, and more. It may be less than 400. It may be advantageous from the viewpoint of improving the compatibility in the pressure-sensitive adhesive layer that the molecular weight of the additive (H RO) is not too large.
  • the molecular weight of the additive ( HRO ) may be, for example, 130 or more, or 150 or more.
  • the molecular weight of the additive (H RO) from the viewpoint of increasing the refractive index of the additive (H RO), preferably at least 170, more preferably 200 or more, 230 It may be 250 or more, 270 or more, 500 or more, 1000 or more, 2000 or more.
  • a polymer having a molecular weight of about 1000-10000 eg, 1000 or more and less than 5000 can be used as the additive (HRO).
  • the molecular weight of the additive (HRO ) is calculated based on the chemical structure, or matrix-assisted laser desorption / ionization. Measurements using time-of-flight mass spectrometry (MALDI-TOF-MS) can be used.
  • MALDI-TOF-MS time-of-flight mass spectrometry
  • Mw weight average molecular weight
  • aromatic ring of the organic compound having an aromatic ring used as an additive (hereinafter, also referred to as “aromatic ring-containing compound”) is the same as that of the aromatic ring of the compound used as the monomer (m1). Can be selected from.
  • the aromatic ring may have one or more substituents on the ring-constituting atom, and may not have a substituent.
  • the substituent includes an alkyl group, an alkoxy group, an aryloxy group, a hydroxyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydroxyalkyl group, a hydroxyalkyloxy group, and a glycidyloxy group.
  • Etc. but are not limited thereto.
  • the number of carbon atoms contained in the substituent is, for example, 1 to 10, preferably 1 to 6, preferably 1 to 4, and more preferably 1 to 3.
  • the aromatic ring has one or more substituents that do not have a substituent on the ring-constituting atom or are selected from the group consisting of an alkyl group, an alkoxy group and a halogen atom (eg, a bromine atom). It can be an aromatic ring having.
  • Examples of the aromatic ring-containing compound which can be used as additives for example: compounds may be used as the monomer (m1); oligomers containing a compound that may be used as the monomer (m1) as a monomer unit; monomer (m1 ), Except for a group having an ethylenically unsaturated group (which may be a substituent bonded to a ring-constituting atom) or a portion of the group constituting an ethylenically unsaturated group, a hydrogen atom or Compounds having a structure replaced with a group having no ethylenically unsaturated group (for example, a hydroxyl group, an amino group, a halogen atom, an alkyl group, an alkoxy group, a hydroxyalkyl group, a hydroxyalkyloxy group, a glycidyloxy group, etc.); However, it is not limited to these.
  • Non-limiting examples of aromatic ring-containing compounds that can be used as additives include benzyl acrylate, m-phenoxybenzyl acrylate, 2- (o-phenylphenoxy) ethyl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol.
  • Aromatic ring-containing compounds such as acrylates, phenoxypolyethylene glycol acrylates, 2-hydroxy-3-phenoxypropyl acrylates, the above-mentioned monomers having a fluorene structure, monomers having a dinaphthophene structure, and monomers having a dibenzothiophene structure; 3-phenoxybenzyl Alcohol, dinaphthophene and derivatives thereof (for example, one or two or more substituents selected from a hydroxy group, a methanol group, a diethanol group, a glycidyl group and the like are bonded to the dinaphthophene ring.
  • Aromatic ring-containing compounds that do not have ethylenically unsaturated groups, such as structural compounds); etc. may be included.
  • the aromatic ring-containing compound is an oligomer containing such an aromatic ring-containing monomer as a monomer unit (preferably an oligomer having a molecular weight of about 5000 or less, more preferably about 1000 or less. For example, a low polymer of about 2 to pentameric. ) Can be.
  • the oligomer is, for example: a homopolymer of an aromatic ring-containing monomer; a copolymer of one or more aromatic ring-containing monomers; a copolymer of one or two or more aromatic ring-containing monomers and another monomer. Coalescence; etc.
  • the other monomer one kind or two or more kinds of monomers having no aromatic ring may be used.
  • the additive ( HRO ) is an organic compound having two or more aromatic rings in one molecule because a high refractive index increasing effect can be easily obtained (hereinafter, “a compound containing a plurality of aromatic rings”). ”) Can be preferably adopted.
  • the compound containing a plurality of aromatic rings may or may not have a polymerizable functional group such as an ethylenically unsaturated group. Further, the compound containing a plurality of aromatic rings may be a polymer or a non-polymer.
  • the polymer is an oligomer containing a monomer containing a plurality of aromatic rings as a monomer unit (preferably an oligomer having a molecular weight of about 5000 or less, more preferably about 1000 or less, for example, a low polymer of about 2 to pentamer).
  • the above oligomers include, for example: a homopolymer of a plurality of aromatic ring-containing monomers; a copolymer of one or more kinds of multiple aromatic ring-containing monomers; and one or more kinds of multiple aromatic ring-containing monomers and other monomers. Copolymer; etc.
  • the other monomer may be an aromatic ring-containing monomer that does not correspond to a monomer containing a plurality of aromatic rings, a monomer having no aromatic ring, or a combination thereof.
  • a non-limiting example of a compound containing a plurality of aromatic rings is a compound having a structure in which two or more non-condensed aromatic rings are bonded via a linking group, and two or more non-condensed aromatic rings directly (that is, other atoms).
  • examples thereof include a compound having a chemically bonded structure (without intervening), a compound having a condensed aromatic ring structure, a compound having a fluorene structure, a compound having a dinaphthophene structure, a compound having a dibenzothiophene structure, and the like.
  • the compound containing a plurality of aromatic rings may be used alone or in combination of two or more.
  • the compound having a fluorene structure examples include the above-mentioned monomer having a fluorene structure, an oligomer which is a homopolymer or a copolymer of such a monomer, and 9,9-bis (4-hydroxyphenyl) fluorene (Refraction rate: 1.68), 9,9-bis (4-aminophenyl) fluorene (refractive rate: 1.73), 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (refractive rate: 1) .68), 9,9-bisphenylfluorene and its derivatives such as 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (refractive index: 1.65) can be mentioned.
  • the compound having a dinaphthophene structure include the above-mentioned monomer having a dinaphthophene structure, an oligomer which is a homopolymer or a copolymer of such a monomer, and dinaphthophene (refractive index: 1.
  • hydroxyalkyl dinaphthophenes such as 6-hydroxymethyldinaphthophene (refractive index: 1.766); dihydroxydinaphthophenes such as 2,12-dihydroxydinaphthophene (refractive index: 1.750); 2 , 12-Dihydrochiethyloxydinaphthophene (refractive index: 1.677) and other dihydroxyalkyloxydinaphthophenes; Naftthiophene; dinaphthophene having two or more ethylenically unsaturated groups such as 2,12-dialyloxydinaphthophene (abbreviation: 2,12-DAODNT, refractive index 1.729); The derivative is mentioned.
  • the compound having the above-mentioned dibenzothiophene structure include the above-mentioned monomer having the dibenzothiophene structure, an oligomer which is a homopolymer or a copolymer of the above-mentioned monomer, and dibenzothiophene (refractive rate: 1.607).
  • examples thereof include 4-dimethyldibenzothiophene (refractive rate: 1.617), 4,6-dimethyldibenzothiophene (refractive rate: 1.617), and the like.
  • heterocyclic also called containing organic compound.
  • thioepoxy compound a compound having a triazine ring, and the like.
  • the thioepoxy compound include bis (2,3-epithiopropyl) disulfide described in Japanese Patent No. 3712653 and a polymer thereof (refractive index 1.74).
  • the compound having a triazine ring include a compound having at least one triazine ring (for example, 3 to 40, preferably 5 to 20) in one molecule.
  • the compound having a triazine ring is also included in the concept of the above-mentioned aromatic ring-containing compound, and the compound having a plurality of triazine rings is also included in the concept of the above-mentioned compound containing a plurality of aromatic rings. Will be done.
  • the additive ( HRO ) may preferably be a compound that does not have an ethylenically unsaturated group.
  • Adopting an additive (H RO ) having no ethylenically unsaturated group means an adhesive optical film having an adhesive layer containing the additive (H RO ), a laminate containing the adhesive optical film, or the like. From the viewpoint of suppressing dimensional changes, deformations (warping, waviness, etc.), occurrence of optical strain, etc. due to the reaction of ethylenically unsaturated groups, it is also preferable.
  • the oligomer in an embodiment in which an oligomer is used as an additive ( HRO ), can be obtained by polymerizing the corresponding monomer component in a known manner.
  • polymerization can be carried out by appropriately adding a polymerization initiator, a chain transfer agent, an emulsifier and the like used for radical polymerization to the above-mentioned monomer component.
  • the polymerization initiator, chain transfer agent, emulsifier and the like used in the above radical polymerization are not particularly limited and can be appropriately selected and used.
  • the weight average molecular weight of the oligomer can be controlled by the amount of the polymerization initiator and the chain transfer agent used, and the reaction conditions, and the amount used is appropriately adjusted according to these types.
  • the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, ⁇ -thioglycerol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2,3-dimercapto-1-propanol and the like. Be done.
  • the chain transfer agent may be used alone or in combination of two or more.
  • the amount of the chain transfer agent used can be set so that an oligomer having a desired weight average molecular weight can be obtained according to the composition of the monomer component used for the synthesis of the oligomer, the type of the chain transfer agent, and the like.
  • the amount of the chain transfer agent used with respect to 100 parts by weight of the total amount of the monomers used in the synthesis of the oligomer is preferably about 15 parts by weight or less, and may be 10 parts by weight or less, and 5 parts by weight. It may be less than or equal to the degree.
  • the lower limit of the amount of the chain transfer agent used with respect to 100 parts by weight of the total amount of the monomers used for the synthesis of the oligomer is not particularly limited, but may be, for example, 0.01 parts by weight or more, 0.1 parts by weight or more, and 0. It may be 5 parts by weight or more, or 1 part by weight or more.
  • the amount of additive to 100 parts by weight of the base polymer (H RO) (in the case of using a plurality of compounds, their total amount), particularly It is not limited and can be set according to the purpose.
  • the amount of the additive ( HRO ) used with respect to 100 parts by weight of the base polymer can be, for example, 1 part by weight or more, and it is advantageous to use 3 parts by weight or more. It is preferably 5 parts by weight or more, 7 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more.
  • the amount of the additive (HRO ) used with respect to 100 parts by weight of the base polymer can be, for example, 80 parts by weight or less, so that the refractive index of the pressure-sensitive adhesive is increased and the deterioration of the pressure-sensitive adhesive properties and the optical properties is suppressed. From the viewpoint of achieving a good balance between the above and the like, it is advantageous to use 60 parts by weight or less, and preferably 45 parts by weight or less. In some embodiments where more adhesive properties and optical properties are emphasized, the amount of the additive (HRO ) used per 100 parts by weight of the base polymer may be, for example, 30 parts by weight or less, 20 parts by weight or less, and 15 parts by weight. It may be 10 parts by weight or less.
  • the pressure-sensitive adhesive layer is a plasticized product having a lower molecular weight than the base polymer, in addition to the base polymer as described above (for example, the acrylic polymer (A)). May include material.
  • the thermoplastic material By using the thermoplastic material, the flexibility of the pressure-sensitive adhesive layer can be increased, and the adhesion to the adherend, the flexibility of the pressure-sensitive optical film as a whole, and the followability to deformation can be improved.
  • the plasticizing material an organic material can be preferably adopted from the viewpoint of compatibility and transparency in the pressure-sensitive adhesive layer.
  • the thermoplastic material may be a material that can also be used as the above-mentioned refractive index improver (for example, the above-mentioned additive ( HRO)).
  • the molecular weight of the plasticizing material may be lower than that of the base polymer, and is not particularly limited.
  • the molecular weight of the plasticizing material may be 30,000 or less, 25,000 or less, less than 10,000, preferably less than 5,000, and less than 3,000 (preferably less than 3,000, from the viewpoint of facilitating the development of the plasticizing effect.
  • less than 1000 is more preferable, and it may be less than 800, less than 600, less than 500, or less than 400.
  • the fact that the molecular weight of the plasticized material is not too large can be advantageous from the viewpoint of improving compatibility in the pressure-sensitive adhesive layer.
  • the molecular weight of the plasticizing material is preferably 130 or more, preferably 150 or more, and may be 170 or more, from the viewpoint of facilitating the exertion of a sufficient plasticizing effect. , 200 or more, 250 or more, 300 or more. In some embodiments, the molecular weight of the thermoplastic material may be 500 or greater, 1000 or greater, or 2000 or greater. It is preferable that the molecular weight of the plasticized material is not too low from the viewpoint of heat resistance and suppression of contamination of the adherend.
  • Non-limiting examples of compounds that can be options for plasticizing materials include compounds that can be used as monomers (m1) (eg, (meth) acrylates having aromatic rings such as benzyl group, phenoxy group, naphthyl group, fluorene structure.
  • m1 eg, (meth) acrylates having aromatic rings such as benzyl group, phenoxy group, naphthyl group, fluorene structure.
  • a low Tg monomer such as n-butyl acrylate or 2-ethylhexyl acrylate may be copolymerized with the oligomer containing a compound that can be used as the monomer (m1) as a monomer unit.
  • the plasticizing material one or more known plasticizers (for example, phthalate ester, terephthalic acid ester, adipate ester, adipate polyester, benzoic acid glycol ester, etc.) may be used. good.
  • thermoplastic material an organic material having a refractive index of about 1.50 or more (more preferably 1.53 or more) can be preferably used.
  • specific examples of compounds that can be options for plasticizing materials include diethylene glycol dibenzoate (refraction: 1.55), dipropylene glycol dibenzoate (refraction: 1.54), 3-phenoxytoluene (refraction: 1.57), 3-Ethylbiphenyl (refraction 1.59), 3-methoxybiphenyl (refraction 1.61), 4-methoxybiphenyl (refraction 1.57), polyethylene glycol dibenzoate, 3-phenoxybenzyl alcohol (refraction 1) .59), triphenyl phosphate (refraction rate 1.56), benzyl benzoate (refraction rate 1.57), 4- (tert-butyl) phenyldiphenyl phosphate (refraction rate 1.56), trimethylphenyl phosphate (refraction rate 1.56) 1.55), butylbenzylphthalate (refraction: 1.55), di
  • the refractive index of the plasticized material is not particularly limited and may be, for example, 3.00 or less.
  • the refractive index of the thermoplastic material is preferably 2.50 or less, 2.00, from the viewpoint of ease of preparation of the pressure-sensitive adhesive composition, compatibility in the pressure-sensitive adhesive, and the like. It is advantageous that it is 1.90 or less, 1.80 or less, or 1.70 or less.
  • the refractive index of the plasticized material is measured using an Abbe refractive index meter under the conditions of a measurement wavelength of 589 nm and a measurement temperature of 25 ° C., similarly to the refractive index of the monomer. If the manufacturer or the like provides a nominal value of the refractive index at 25 ° C., the nominal value can be adopted.
  • the amount of the plasticized material used with respect to 100 parts by weight of the base polymer is not particularly limited and can be set according to the purpose.
  • the amount of the plasticizing material used with respect to 100 parts by weight of the base polymer may be, for example, 0.1 part by weight or more, 0.5 parts by weight or more, and higher plasticization. From the viewpoint of obtaining the effect, it is preferably 1 part by weight or more, more preferably 3 parts by weight or more, 5 parts by weight or more, 7 parts by weight or more, 10 parts by weight or more, and 15 parts by weight. It may be more than 20 parts by weight.
  • the amount of the plasticizing material used with respect to 100 parts by weight of the base polymer is about 100 parts by weight or less. It is preferably 80 parts by weight or less, more preferably 60 parts by weight or less, 45 parts by weight or less, 35 parts by weight or less, or 25 parts by weight or less. In some embodiments where more adhesive properties and optical properties are emphasized, the amount of the thermoplastic material used with respect to 100 parts by weight of the base polymer may be 15 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.
  • the pressure-sensitive adhesive composition used to form the pressure-sensitive adhesive layer includes an improvement in the appearance of the pressure-sensitive adhesive layer formed from the composition (for example, improvement in thickness uniformity) and the above-mentioned pressure-sensitive adhesive composition.
  • a leveling agent can be contained as needed for the purpose of improving the coatability of the above.
  • Non-limiting examples of the leveling agent include an acrylic leveling agent, a fluorine-based leveling agent, a silicone-based leveling agent, and the like.
  • an appropriate leveling agent can be selected from commercially available leveling agents and used by a conventional method.
  • a monomer raw material containing a monomer having a polyorganosiloxane skeleton hereinafter, also referred to as “monomer S1” and an acrylic monomer (hereinafter, also referred to as “monomer raw material B”).
  • a polymer (hereinafter, also referred to as “polymer (B)”) which is a polymer of the above can be preferably used.
  • the polymer (B) can be said to be a copolymer of the monomer S1 and the acrylic monomer.
  • the polymer (B) can be used alone or in combination of two or more.
  • the monomer S1 is not particularly limited, and any monomer containing a polyorganosiloxane skeleton can be used.
  • a monomer having a structure having a polymerizable reactive group at one end can be preferably used. Among them, it has a polymerizable reactive group at one end and causes a cross-linking reaction with a base polymer (refers to a base polymer of a pressure-sensitive adhesive composition containing the leveling agent, for example, an acrylic polymer) at the other end.
  • a monomer S1 having a structure having no functional group can be preferably adopted. Examples of commercially available products include one-ended reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. (for example, product numbers of X-22-174ASX, X-22-2426, X-22-2475, KF-2012, etc.). .. Monomer S1 can be used alone or in combination of two or more.
  • the functional group equivalent of the monomer S1 can be, for example, about 100 g / mol to 30,000 g / mol. In some preferred embodiments, the functional group equivalent may be, for example, 500 g / mol or more, 800 g / mol or more, 1500 g / mol or more, or 2000 g / mol or more. The functional group equivalent may be, for example, 20000 g / mol or less, less than 10000 g / mol, 7000 g / mol or less, or 5500 g / mol or less. When the functional group equivalent of the monomer S1 is within the above range, a good leveling effect is likely to be exhibited.
  • the functional group equivalent of the monomer S1 is the sum of the products of the functional group equivalents of each type of monomer and the weight fraction of the monomer. be able to.
  • the "functional group equivalent” means the weight of the main skeleton (for example, polydimethylsiloxane) bonded to each functional group.
  • the title unit g / mol is converted to 1 mol of functional group.
  • the functional group equivalent of the monomer S1 can be calculated, for example, from the spectral intensity of 1 H-NMR (proton NMR) based on nuclear magnetic resonance (NMR). 1
  • the calculation of the functional group equivalent (g / mol) of the monomer S1 based on the spectral intensity of 1 H-NMR is based on the general structural analysis method related to 1 1 H-NMR spectrum analysis, and if necessary, the Japanese Patent No. 1 This can be done with reference to the description in Publication No. 5591153.
  • the functional group means a polymerizable functional group (for example, an ethylenically unsaturated group such as a (meth) acryloyl group, a vinyl group or an allyl group).
  • the content of the monomer S1 in the monomer raw material B can be an appropriate value within a range in which the desired effect is exhibited by using the monomer S1, and is not limited to a specific range. In some embodiments, the content of the monomer S1 in the monomer raw material B may be, for example, 5-60% by weight, 10-50% by weight, or 15-40% by weight.
  • the monomer raw material B contains an acrylic monomer copolymerizable with the monomer S1 in addition to the monomer S1. Thereby, the compatibility of the polymer (B) in the pressure-sensitive adhesive layer can be improved.
  • the acrylic monomer that can be used for the monomer raw material B include acrylic acid alkyl esters.
  • alkyl refers to a chain-like (including linear and branched-chain) alkyl (groups), and does not include the alicyclic hydrocarbon group described later.
  • the monomer raw material B is a (meth) acrylic acid C 4-12 alkyl ester (preferably a (meth) acrylic acid C 4-10 alkyl ester, eg, a (meth) acrylic acid C 6-10 alkyl ester). Can contain at least one of. In some other embodiments, the monomer raw material B may contain at least one of a methacrylic acid C 1-18 alkyl ester (preferably a methacrylic acid C 1-14 alkyl ester, such as a methacrylic acid C 1-10 alkyl ester). ..
  • the monomer raw material B may contain, for example, one or more selected from methyl methacrylate (MMA), n-butyl methacrylate (BMA) and 2-ethylhexyl methacrylate (2EHMA) as the acrylic monomer.
  • MMA methyl methacrylate
  • BMA n-butyl methacrylate
  • EHMA 2-ethylhexyl methacrylate
  • acrylic monomer is a (meth) acrylic acid ester having an alicyclic hydrocarbon group.
  • cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate and the like can be used. It is not necessary to use a (meth) acrylic acid ester having an alicyclic hydrocarbon group.
  • the content of the (meth) acrylic acid alkyl ester and the (meth) acrylic acid ester having an alicyclic hydrocarbon group in the monomer raw material B may be, for example, 10% by weight or more and 95% by weight or less, and 20% by weight. It may be 95% by weight or less, 30% by weight or more and 90% by weight or less, 40% by weight or more and 90% by weight or less, and 50% by weight or more and 85% by weight or less. May be good.
  • the monomer that can be contained in the monomer raw material B together with the monomer S1 the carboxy group-containing monomer, the acid anhydride group-containing monomer, the hydroxyl group-containing monomer, and the epoxy group-containing monomer exemplified above as the monomers that can be used for the acrylic polymer.
  • examples thereof include (meth) acrylic acid ester and halogen atom-containing (meth) acrylate.
  • the Mw of the polymer (B) may be, for example, 5,000 or more, preferably 10,000 or more, and may be 15,000 or more.
  • the Mw of the polymer (B) may be, for example, 200,000 or less, preferably 100,000 or less, 50,000 or less, or 30,000 or less.
  • the polymer (B) can be produced, for example, by polymerizing the above-mentioned monomer by a known method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or a photopolymerization method.
  • Chain transfer agents can be used as needed to adjust the molecular weight of the polymer (B). Examples of chain transfer agents used include compounds having a mercapto group such as t-dodecyl mercaptoethanol, mercaptoethanol, ⁇ -thioglycerol; thioglycolic acid esters such as thioglycolic acid and methyl thioglycolate; ⁇ -methylstyrene.
  • the amount of the chain transfer agent used is not particularly limited, and can be appropriately set so that the polymer (B) having a desired molecular weight can be obtained.
  • the amount of the chain transfer agent used per 100 parts by weight of the monomer may be, for example, 0.1 to 5 parts by weight, 0.2 to 3 parts by weight, or 0.5 to 2 parts by weight. good.
  • the amount of the polymer (B) used with respect to 100 parts by weight of the base polymer can be, for example, 0.001 part by weight or more, and 0.01 part by weight or more from the viewpoint of obtaining a higher use effect. It may be 0.03 part by weight or more.
  • the amount of the polymer (B) used may be, for example, 3 parts by weight or less, and it is appropriate to use 1 part by weight or less from the viewpoint of reducing the influence on the refractive index, and 0.5 parts by weight or less. However, it may be 0.1 parts by weight or less.
  • inorganic particles The technique disclosed herein can be preferably carried out in a manner in which inorganic particles as a refractive index improver are substantially not used.
  • the refractive index is such that the desired optical properties (total light transmittance, haze value) are satisfied and the properties as an adhesive are not significantly impaired. It may be acceptable to use inorganic particles as the improver.
  • examples of inorganic particles that can be used as a refractive index improver include titania (titanium oxide, TiO 2 ), zirconia ( zinc oxide, ZrO 2 ), aluminum oxide, zinc oxide, tin oxide, copper oxide, barium titanate, and oxidation.
  • Examples thereof include inorganic particles composed of inorganic oxides (specifically, metal oxides) such as niobium (Nb 2 O 5 and the like).
  • the average particle size of the inorganic particles (referring to the 50% volume average particle size based on the laser scattering / diffraction method) can be selected from the range of, for example, about 10 nm to 100 nm.
  • the refractive index of the inorganic particles is determined by using a commercially available spectroscopic ellipsometer for a single-layer film (a film thickness capable of measuring the refractive index) of the material constituting the inorganic particles, with a measurement wavelength of 589 nm and a measurement temperature. It is measured under the condition of 23 ° C.
  • the product name "EC-400" manufactured by JA.Woolam
  • the amount used is preferably less than 5 parts by weight and more preferably less than 1 part by weight with respect to 100 parts by weight of the base polymer.
  • the amount of the inorganic particles used is preferably 2 times or less, preferably 1 times or less, or less than twice the amount of the additive (H RO) used on a weight basis. More preferably, it is 0.5 times or less.
  • the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer may contain a cross-linking agent, if necessary, for the purpose of adjusting the cohesive force of the pressure-sensitive adhesive.
  • a cross-linking agent known in the field of adhesives such as an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, an aziridine-based cross-linking agent, an oxazoline-based cross-linking agent, a melamine-based resin, and a metal chelate-based cross-linking agent shall be used. Can be done. Of these, an isocyanate-based cross-linking agent can be preferably used.
  • Another example of the cross-linking agent is a monomer having two or more ethylenically unsaturated groups in one molecule, that is, a polyfunctional monomer.
  • the cross-linking agent may be used alone or in combination of two or more.
  • a bifunctional or higher functional isocyanate compound can be used, for example, aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), and dimerate diisocyanate; cyclopentylene diisocyanate.
  • aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), and dimerate diisocyanate
  • HDI hexamethylene diisocyanate
  • dimerate diisocyanate dimerate diisocyanate
  • Aromatic isocyanates such as XDI); polyisocyanate modified products obtained by modifying the above isocyanate compounds with allophanate bonds, biuret bonds, isocyanurate bonds, uretdione bonds, urea bonds, carbodiimide bonds, uretonimine bonds, oxadiazine trione bonds, etc.
  • the isocyanate compound may be used alone or in combination of two or more.
  • a bifunctional isocyanate compound and a trifunctional or higher functional isocyanate compound may be used in combination.
  • epoxy-based cross-linking agent examples include bisphenol A, epichlorohydrin-type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, and trimethylol.
  • polyfunctional monomer examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like.
  • the amount used is not particularly limited, and is, for example, in the range of about 0.001 part by weight to 5.0 parts by weight with respect to 100 parts by weight of the base polymer. can do.
  • the amount of the cross-linking agent used with respect to 100 parts by weight of the base polymer is preferably 3.0 parts by weight or less, more preferably 2.0 parts by weight or less. It may be 1.0 part by weight or less, 0.5 part by weight or less, or 0.2 part by weight or less.
  • the amount of the cross-linking agent used with respect to 100 parts by weight of the base polymer may be, for example, 0.005 parts by weight or more, and 0.01 weight by weight. It may be parts or more, 0.05 parts by weight or more, or 0.08 parts by weight or more.
  • a cross-linking catalyst may be used to allow the cross-linking reaction to proceed more effectively.
  • the cross-linking catalyst include metal-based cross-linking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, ferric nasem, butyl tin oxide, and dioctyl tin dilaurate. Of these, tin-based cross-linking catalysts such as dioctyl tin dilaurate are preferable.
  • the amount of the cross-linking catalyst used is not particularly limited.
  • the amount of the cross-linking catalyst used with respect to 100 parts by weight of the base polymer is, for example, in the range of about 0.0001 parts by weight or more and 1 part by weight or less in consideration of the balance between the speed of the cross-linking reaction rate and the length of the pot life of the pressure-sensitive adhesive composition.
  • the range is preferably 0.001 part by weight or more and 0.5 part by weight or less.
  • the pressure-sensitive adhesive composition can contain a compound that causes keto-enol tautomerism as a cross-linking retarder. Thereby, the effect of extending the pot life of the pressure-sensitive adhesive composition can be realized.
  • a compound that causes keto-enol tautomerism can be preferably used in a pressure-sensitive adhesive composition containing an isocyanate-based cross-linking agent.
  • Various ⁇ -dicarbonyl compounds can be used as the compound that causes keto-enol telecommunication.
  • ⁇ -diketones acetylacetone, 2,4-hexanedione, etc.
  • acetoacetic esters methyl acetoacetate, ethyl acetoacetate, etc.
  • the compounds that cause keto-enol tautomerism can be used alone or in combination of two or more.
  • the amount of the compound that causes keto-enol telecommunication can be, for example, 0.1 parts by weight or more and 20 parts by weight or less, and 0.5 parts by weight or more and 10 parts by weight or less, based on 100 parts by weight of the base polymer. It may be 1 part by weight or more and 5 parts by weight or less.
  • the pressure-sensitive adhesive layer in the technique disclosed herein may contain a pressure-sensitive adhesive.
  • the pressure-sensitive adhesive include rosin-based pressure-sensitive adhesive resin, terpen-based pressure-sensitive adhesive resin, phenol-based pressure-sensitive adhesive resin, hydrocarbon-based pressure-sensitive adhesive resin, ketone-based pressure-sensitive adhesive resin, polyamide-based pressure-sensitive adhesive resin, epoxy-based pressure-sensitive adhesive resin, and elastomer.
  • a known pressure-sensitive adhesive resin such as a system-based pressure-sensitive adhesive resin can be used. These can be used alone or in combination of two or more.
  • the amount of the tackifying resin used is not particularly limited, and can be set so as to exhibit appropriate adhesive performance according to the purpose and application.
  • the amount of the tackifier used is 30 parts by weight or less with respect to 100 parts by weight of the base polymer of the pressure-sensitive adhesive layer, and 10 parts by weight. It is preferably less than or equal to, and more preferably less than or equal to 5 parts by weight.
  • the techniques disclosed herein can be preferably performed in a manner that does not use a tackifier.
  • the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer is a plasticizer, a softener, a colorant, an antistatic agent, and an anti-aging agent as long as the effects of the present invention are not significantly impaired.
  • UV absorbers, antioxidants, light stabilizers, preservatives, and other known additives that can be used in the pressure-sensitive adhesive composition may be included, if necessary.
  • conventionally known ones can be used by a conventional method and do not particularly characterize the present invention, and thus detailed description thereof will be omitted.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is a pressure-sensitive adhesive composition in the form of a solvent type, an active energy ray-curable type, an aqueous dispersion type, a hot melt type, etc. It may be a pressure-sensitive adhesive cured by cooling or the like, that is, a cured product of the above-mentioned pressure-sensitive adhesive composition.
  • the curing means for example, drying, cross-linking, polymerization, cooling, etc.
  • only one type may be applied, or two or more types may be applied simultaneously or in multiple stages.
  • the composition can typically be dried (preferably further crosslinked) to form a pressure-sensitive adhesive.
  • a pressure-sensitive adhesive is typically formed by irradiating with active energy rays to proceed with a polymerization reaction and / or a cross-linking reaction. When it is necessary to dry with the active energy ray-curable pressure-sensitive adhesive composition, it is advisable to irradiate the active energy ray after drying.
  • the pressure-sensitive adhesive layer of the pressure-sensitive optical film disclosed herein can be formed by applying (for example, applying) a pressure-sensitive adhesive composition to an appropriate surface and then curing the composition.
  • the application of the pressure-sensitive adhesive composition can be carried out using a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater.
  • the pressure-sensitive adhesive layer of the pressure-sensitive optical film disclosed herein may be a pressure-sensitive adhesive layer having post-curability, or may be a pressure-sensitive adhesive layer having no post-curability.
  • the pressure-sensitive adhesive layer having post-curability refers to a pressure-sensitive adhesive layer that can be further cured by irradiation with heat or active energy rays (for example, ultraviolet rays).
  • the post-curable pressure-sensitive adhesive layer include a pressure-sensitive adhesive layer having an unreacted ethylenically unsaturated group in the side chain of the base polymer, and a pressure-sensitive adhesive layer containing an unreacted polyfunctional monomer.
  • the pressure-sensitive adhesive layer preferably does not have post-curing properties.
  • the pressure-sensitive adhesive layer having no post-curing property does not cause a dimensional change due to the post-curing reaction (that is, has good dimensional stability)
  • the warpage of the adhesive optical film or the laminate containing the adhesive optical film is suppressed. It's easy to do.
  • the fact that dimensional changes (for example, curing shrinkage) due to post-curing do not occur can be advantageous from the viewpoint of suppressing optical distortion of the pressure-sensitive adhesive layer.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, and can be, for example, 3 ⁇ m or more, preferably 5 ⁇ m or more. According to the pressure-sensitive adhesive layer having a thickness of 5 ⁇ m or more, good pressure-sensitive adhesive properties can be easily obtained. Further, the pressure-sensitive adhesive layer having such a thickness absorbs irregularities that may exist on the surface of the adherend and is easily bonded to the adherend with good adhesion. It is preferable that the thickness of the pressure-sensitive adhesive layer is 5 ⁇ m or more from the viewpoint of preventing coloring and color unevenness due to light interference.
  • the thickness of the pressure-sensitive adhesive layer may be 10 ⁇ m or greater, 20 ⁇ m or greater, 30 ⁇ m or greater, 50 ⁇ m or greater, 70 ⁇ m or greater, or 85 ⁇ m or greater. Further, in some embodiments, the thickness of the pressure-sensitive adhesive layer may be, for example, 300 ⁇ m or less, 250 ⁇ m or less, 200 ⁇ m or less, 150 ⁇ m or less, or 120 ⁇ m or less. It is possible that the thickness of the pressure-sensitive adhesive layer is not too large, which is advantageous from the viewpoint of reducing the thickness of the pressure-sensitive optical film.
  • the technique disclosed herein can be preferably carried out, for example, in an embodiment in which the thickness of the pressure-sensitive adhesive layer is in the range of 3 ⁇ m to 200 ⁇ m (more preferably 5 ⁇ m to 100 ⁇ m).
  • the thickness of the pressure-sensitive adhesive layer described above is at least the first pressure-sensitive adhesive layer.
  • the thickness of the second pressure-sensitive adhesive layer can be selected from the same range.
  • the peel strength of the adhesive optical film with respect to the glass plate is approximately 1.0 N / 25 mm or more (for example, 1.5 N / 25 mm or more). It is preferably 2N / 25mm or more, more preferably 3N / 25mm or more, 4N / 25mm or more, 6N / 25mm or more, 8N / 25mm or more, 10N / 25mm or more, 12N / It may be 25 mm or more.
  • the upper limit of the peel strength is not particularly limited, and may be, for example, 30 N / 25 mm or less, 25 N / 25 mm or less, or 20 N / 25 mm or less.
  • the peel strength is such that the peel strength is pressure-bonded to an alkaline glass plate as an adherend, left to stand in an environment of 23 ° C. and 50% RH for 30 minutes, and then put into a pressure defoaming device (autoclave) to have a temperature of 50 ° C. After autoclaving for 30 minutes under the condition of pressure of 0.5 MPa and further leaving for 24 hours in the atmosphere of 23 ° C. and 50% RH, peeling off by 180 ° under the condition of peeling angle of 180 degrees and tensile speed of 300 mm / min. It is grasped by measuring the adhesive strength.
  • autoclave autoclave
  • an appropriate backing material for example, a polyethylene terephthalate (PET) film having a thickness of about 25 ⁇ m to about 50 ⁇ m
  • PET polyethylene terephthalate
  • the peel strength can be measured according to the method described in Examples described later.
  • the adhesive optical film disclosed herein is in the form of a double-sided adhesive optical film having a first adhesive surface and a second adhesive surface
  • the above-mentioned peel strength is preferably at least the first adhesive. It is applied to the surface, more preferably to both the first adhesive surface and the second adhesive surface.
  • the peel strength of the first adhesive surface to the glass plate and the peel strength of the second adhesive surface to the glass may be the same or different.
  • the material of the light transmissive member is not particularly limited, and can be appropriately selected depending on the purpose of use, the mode of use, and the like of the adhesive optical film.
  • the light-transmitting member constituting the adhesive optical film include an optical member (for example, a functional film such as a polarizing plate) described later.
  • various film substrates can be preferably used as the light transmissive member.
  • the film base material preferably contains a resin film (self-supporting or independent) whose shape can be maintained independently as a base film.
  • the "resin film” means a resin film (of voidless) having a non-porous structure and typically containing substantially no bubbles. Therefore, the resin film is a concept that is distinguished from foam films and non-woven fabrics.
  • the resin film one that can independently maintain its shape (self-supporting or independent) can be preferably used.
  • the resin film may have a single-layer structure or a multi-layer structure having two or more layers (for example, a three-layer structure).
  • Examples of the material constituting the resin film include a polyester-based resin containing a polyester as a main component, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyethylene (PE), and polypropylene (PP).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PE polyethylene
  • PP polypropylene
  • Polyimide-propylene copolymer polyolefin-based resin such as ethylene-butene copolymer, cellulose resin such as triacetyl cellulose, acetate resin, polysulfone resin, polyethersulfone resin, polycarbonate Polyaceous resins, nylon 6, nylon 66, polyamide (PA) resins such as partially aromatic polyamide, polyimide (PI) resins, transparent polyimide resins, polyamideimide (PAI), polyether ether ketone (PEEK), polyether sulfone (PES), cyclic polyolefin resin such as norbornene resin, (meth) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer resin, Ethylene-vinyl alcohol copolymer resin, polyallylate resin, polyphenylene sulfide (PPS) resin, polyurethane
  • the resin film may be formed by using a resin material containing one kind of such a resin alone, or may be formed by using a resin material in which two or more kinds are blended. May be good.
  • the resin film may be unstretched or stretched (for example, uniaxially stretched or biaxially stretched).
  • CPP unstretched polypropylene
  • OPP biaxially stretched polypropylene
  • LLDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • PP / PE blend film and the like can be preferably used.
  • preferable resin films from the viewpoint of strength and dimensional stability include PET film, PEN film, PPS film and PEEK film. From the viewpoint of availability, PET film and PPS film are particularly preferable, and PET film is particularly preferable.
  • Known resin films include light stabilizers, antioxidants, antistatic agents, colorants (dyees, pigments, etc.), fillers, slip agents, antiblocking agents, etc., as long as the effects of the present invention are not significantly impaired.
  • Additives can be blended as needed.
  • the blending amount of the additive is not particularly limited, and can be appropriately set according to the application of the adhesive optical film and the like.
  • the manufacturing method of the resin film is not particularly limited.
  • conventionally known general resin film molding methods such as extrusion molding, inflation molding, T-die casting molding, and calendar roll molding can be appropriately adopted.
  • the light transmissive member may be substantially composed of such a base film.
  • the light transmissive member may include an auxiliary layer in addition to the base film.
  • the auxiliary layer include an optical property adjusting layer (for example, a coloring layer and an antireflection layer), a surface such as a printing layer or a laminating layer for imparting a desired appearance, an antistatic layer, an undercoat layer, and a peeling layer.
  • a processing layer can be mentioned.
  • the total light transmittance of the light transmissive member may be, for example, more than 50%, and may be 70% or more. In some preferred embodiments, the total light transmittance of the light transmissive member is 80% or more, more preferably 90% or more, and may be 95% or more (for example, 95 to 100%).
  • the total light transmittance is measured using a commercially available transmittance meter in accordance with JIS K 7136: 2000. As the transmittance meter, the product name "HAZEMETER HM-150" manufactured by Murakami Color Technology Research Institute or its equivalent is used.
  • a preferable example of the light-transmitting member is a resin film having light-transmitting property.
  • the light transmissive member may be an optical film.
  • the materials that can be used in the construction of the light transmissive member include, for example, copper, silver, gold, iron, tin, palladium, aluminum, nickel, titanium, chromium, indium, zinc and the like, or these.
  • Metallic materials such as alloys containing two or more of the above, for example, polyimide resins, acrylic resins, polyether nitrile resins, polyether sulfone resins, polyester resins (PET resins, polyethylene naphthalate resins, etc.), Polyvinyl chloride resin, polyphenylene sulfide resin, polyether ether ketone resin, polyamide resin (so-called aramid resin, etc.), polyarylate resin, fluorine resin, polycarbonate resin, cellulose such as diacetyl cellulose and triacetyl cellulose
  • Various resin materials such as based polymers, vinyl butyral polymers, liquid crystal polymers, carbon materials such as carbon nanotubes and graphene, and polymer materials represented by PEDOT (poly (3,4-ethylenedioxythiophene)) and polyaniline.
  • Metal oxides such as (typically plastic materials), alumina, zirconia, titania, SiO 2 , ITO (indium tin oxide), ATO (antimony-doped tin oxide) and mixtures thereof, aluminum nitride, silicon nitride, titanium nitride, Examples thereof include nitrides such as gallium nitride and indium nitride and their composites, inorganic materials such as alkaline glass, non-alkali glass, quartz glass, borosilicate glass and sapphire glass, and mixtures and composites thereof. Not limited.
  • the thickness of the light-transmitting member is not particularly limited, and can be selected according to the purpose of use, the mode of use, etc. of the adhesive optical film.
  • the thickness of the light transmissive member may be, for example, 500 ⁇ m or less, preferably 300 ⁇ m or less from the viewpoint of handleability and workability, 150 ⁇ m or less, 100 ⁇ m or less, 50 ⁇ m or less, 25 ⁇ m or less. It may be 10 ⁇ m or less. As the thickness of the light transmissive member becomes smaller, the ability to follow the surface shape of the adherend tends to improve. Further, from the viewpoint of handleability, workability, and the like, the thickness of the light transmitting member may be, for example, 2 ⁇ m or more, 10 ⁇ m or more, or 25 ⁇ m or more.
  • the surface of the light-transmitting member on the side where the pressure-sensitive adhesive layer is laminated is coated with a corona discharge treatment, a plasma treatment, an ultraviolet irradiation treatment, an acid treatment, an alkali treatment, or an undercoating agent (primer).
  • a corona discharge treatment a plasma treatment, an ultraviolet irradiation treatment, an acid treatment, an alkali treatment, or an undercoating agent (primer).
  • Conventionally known surface treatments such as layer formation may be applied.
  • Such a surface treatment may be a treatment for improving the anchoring property of the pressure-sensitive adhesive layer on the light-transmitting member.
  • the composition of the primer used for forming the undercoat layer is not particularly limited, and can be appropriately selected from known ones.
  • the thickness of the undercoat layer is not particularly limited, but is usually about 0.01 ⁇ m to 1 ⁇ m, preferably about 0.1 ⁇ m to 1 ⁇ m.
  • Other treatments that can be applied to the light transmissive member as needed include an antistatic layer
  • the thickness of the adhesive optical film disclosed herein may be, for example, 1000 ⁇ m or less, 350 ⁇ m or less, 200 ⁇ m or less, 120 ⁇ m or less, 75 ⁇ m or less, or 50 ⁇ m or less.
  • the thickness of the adhesive optical film may be, for example, 10 ⁇ m or more, 25 ⁇ m or more, 80 ⁇ m or more, or 130 ⁇ m or more from the viewpoint of handleability and the like.
  • the thickness of the adhesive optical film means the thickness of the portion to be attached to the adherend.
  • it refers to the thickness from the first surface (adhesive surface) 10A of the pressure-sensitive adhesive layer to the second surface 20B of the light-transmitting member, and is the thickness of the release liner 30. Does not include.
  • the adhesive optical film disclosed herein may take the form of an adhesive product in which the surface (adhesive surface) of the adhesive layer is brought into contact with the release surface of the release liner. Accordingly, according to this specification, an adhesive optical film with a release liner comprising any of the adhesive optical films disclosed herein and a release liner having a release surface that abuts the adhesive surface of the adhesive optical film. Adhesive products) are provided.
  • the release liner is not particularly limited, and for example, a release liner having a release treatment layer on a release liner base material such as a resin film or paper (paper in which a resin such as polyethylene is laminated) or a fluorine-based release liner.
  • a release liner base material such as a resin film or paper (paper in which a resin such as polyethylene is laminated) or a fluorine-based release liner.
  • a release liner made of a resin film formed of a low adhesive material such as a polymer (polytetrafluoroethylene or the like) or a polyolefin resin (polyethylene, polypropylene, etc.) can be used.
  • the peeling treatment layer may be formed by surface-treating the peeling liner base material with a peeling treatment agent.
  • the stripping agent may be a known stripping agent such as a silicone-based stripping agent, a long-chain alkyl-based stripping agent, a fluorine-based stripping agent, or molybdenum sulfide (IV).
  • a release liner having a release treatment layer with a silicone-based release treatment agent can be preferably adopted.
  • the thickness and forming method of the peeling treatment layer are not particularly limited, and can be set so that appropriate peeling property is exhibited on the adhesive surface side surface of the peeling liner.
  • a release liner having a release treatment layer on a resin film (hereinafter, also referred to as a release film base material) as a release liner base material (hereinafter, peeling).
  • a release film base material a resin film
  • peeling a release liner base material
  • a film a release liner base material
  • Various plastic films can be used as the release film base material.
  • a plastic film is typically a non-porous sheet, a concept that distinguishes it from, for example, non-woven fabrics (ie, does not include non-woven fabrics).
  • polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP), and ethylene-propylene co-weight.
  • polyolefin resin such as ethylene-butene copolymer, cellulose resin such as triacetyl cellulose, acetate resin, polysulfone resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, norbornene resin
  • Cyclic polyolefin resin such as resin, (meth) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol co-weight Examples thereof include a coalesced resin, a polyarylate resin, and a polyphenylene sulfide resin.
  • a release film base material formed from any one or a mixture of two or more of these resins can be used.
  • a preferable release film base material includes a polyester-based resin film (for example, PET film) formed from a polyester-based resin.
  • the plastic film used as the above-mentioned release film base material may be any of a non-stretched film, a uniaxially stretched film, and a biaxially stretched film. Further, the plastic film may have a single-layer structure or a multi-layer structure including two or more sub-layers.
  • the plastic film is an adhesive sheet containing antioxidants, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, colorants such as pigments and dyes, lubricants, fillers, antioxidants, nucleating agents, etc.
  • a known additive that can be used for the release film base material of the above may be blended. In the multi-layered plastic film, each additive may be blended in all sublayers or only in some sublayers.
  • the release film substrate (typically a plastic film) contains particles such as inorganic particles (eg, pigments, lubricants, fillers, etc.) in the layer on the release surface side thereof. Those with a limited amount or substantially free of such particles may be preferably used.
  • substantially not contained means that the amount of particles (for example, inorganic particles) in the layer is less than 1% by weight, preferably less than 0.1% by weight (for example, 0 to 0.01% by weight). ).
  • a release film provided with such a release film base material tends to have a low arithmetic mean roughness Ra and maximum height Rz of the release surface.
  • the particle content in the layer on the release surface side is 1 / of the particle content in the layers other than the release surface side layer. It can be 10 or less (for example, 1/50 or less).
  • a release liner (hereinafter, also referred to as one release liner) arranged on one of the adhesive surfaces.
  • the release liner (hereinafter, also referred to as the other release liner) arranged on the other adhesive surface may have the same material and composition, or may have a different material and composition. May be good.
  • the thickness of the release liner (preferably the release film) is not particularly limited, and may be, for example, about 10 ⁇ m to 500 ⁇ m. From the viewpoint of the strength and dimensional stability of the release liner, the thickness of the release liner is preferably 20 ⁇ m or more, preferably 30 ⁇ m or more, 35 ⁇ m or more, 40 ⁇ m or more, or 45 ⁇ m or more. good. Further, from the viewpoint of handleability of the release liner (for example, ease of winding), the thickness of the release liner is preferably 300 ⁇ m or less, preferably 250 ⁇ m or less, and may be 200 ⁇ m or less. It may be 150 ⁇ m or less, or 130 ⁇ m or less.
  • the thickness of the release liner is approximately 125 ⁇ m or less, may be approximately 115 ⁇ m or less, may be approximately 105 ⁇ m or less, may be approximately 90 ⁇ m or less, and may be approximately 70 ⁇ m or less.
  • the thicknesses of the release liners may be the same or different. In some aspects, from the viewpoint of peeling workability and the like, it is preferable that one peeling liner and the other peeling liner have different thicknesses, for example, the thicker peeling liner has a thinner thickness.
  • the thickness of the release liner is preferably about 1.1 times or more (for example, about 1.25 times or more. The upper limit is not particularly limited, but for example, 5 times or less).
  • the release liner (preferably the release film) is often limited in that the arithmetic mean roughness Ra of the surface on the adhesive surface side is limited to a predetermined value or less (for example, about 100 nm or less, further less than 50 nm). It is preferable from the viewpoint of realizing an adhesive surface having surface smoothness.
  • the arithmetic mean roughness Ra of the adhesive surface side surface of the release liner is, for example, preferably about 30 nm or less, more preferably about 25 nm or less, about 20 nm or less, and about 18 nm or less. It may be.
  • the arithmetic mean roughness Ra may be, for example, about 5 nm or more, about 10 nm or more, or about 15 nm or more. ..
  • the surface on the adhesive surface side of both release liners is any of the above-mentioned arithmetic mean roughness Ra. It is preferable to satisfy.
  • the arithmetic mean roughness Ra of the adhesive surface side surfaces of both release liners may be about the same or different.
  • the release liner (preferably a release film) preferably has a maximum height Rz of the surface on the adhesive surface side of 700 nm or less from the viewpoint of realizing an adhesive surface having high surface smoothness.
  • the maximum height Rz of the adhesive surface side surface of the release liner is preferably about 600 nm or less, may be about 500 nm or less, may be about 400 nm or less, and may be about 300 nm or less.
  • the maximum height Rz may be, for example, about 50 nm or more, about 80 nm or more, or about 100 nm or more. It may be about 150 nm or more, and may be about 200 nm or more.
  • the adhesive surface side surfaces of both release liners both have the maximum height Rz of any of the above. It is preferable to satisfy.
  • the maximum height Rz of the adhesive surface side surfaces of both release liners may be about the same or different.
  • the arithmetic mean roughness Ra and the maximum height Rz of the back surface (opposite surface of the adhesive layer side) of the release liner (preferably the release film) are not particularly limited.
  • the arithmetic mean roughness Ra on the back surface of the peeling liner may be, for example, more than 30 nm (for example, more than 35 nm, more preferably about 50 nm or more) from the viewpoint of productivity and the like.
  • the maximum height Rz of the back surface of the release liner may be, for example, more than 400 nm (for example, about 500 nm or more) or more than 800 nm (for example, 1000 nm or more) from the viewpoint of productivity and the like.
  • the arithmetic mean roughness Ra and the maximum height Rz of the peeled film surface can be adjusted by the selection of the film material, the molding method, the surface treatment such as the peeling treatment, and the like. For example, adjusting the smoothness of the layers constituting the peelable surface (anti-blocking layer, hard coat layer, oligomer prevention layer, etc.), reducing the amount of filler particles in the surface layer or the release film base material, or eliminating the use (particle-free). ), In addition, adjustment of stretching conditions and the like can be mentioned.
  • the arithmetic mean roughness Ra and the maximum height Rz of the surface of the release liner (preferably the release film) are measured using a non-contact type surface roughness measuring device.
  • a non-contact type surface roughness measuring device a light interference type surface roughness measuring device is used, and for example, a three-dimensional optical profiler (trade name "NewView7300", manufactured by ZYGO) or an equivalent product thereof can be used.
  • a glass plate sida lime glass plate manufactured by MATSUNAMI, thickness 1.3 mm
  • the surface shape can be measured using a three-dimensional optical profiler (trade name "NewView7300", manufactured by ZYGO).
  • the adhesive optical film disclosed herein can be used by being bonded to various adherends.
  • the constituent material (adhesion material) of the adherend is not particularly limited, but for example, copper, silver, gold, iron, tin, palladium, aluminum, nickel, titanium, chromium, indium, and zinc. Etc., or metal materials such as alloys containing two or more of these, for example, polyimide-based resin, acrylic-based resin, polyether nitrile-based resin, polyether sulfone-based resin, polyester-based resin (PET-based resin, polyethylene naphthalate-based).
  • Resins etc.
  • Polyvinyl chloride resins polyphenylene sulfide resins, polyether ether ketone resins, polyamide resins (so-called aramid resins, etc.), polyarylate resins, fluorine resins, polycarbonate resins, diacetyl celluloses and triacetyls.
  • Various resin materials typically plastic materials
  • cellulose-based polymers such as cellulose, vinyl butyral-based polymers, liquid crystal polymers, and carbon materials such as graphene , and metal oxidation of alumina, zirconia, titania, SiO 2 , ITO, ATO, etc.
  • nitrides such as aluminum nitride, silicon nitride, titanium nitride, gallium nitride, indium nitride and their composites, inorganic materials such as alkaline glass, non-alkali glass, quartz glass, borosilicate glass and sapphire glass.
  • the adhesive optical film disclosed herein can be used by being attached to a member (for example, an optical member) whose surface is made of the above material at least.
  • the adhesive optical film disclosed herein is used in a sticking mode that does not require a treatment of sticking to an adherend and then heating to a temperature higher than a temperature range of about room temperature (for example, 20 ° C. to 35 ° C.). obtain. Further, if it is permissible depending on the constituent material of the adhesive optical film (for example, the material of the light transmitting member) and the type of the adherend, after the bonding to the adherend, at the time of bonding, and at the time of bonding, and The heat treatment may be performed at least at any timing before bonding. The heat treatment can be performed for the purpose of improving the adhesion of the pressure-sensitive adhesive to the adherend and promoting adhesion.
  • the heat treatment temperature is appropriately set so as to obtain a desired effect in consideration of the surface condition of the adherend and the like within an allowable range depending on the constituent material of the adhesive optical film and the type of the adherend. For example, it may be about 100 ° C. or lower, 80 ° C. or lower, 60 ° C. or lower, or 50 ° C. or lower.
  • the member or material to which the adhesive optical film is attached may have light transmittance.
  • the total light transmittance of the adherend may be, for example, more than 50%, and may be 70% or more.
  • the total light transmittance of the adherend is 80% or more, more preferably 90% or more, still more preferably 95% or more (for example, 95 to 100%).
  • the adhesive optical film disclosed herein can be preferably used in a mode of being attached to an adherend (for example, an optical member) having a total light transmittance of a predetermined value or more.
  • the total light transmittance is measured using a commercially available transmittance meter in accordance with JIS K 7136: 2000.
  • the transmittance meter the product name "HAZEMETER HM-150" manufactured by Murakami Color Technology Research Institute or its equivalent is used.
  • the refractive index of the pressure-sensitive adhesive layer and the refractive index of the adherend may be the same or different.
  • the refractive index of the pressure-sensitive adhesive layer may be, for example, 1.55 or less, 1.50 or less, 1.48 or less, 1.45 or less, less than 1.45, or, for example, 1. It can be .10 or higher, 1.20 or higher, 1.30 or higher, or 1.35 or higher.
  • the light incident on the adherend from the pressure-sensitive adhesive layer side can be refracted to the front side to increase the front luminance.
  • the refractive index of the adherend may be, for example, 1.60 or more, 1.65 or more or 1.70 or more, and for example, 3.00 or less, 2.50 or less or 2.00 or less. Can be.
  • the refractive index of the adherend may be about 1.55 to 1.80, about 1.55 to 1.75, or about 1.60 to 1.70.
  • the refractive index of the adherend can be measured in the same manner as the refractive index of the pressure-sensitive adhesive.
  • the adherend may have any of the refractive indexes described above and any of the total light transmittances described above. In such a mode of sticking to an adherend, the effect of the technique disclosed herein is particularly preferably exhibited.
  • An example of a preferable application is an optical application. More specifically, it is disclosed herein as, for example, an optical adhesive sheet used for bonding optical members (for bonding optical members), manufacturing products using the above optical members (optical products), and the like.
  • the adhesive type optical film to be used can be preferably used.
  • the optical member is a member having optical characteristics (for example, polarization, light refraction, light scattering, light reflection, light transmission, light absorption, light diffractivity, light turning property, visibility, etc.). say.
  • the optical member is not particularly limited as long as it has optical characteristics, but is used, for example, as a member constituting a device (optical device) such as a display device (image display device) or an input device, or a member thereof. Examples include polarizing plates, wavelength plates, retardation plates, optical compensation films, brightness improving films, light guide plates, reflective films, antireflection films, hard coat (HC) films, shock absorbing films, antifouling films, and the like.
  • Photochromic film, dimming film, transparent conductive film (ITO film), design film, decorative film, surface protection plate, prism, lens, color filter, transparent substrate, and members in which these are laminated (collectively referred to as these). (Sometimes referred to as a “functional film”) and the like.
  • the above-mentioned “plate” and “film” are assumed to include a plate-like, a film-like, a sheet-like form, respectively, and for example, a “polarizing film” includes a “polarizing plate”, a “polarizing sheet”, and the like.
  • the “light guide plate” shall include a “light guide film”, a “light guide sheet” and the like. Further, the above-mentioned “polarizing plate” includes a circular polarizing plate.
  • Examples of the display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a micro LED ( ⁇ LED), a mini LED (miniLED), a PDP (plasma display panel), and electronic paper. Further, examples of the input device include a touch panel and the like.
  • the optical member is not particularly limited, and examples thereof include members made of glass, acrylic resin, polycarbonate, polyethylene terephthalate, a metal thin film, and the like (for example, sheet-shaped, film-shaped, and plate-shaped members).
  • the "optical member” in this specification also includes a member (design film, decorative film, surface protective film, etc.) that plays a role of decoration and protection while maintaining the visibility of the display device and the input device.
  • the techniques disclosed herein include, for example, an optical film such as a film or a fluorescent film having one or more functions such as light transmission, reflection, diffusion, waveguide, condensing, and diffraction, and other optical members ( It can be preferably used for bonding to other optical films.).
  • an optical film such as a film or a fluorescent film having one or more functions such as light transmission, reflection, diffusion, waveguide, condensing, and diffraction
  • other optical members It can be preferably used for bonding to other optical films.
  • the light transmissive member has a high refractive index pressure-sensitive adhesive layer (bonding layer). )
  • a structure bonded to the other optical member can be formed.
  • the other optical member can be attached to the other optical member via a pressure-sensitive adhesive layer having a high refractive index.
  • a structure joined to the light transmissive member can be formed.
  • the entire bulk of the bonding layer has a high refractive index, and the techniques disclosed herein are preferably applied.
  • the technique disclosed herein can be preferably used for bonding optical films such as a light guide film, a diffusion film, a fluorescent film, a toning film, a prism sheet, a lenticular film, and a microlens array film. In these applications, thinning and improvement of light extraction efficiency are required from the viewpoint of miniaturization and high performance of optical members.
  • the technique disclosed herein can be preferably used as an adhesive optical film provided with an adhesive capable of meeting such demands. More specifically, for example, in joining a light guide film or a diffusion film, it is possible to contribute to thinning by adjusting the refractive index of the pressure-sensitive adhesive layer as the bonding layer (for example, increasing the refractive index).
  • the light extraction efficiency (which can also be grasped as the luminous efficiency) can be improved by appropriately adjusting the difference in the refractive index between the fluorescent light emitter and the pressure-sensitive adhesive.
  • the scattering component can be reduced and the light transmittance can be improved by appropriately adjusting the refractive index of the pressure-sensitive adhesive so that the difference in the refractive index from the toning pigment is small.
  • the diffraction of light can be controlled by appropriately adjusting the refractive index of the pressure-sensitive adhesive, which can contribute to the improvement of brightness and / or viewing angle.
  • the adhesive optical film disclosed herein is preferably used in a manner of being attached to an adherend having a high refractive index (which may be a layer or a member having a high refractive index), and is an interface with the adherend. Reflection can be suppressed.
  • the adhesive optical film used in such an embodiment preferably has a small difference in refractive index from the adherend and has high adhesion at the interface with the adherend. Further, from the viewpoint of enhancing the homogeneity of the appearance, it is preferable that the thickness of the pressure-sensitive adhesive layer is high, and for example, the surface smoothness of the pressure-sensitive adhesive surface is high.
  • the thickness of the adherend with a high refractive index is relatively small (for example, when it is 5 ⁇ m or less, 4 ⁇ m or less, or 2 ⁇ m or less), from the viewpoint of suppressing coloring and color unevenness due to the interference of reflected light, at the interface. Suppressing reflexes is especially meaningful.
  • the pressure-sensitive optical film disclosed herein is suitable for increasing the refractive index of the pressure-sensitive adhesive layer, it can be used as a light-emitting layer such as an optical semiconductor (for example, a high-refraction light-emitting layer mainly composed of an inorganic material). It can be preferably used in a manner in which it is attached. By reducing the difference in refractive index between the light emitting layer and the pressure-sensitive adhesive layer, reflection at their interfaces can be suppressed and the light extraction efficiency can be improved.
  • the pressure-sensitive optical film used in such an embodiment preferably includes a pressure-sensitive adhesive layer having a high refractive index.
  • the water absorption rate of the pressure-sensitive adhesive layer is low.
  • the adhesive optical film is preferably low in color. This can also be advantageous from the viewpoint of suppressing unintentional coloring caused by the adhesive optical film.
  • the adhesive disclosed in this specification is a microlens or other lens member used as a constituent member of a camera, a light emitting device, or the like (for example, a microlens constituting a microlens array film or a lens member such as a camera microlens). ), A coating layer covering the lens surface, a bonding layer with a member facing the lens surface (for example, a member having a surface shape corresponding to the lens surface), and a filling filled between the lens surface and the member. It can be preferably used as a layer, etc.
  • the pressure-sensitive adhesive disclosed herein is suitable for increasing the refractive index
  • a lens having a high refractive index for example, a lens made of a high refractive index resin or a lens having a surface layer made of a high refractive index resin
  • Even if there is, the difference in refractive index from the lens can be reduced. This is advantageous from the viewpoint of reducing the thickness of the lens and the product provided with the lens, and can also contribute to the suppression of aberration and the improvement of the Abbe number.
  • the pressure-sensitive adhesive disclosed herein can also be used as a lens resin by itself, for example, in the form of being filled in the recesses or voids of a suitable transparent member.
  • the adhesive optical film disclosed here can also be grasped as an adhesive optical member. Further, when the functional film is used as the light transmissive member in the adhesive optical film disclosed herein, the adhesive optical film disclosed herein is disclosed here on at least one side of the functional film. It can also be grasped as a "adhesive type functional film" having an adhesive layer to be formed.
  • a laminate comprising the adhesive optical film disclosed herein.
  • the member to which the adhesive optical film is attached may have the refractive index of the adherend material described above.
  • the difference between the refractive index of the adhesive optical film and the refractive index of the member may be the difference in refractive index between the adherend and the adhesive optical film described above. Since the members constituting the laminated body have been described as the above-mentioned members, materials, and adherends, the overlapping description will not be repeated.
  • An adhesive sheet containing an adhesive layer It has an adhesive surface composed of the above adhesive layer and has an adhesive surface.
  • the pressure-sensitive adhesive layer is a pressure-sensitive adhesive sheet having a refractive index of more than 1.570, a total light transmittance of 86% or more, and a haze value of 3.0% or less.
  • Adhesive sheet with release liner including.
  • An adhesive optical film comprising a light-transmitting member and an adhesive layer laminated on the light-transmitting member. It has an adhesive surface composed of the above adhesive layer and has an adhesive surface.
  • the pressure-sensitive adhesive layer is an adhesive optical film having a refractive index of more than 1.570, a total light transmittance of 86% or more, and a haze value of 3.0% or less.
  • Adhesive composition Adhesive composition.
  • the additive (H RO ) according to any one of the above [11] to [13], which comprises at least one compound selected from the group consisting of an aromatic ring-containing compound and a heterocyclic ring-containing compound.
  • Adhesive composition [15] The pressure-sensitive adhesive composition according to any one of [11] to [14] above, wherein the additive (H RO) contains a compound having two or more aromatic rings in one molecule.
  • the additive ( HRO ) is a compound having two or more aromatic rings in one molecule. (I) Containing a structure in which two non-condensed aromatic rings are directly chemically bonded, and (ii) Containing a structure in which two non-condensed aromatic rings are condensed.
  • the content of the aromatic ring-containing monomer (m1) is more than 70% by weight and less than 100% by weight.
  • An interlayer sheet used by arranging between layers of a laminated body in optical applications Refractive index n 1 comprises a viscoelastic layer V 1 is 1.570 or more, and the total light transmittance is 86% or more; Haze value is 1.0% or less; and The storage modulus G'at 25 ° C. is 30 kPa to 700 kPa; An interlayer sheet that meets the requirements.
  • the interlayer sheet according to the above [24] which has a thickness of 5 ⁇ m or more.
  • the viscoelastic layer V 1 was a layer formed from the pressure-sensitive adhesive composition according to any one of [11] - [18], according to any one of [24] - [29] Layered sheet.
  • a release liner that covers at least one surface of the interlayer sheet, Interlayer sheet with release liner, including.
  • the acrylic polymer A1 has a Tg (that is, Tg T ) based on the composition of the monomer component at ⁇ 35 ° C. and a Tg (that is, Tg m1 ) based on the composition of the aromatic ring-containing monomer at ⁇ 35 ° C.
  • a PET film R2 (thickness 25 ⁇ m, arithmetic mean roughness Ra of the silicone-treated surface Ra 15 nm, maximum height Rz 180 nm) in which one side of the surface (first adhesive surface) of the pressure-sensitive adhesive layer was treated with silicone was applied.
  • the silicone-treated surfaces were bonded together.
  • a base material-less double-sided pressure-sensitive adhesive sheet S1 composed of the pressure-sensitive adhesive layer was obtained. Both sides of the adhesive sheet S1 are protected by PET films (release liners) R1 and R2.
  • the release liner R2 bonded to the first adhesive surface is relatively lightly peeled as compared with the release liner R1 (release liner to which the pressure-sensitive adhesive composition is applied) that protects the second adhesive surface.
  • Examples 2 to 3, 7 to 8, 10 to 14 The solutions of the acrylic polymers A2 to 3,7 to 8,10 to 14 according to each example were prepared in the same manner as in the preparation of the acrylic polymer solution in Example 1 except that the composition of the monomer components was changed as shown in Table 1. Prepared.
  • the acrylic pressure-sensitive adhesive composition C2 according to each example was prepared in the same manner as in the preparation of the pressure-sensitive adhesive composition in Example 1 except that the solution of the acrylic polymer according to each of the above examples was used instead of the solution of the acrylic polymer A1.
  • ⁇ 3,7 ⁇ 8,10 ⁇ 14 were prepared.
  • Example 4 The solution (50%) of the acrylic polymer A3 prepared in Example 3 was diluted to 30% with ethyl acetate, and 6-acryloyloxymethyldi as an additive (HRO) was added to 334 parts (100 parts of non-volatile content) of this solution.
  • HRO 6-acryloyloxymethyldi as an additive
  • an acrylic pressure-sensitive adhesive composition C4 was prepared. Similar to the production of the pressure-sensitive adhesive sheet in Example 1, except that the acrylic pressure-sensitive adhesive composition C4 was used instead of the acrylic pressure-sensitive adhesive composition C1 and the thickness of the pressure-sensitive adhesive layer was 25 ⁇ m. An adhesive sheet (base-less double-sided adhesive sheet composed of an adhesive layer) S4 was produced.
  • Examples 5 to 6 Similar to the preparation of the acrylic pressure-sensitive adhesive composition C4 in Example 4, except that the type of additive (H RO ) and the amount used per 100 parts of the acrylic polymer (phr; per hundred resin) were changed as shown in Table 1. Then, the acrylic pressure-sensitive adhesive compositions C5 and C6 according to Examples 5 and 6 were prepared.
  • "BPFL” in Table 1 represents 9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.68), and "BAFL” is 9,9-bis. It represents (4-aminophenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.73).
  • the pressure-sensitive adhesive sheets (from the pressure-sensitive adhesive layer) according to Examples 5 and 6 are the same as in the production of the pressure-sensitive adhesive sheet in Example 4, except that the acrylic pressure-sensitive adhesive compositions C5 and C6 are used instead of the acrylic pressure-sensitive adhesive composition C4, respectively.
  • a base material-less double-sided adhesive sheet) was produced.
  • Example 9 The solution of the acrylic polymer A8 prepared in Example 8 (50%) was diluted to 30% with ethyl acetate, to the solution 334 parts (nonvolatile content 100 parts), 10 parts of BPFL as an additive (H RO), crosslinked 10 parts (0.1 part non-volatile content) of a 1% ethyl acetate solution of an isocyanurate compound of hexamethylene diisocyanate (manufactured by Toso Co., Ltd., trade name "Coronate HX", trifunctional isocyanate compound) was used as an agent, and acetylacetone was used as a cross-linking retarder.
  • an isocyanurate compound of hexamethylene diisocyanate manufactured by Toso Co., Ltd., trade name "Coronate HX", trifunctional isocyanate compound
  • an acrylic pressure-sensitive adhesive composition C9 Similar to the production of the pressure-sensitive adhesive sheet in Example 8 except that the acrylic pressure-sensitive adhesive composition C9 was used instead of the acrylic pressure-sensitive adhesive composition C8, the pressure-sensitive adhesive sheet (base-less double-sided surface composed of the pressure-sensitive adhesive layer) was obtained in the same manner as in Example 8. Adhesive sheet) S9 was produced.
  • Example 15 The composition of the monomer component was changed to 90 parts of 2-ethylhexyl acrylate (2EHA) and 10 parts of 4HBA, but the solution of the acrylic polymer A14 (40%) was the same as the preparation of the acrylic polymer solution in Example 1. ) was prepared.
  • the solution (40%) of the acrylic polymer A14 is diluted to 20% with ethyl acetate, and in 500 parts (100 parts of non-volatile content) of this solution, 10 parts of zirconia particle dispersion is added based on the solid content, and hexamethylene as a cross-linking agent.
  • the zirconia particle dispersion is a surface-treated zirconia particle (average particle size 20 nm, solid content refractive index: 1.64, surface treatment: carboxylic acid / phosphoric acid hydrophobization, manufactured by Kyoeisha Chemical Co., Ltd.).
  • PGME propylene glycol monomethyl ether
  • a surface-treated zirconia particle dispersion was used. Similar to the production of the pressure-sensitive adhesive sheet in Example 14, except that the acrylic pressure-sensitive adhesive composition C15 was used instead of the acrylic pressure-sensitive adhesive composition C14, the pressure-sensitive adhesive sheet according to Example 15 (base-less double-sided surface composed of a pressure-sensitive adhesive layer). Adhesive sheet) S15 was produced.
  • the obtained adhesive sheet was sufficiently acclimatized to an environment of 23 ° C. and 50% RH, and then used for the following measurements and evaluations.
  • Total light transmittance and haze value Using a test piece in which the pressure-sensitive adhesive layer according to each example was bonded to non-alkali glass (thickness 0.8 to 1.0 mm, total light transmittance 92%, haze 0.4%), under a measurement environment of 23 ° C.
  • the total light transmittance and haze of the test piece were measured using a haze meter (manufactured by Murakami Color Technology Laboratory, trade name "HAZEMETER HM-150").
  • the value obtained by subtracting the total light transmittance and haze of the non-alkali glass from the measured value was taken as the total light transmittance and haze value of the pressure-sensitive adhesive layer.
  • Table 1 The results are shown in Table 1.
  • Example 16 the coating amount of the acrylic pressure-sensitive adhesive composition C3 was adjusted so as to form a pressure-sensitive adhesive layer having a thickness of 5 ⁇ m, as in the production of the base material-less double-sided pressure-sensitive adhesive sheet S3 according to Example 3. A substrate-less double-sided pressure-sensitive adhesive sheet S16 was obtained.
  • the base material-less double-sided adhesive sheet according to each example was cut into a size of 150 mm in length and 50 mm in width for each of the release liners R1 and R2 for protecting the first and second adhesive surfaces to prepare a measurement sample.
  • the release liner R1 side of this measurement sample is fixed to a test plate, and a tensile tester (device name "Autograph AG-IS", manufactured by Shimadzu Corporation) is used to pull the tensile speed at 23 ° C. and 50% RH.
  • the peeling liner R2 was peeled off from the first adhesive surface of the measurement sample to expose the first adhesive surface.
  • the surface shape of the first adhesive surface was measured using a three-dimensional optical profiler (trade name "NewView7300", manufactured by ZYGO) in an environment of 23 ° C. and 50% RH.
  • Arithmetic surface roughness Ra was calculated from the measured data according to JIS B 0601-2001.
  • the maximum height (Rz) is the height Rp of the highest mountain on the upper side of the average line of the roughness curve and the lower side of the average line of the data (roughness curve) obtained by the above measurement.
  • defoaming treatment was performed with a pressure defoaming device (autoclave) to remove the influence of minute air bubbles (treatment). Conditions: 50 ° C., 0.5 MPa, 30 minutes). After allowing to cool at room temperature for 30 minutes or more, the release film R1 was peeled off to expose the second adhesive surface to prepare an optical strain evaluation sample (a laminate composed of an adhesive sheet and a mirror). The evaluation sample was arranged so that the pressure-sensitive adhesive sheet side was directed toward the point light source side and the angle with respect to the light beam from the point light source was about 45 degrees. A white screen was installed at the tip of the light beam to reflect the reflected image.
  • the point light source As the point light source, the trade name "xenon lamp C2577” manufactured by Hamamatsu Photonics Co., Ltd. or an equivalent product can be used, and the above trade name “xenon lamp C2577” was used in this experiment.
  • the point light source, the evaluation sample, and the screen were arranged so that the distance between the evaluation sample and the point light source and the distance between the evaluation sample and the screen were about 50 cm, respectively.
  • the presence or absence and degree of optical distortion were evaluated at the following three levels by turning on the point light source and visually observing the image reflected by the sample and projected on the screen. E: No optical distortion is observed. A: Some optical distortion is observed, but it is practically acceptable. P: Clear optical distortion is observed.
  • a release liner was peeled off from one surface of an adhesive sheet under a measurement environment of 23 ° C. and 50% RH, a PET film having a thickness of 50 ⁇ m was attached and lined, and then cut into a size of 25 mm in width and 100 mm in length. Was used as a test piece.
  • the peeling liner on the other side is peeled off from the test piece, and a 2 kg roller is reciprocated once on the surface of the alkaline glass plate (Matsunami Glass Ind., 1.35 mm thick, blue plate edge polished product) as an adherend. And crimped.
  • Example 16 showed a high refractive index exceeding 1.570 and high transparency. Further, as shown in Table 2, it showed practical peel strength as an adhesive and was also excellent in surface smoothness. In comparison between Example 3 and Example 16 using the same pressure-sensitive adhesive composition, Example 16 gave better results in the evaluation of optical strain. Although not shown in Table 2, the water absorption rate of Example 16 was 0.2%.
  • the refractive index is more than 1.570, the total light transmittance is 86% or more, and the haze value is 3.
  • a pressure-sensitive optical film having a pressure-sensitive adhesive layer of 0.0% or less on a light-transmitting member can be easily produced.
  • Example 15 in which the refractive index was improved by blending inorganic particles having a high refractive index was clearly inferior in transparency (particularly, the haze was remarkably high) as compared with Examples 1 to 13, as shown in Table 2.
  • the surface smoothness was also low, obvious optical distortion was observed, and the adhesive performance (peeling strength) suitable for practical use as an adhesive was not exhibited.
  • Examples 17, 18, 23> A solution of the acrylic polymer according to each of Examples 17, 18 and 23 was prepared in the same manner as in Example 1 except that the composition of the monomer component was as shown in Table 3, and an acrylic pressure-sensitive adhesive composition was prepared. .. The same as in the production of the pressure-sensitive adhesive sheet in Example 1, except that the acrylic pressure-sensitive adhesive composition according to each example was used instead of the acrylic pressure-sensitive adhesive composition C1 and the thickness of the pressure-sensitive adhesive layer was 25 ⁇ m. Adhesive sheets according to each example were produced.
  • BZA is benzyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “Viscort # 160", refractive index (nD20): 1.519, homopolymer Tg: 6 ° C.), and "PEA” is phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “Viscoat # 192", refractive index (nD20): 1.517, homopolymer Tg: 2 ° C.), " “P2HA” represents phenoxydiethylene glycol acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name "light acrylate P2HA", refractive index: 1.510, homopolymer Tg: -35 ° C.), and HEMA is 2-hydroxyethyl. Methacrylate and CBA represent ethyl carbitol acrylate, respectively.
  • Example 19 A solution of the acrylic polymer A19 according to this example was prepared in the same manner as in Example 1 except that the composition of the monomer components was as shown in Table 3. Using the solution of the acrylic polymer A19 in place of the solution of the acrylic polymer A3, additives (H RO) as 2,12- diallyloxymethyl Gina shift thiophene (Sugaikagakukogyo Co., abbreviation: 2,12-DAODNT , Refractive rate: 1.729) The acrylic pressure-sensitive adhesive composition according to this example was prepared in the same manner as in Example 4 except that 10 phr was used, and a pressure-sensitive adhesive sheet was prepared.
  • H RO 2,12- diallyloxymethyl Gina shift thiophene
  • the adhesive sheets of Examples 17 to 23 shown in Table 3 all showed a high refractive index exceeding 1.570 and high transparency. Of these, the pressure-sensitive adhesive sheet of Example 23 had a harder feel and a higher water absorption rate than the pressure-sensitive adhesive sheets of Examples 17 to 22. From the above, the pressure-sensitive adhesive sheets of Examples 1 to 14, Examples 16, and Examples 17 to 23 (base-less double-sided pressure-sensitive adhesive sheets composed of an adhesive layer) have a high refractive index while suppressing deterioration of optical characteristics. In the form of an adhesive optical film in which the pressure-sensitive adhesive layer is laminated on a light-transmitting member, bonding of optical members (for example, an optical film having at least one function of waveguideing, condensing, and refracting light), etc. Suitable for applications.
  • optical members for example, an optical film having at least one function of waveguideing, condensing, and refracting light
  • Adhesive type optical film 10 Adhesive layer 10A First surface (adhesive surface) 10B Second surface 20 Light transmissive member 20A First surface 20B Second surface (back surface) 30, 31, 32 Release liner 50 Adhesive optical film with release liner 70 Optical member (adhesive body) 100 optical laminate

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Abstract

The present invention provides an adhesive optical film which comprises a light-transmitting member and an adhesive layer that is superposed on the light-transmitting member. This adhesive optical film has an adhesive surface that is composed of the adhesive layer. The adhesive layer has a refractive index of more than 1.570, a total light transmittance of 86% or more, and a haze value of 3.0% or less.

Description

粘着型光学フィルムAdhesive optical film
 本発明は、粘着型光学フィルムに関し、詳しくは、光透過性部材と該光透過性部材に接合している粘着剤層とを含む粘着型光学フィルムに関する。
 本出願は、2020年3月24日に出願された日本国特許出願2020-052408号、2020年9月30日に出願された日本国特許出願2020-166427号、および2021年3月23日に出願された日本国特許出願2021-049060号に基づく優先権を主張しており、それらの出願の全内容は本明細書中に参照として組み入れられている。
The present invention relates to an adhesive optical film, and more particularly to an adhesive optical film including a light transmitting member and an adhesive layer bonded to the light transmitting member.
This application is filed on March 24, 2020, Japanese Patent Application No. 2020-052408, Japanese Patent Application No. 2020-166427 filed on September 30, 2020, and March 23, 2021. Priority is claimed under the Japanese patent application 2021-049060 filed, and the entire contents of those applications are incorporated herein by reference.
 一般に、粘着剤(感圧接着剤ともいう。以下同じ。)は、室温付近の温度域において柔らかい固体(粘弾性体)の状態を呈し、圧力により簡単に被着体に接着する性質を有する。このような性質を活かして、粘着剤は、家電製品から自動車、各種機械、電気機器、電子機器等の様々な産業分野において、接合や固定、保護等の目的で広く利用されている。粘着剤の用途の一例として、液晶表示装置や有機EL表示装置等のような表示装置において、偏光フィルム、位相差フィルム、カバーウィンドウ部材、その他種々の光透過性部材と、他の部材とを接合する用途が挙げられる。光学部材用の粘着剤に関する技術文献として特許文献1、2が挙げられる。 Generally, an adhesive (also referred to as a pressure-sensitive adhesive; the same applies hereinafter) exhibits a soft solid (viscous elastic body) state in a temperature range near room temperature, and has a property of easily adhering to an adherend by pressure. Taking advantage of these properties, adhesives are widely used for the purpose of joining, fixing, protecting, etc. in various industrial fields such as home appliances, automobiles, various machines, electric devices, and electronic devices. As an example of the use of the pressure-sensitive adhesive, in a display device such as a liquid crystal display device or an organic EL display device, a polarizing film, a retardation film, a cover window member, and various other light-transmitting members are joined to another member. Uses to be mentioned. Patent Documents 1 and 2 are listed as technical documents relating to adhesives for optical members.
日本国特許出願公開2014-169382号公報Japanese Patent Application Publication No. 2014-169382 日本国特許出願公開2017-128732号公報Japanese Patent Application Publication No. 2017-128732
 特許文献1、2は、モノマー単位として芳香環を複数有するモノマーを含有する(メタ)アクリル酸エステル重合体を主成分とする粘着剤組成物、および該粘着剤組成物を架橋してなる粘着剤を提案しているが、屈折率が1.570を超える具体的な粘着剤を開示してはいない。一方、高屈折率の無機材料からなる粒子(例えば、酸化ジルコニウム粒子や酸化チタン粒子等の無機粒子)を樹脂に配合して屈折率を高める技術も知られているが、無機粒子が配合された粘着剤は屈折率と粘着特性(例えば剥離強度、柔軟性等)とがトレードオフの関係にあるため、粘着剤の分野への適用は難しい。特に光学用途向けの粘着剤では、無機粒子の配合にあたっては光学特性(例えば全光線透過率、ヘイズ等)への影響にも配慮する必要がある。そのため、1.570を超える屈折率と、良好な光学特性(透明性)とを両立した粘着剤層を光透過性部材(例えば光学フィルム)の上に備え、実用的な粘着性能を示す粘着型光学フィルムを実現することは容易ではない。 Patent Documents 1 and 2 describe a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester polymer containing a monomer having a plurality of aromatic rings as a monomer unit as a main component, and a pressure-sensitive adhesive obtained by cross-linking the pressure-sensitive adhesive composition. However, it does not disclose a specific pressure-sensitive adhesive having a refractive index exceeding 1.570. On the other hand, there is also known a technique of blending particles made of an inorganic material having a high refractive index (for example, inorganic particles such as zirconium oxide particles and titanium oxide particles) into a resin to increase the refractive index, but inorganic particles are blended. Since the refractive index and the adhesive properties (for example, peel strength, flexibility, etc.) of the adhesive have a trade-off relationship, it is difficult to apply the adhesive to the field of the adhesive. In particular, in adhesives for optical applications, it is necessary to consider the influence on optical properties (for example, total light transmittance, haze, etc.) when blending inorganic particles. Therefore, an adhesive layer having a refractive index exceeding 1.570 and good optical characteristics (transparency) is provided on a light-transmitting member (for example, an optical film), and an adhesive type exhibiting practical adhesive performance. Realizing an optical film is not easy.
 本発明は、上記の状況に鑑みて創出されたものであり、高い屈折率と良好な光学特性とを兼ね備えた粘着剤層を有する粘着型光学フィルムを提供することを目的とする。本発明の他の目的は、上記粘着型光学フィルムを含む剥離ライナー付き粘着型光学フィルムを提供することである。 The present invention has been created in view of the above circumstances, and an object of the present invention is to provide an adhesive optical film having an adhesive layer having a high refractive index and good optical characteristics. Another object of the present invention is to provide an adhesive optical film with a release liner including the adhesive optical film.
 この明細書によると、光透過性部材と、該光透過性部材上に積層された粘着剤層と、を含む、粘着型光学フィルムが提供される。上記粘着型光学フィルムは、上記粘着剤層により構成された粘着面を有する。上記粘着剤層は、屈折率が1.570超であり、全光線透過率が86%以上であり、かつヘイズ値が3.0%以下である。このような粘着型光学フィルムでは光透過性部材と粘着剤層とが一体化しているので、該粘着型光学フィルムを用いることにより、上記粘着剤層を介して上記光透過性部材と被着体とが積層した構造を効率よくかつ精度よく形成することができる。 According to this specification, an adhesive optical film including a light transmitting member and an adhesive layer laminated on the light transmitting member is provided. The adhesive optical film has an adhesive surface composed of the adhesive layer. The pressure-sensitive adhesive layer has a refractive index of more than 1.570, a total light transmittance of 86% or more, and a haze value of 3.0% or less. In such an adhesive optical film, the light transmissive member and the adhesive layer are integrated. Therefore, by using the adhesive optical film, the light transmissive member and the adherend are formed through the adhesive layer. It is possible to efficiently and accurately form a structure in which and is laminated.
 いくつかの態様では、上記粘着剤層の厚さは5μm以上である。このような厚さを有する粘着剤層によると、良好な粘着特性が得られやすい。また、このような厚さを有する粘着剤層は、被着体表面に存在し得る凹凸を吸収して該被着体に密着性よく接合させやすいので、被着体上に高屈折率の粘着剤層を適切に設けることができる。 In some embodiments, the thickness of the pressure-sensitive adhesive layer is 5 μm or more. According to the pressure-sensitive adhesive layer having such a thickness, good pressure-sensitive adhesive properties can be easily obtained. Further, since the pressure-sensitive adhesive layer having such a thickness absorbs irregularities that may exist on the surface of the adherend and is easily bonded to the adherend with good adhesion, adhesion having a high refractive index on the adherend. The agent layer can be appropriately provided.
 いくつかの態様では、上記粘着型光学フィルムのガラス板に対する剥離強度(粘着力)が3N/25mm以上である。このような粘着力を有することは、被着体との接合信頼性の観点から好ましい。 In some aspects, the peel strength (adhesive strength) of the adhesive optical film with respect to the glass plate is 3N / 25 mm or more. Having such adhesive strength is preferable from the viewpoint of bonding reliability with the adherend.
 いくつかの態様では、上記粘着面は、算術平均粗さRaが100nm以下である。このように高平滑な粘着面を有することは、光学的均質性の観点から好ましい。例えば、上記粘着面を通じて光が取り出される使用態様(発光装置において上記粘着剤層が自発光素子よりも視点側に配置される態様等)において、粘着剤層の表面状態に起因する輝度ムラの発生を抑えることができる。 In some embodiments, the adhesive surface has an arithmetic mean roughness Ra of 100 nm or less. Having such a highly smooth adhesive surface is preferable from the viewpoint of optical homogeneity. For example, in a usage mode in which light is extracted through the pressure-sensitive adhesive surface (a mode in which the pressure-sensitive adhesive layer is arranged on the viewpoint side of the self-luminous element in a light emitting device, etc.), uneven brightness occurs due to the surface state of the pressure-sensitive adhesive layer. Can be suppressed.
 いくつかの態様では、上記粘着剤層の吸水率は1.0%以下である。吸水率の低い粘着剤層によると、該粘着剤層中の水分量の変動による粘着剤層の寸法変化を抑制することができる。これにより、粘着型光学フィルムまたは該粘着型光学フィルムを含む積層体の反りを抑制することができる。 In some embodiments, the water absorption rate of the pressure-sensitive adhesive layer is 1.0% or less. According to the pressure-sensitive adhesive layer having a low water absorption rate, it is possible to suppress a dimensional change of the pressure-sensitive adhesive layer due to a fluctuation in the amount of water in the pressure-sensitive adhesive layer. Thereby, the warp of the adhesive type optical film or the laminated body containing the adhesive type optical film can be suppressed.
 いくつかの態様では、上記粘着型光学フィルムは、上記粘着剤層と、上記光透過性部材としての樹脂フィルムと、を含む積層体として構成されている。このような構成の粘着型光学フィルムを被着体に貼り付けることにより、該被着体と上記光透過性部材とが高屈折率の粘着剤層を介して積層した構造を容易に形成することができる。 In some embodiments, the pressure-sensitive optical film is configured as a laminate containing the pressure-sensitive adhesive layer and the resin film as a light-transmitting member. By attaching an adhesive optical film having such a structure to an adherend, a structure in which the adherend and the light transmissive member are laminated via an adhesive layer having a high refractive index can be easily formed. Can be done.
 また、この明細書によると、ここに開示されるいずれかの粘着型光学フィルムと、上記粘着型光学フィルムの粘着面上に配置された剥離ライナーとを含む、剥離ライナー付き粘着型光学フィルムが提供される。ここに開示される粘着型光学フィルムは、このように粘着面上に剥離ライナーが配置された剥離ライナー付き粘着型光学フィルムの形態で製造、保管、流通、加工等を行い、被着体への貼付け前に粘着面から剥離ライナーを剥がす態様で好ましく用いられ得る。 Further, according to the present specification, there is provided an adhesive optical film with a release liner, which comprises any of the adhesive optical films disclosed herein and a release liner arranged on the adhesive surface of the adhesive optical film. Will be done. The adhesive optical film disclosed herein is manufactured, stored, distributed, processed, etc. in the form of an adhesive optical film with a release liner in which a release liner is arranged on the adhesive surface in this way, and is applied to an adherend. It can be preferably used in a mode in which the release liner is peeled off from the adhesive surface before sticking.
 なお、本明細書に記載された各要素を適宜組み合わせたものも、本件特許出願によって特許による保護を求める発明の範囲に含まれ得る。 It should be noted that an appropriate combination of the elements described in the present specification may be included in the scope of the invention for which protection by the patent is sought by the present patent application.
一実施形態に係る粘着型光学フィルムの構成を模式的に示す断面図である。It is sectional drawing which shows typically the structure of the adhesive type optical film which concerns on one Embodiment. 一実施形態に係る粘着型光学フィルムを含む光学積層体の構成を模式的に示す断面図である。It is sectional drawing which shows typically the structure of the optical laminate containing the adhesive type optical film which concerns on one Embodiment.
 以下、本発明の好適な実施形態を説明する。本明細書において特に言及している事項以外の事柄であって本発明の実施に必要な事柄は、本明細書に記載された発明の実施についての教示と出願時の技術常識とに基づいて当業者に理解され得る。本発明は、本明細書に開示されている内容と当該分野における技術常識とに基づいて実施することができる。
 なお、以下の図面において、同じ作用を奏する部材・部位には同じ符号を付して説明することがあり、重複する説明は省略または簡略化することがある。また、図面に記載の実施形態は、本発明を明瞭に説明するために模式化されており、実際に提供される製品のサイズや縮尺を必ずしも正確に表したものではない。
Hereinafter, preferred embodiments of the present invention will be described. Matters other than those specifically mentioned in the present specification and necessary for the practice of the present invention are based on the teachings regarding the practice of the invention described in the present specification and the common general knowledge at the time of filing. Can be understood by those skilled in the art. The present invention can be carried out based on the contents disclosed in the present specification and common general technical knowledge in the art.
In the following drawings, members / parts having the same function may be described with the same reference numerals, and duplicate description may be omitted or simplified. Further, the embodiments described in the drawings are modeled for clearly explaining the present invention, and do not necessarily accurately represent the size and scale of the actually provided product.
 この明細書において、自発光素子とは、流れる電流値によって発光輝度を制御することが可能な発光素子を意味する。自発光素子は、単一体で構成されていてもよく、集合体で構成されていてもよい。自発光素子の具体例には、発光ダイオード(LED)および有機ELが含まれるが、これらに限定されない。この明細書において発光装置に言及する場合、該発光装置は、このような自発光素子を構成要素として含み得る。上記発光装置の例には、照明として利用される光源モジュール装置(例えば、面状発光体モジュール)や、画素を形成した表示装置が含まれるが、これらに限定されない。 In this specification, the self-luminous element means a light emitting element capable of controlling the emission brightness by the flowing current value. The self-luminous element may be composed of a single body or an aggregate. Specific examples of the self-luminous element include, but are not limited to, a light emitting diode (LED) and an organic EL. When referring to a light emitting device in the present specification, the light emitting device may include such a self-luminous element as a component. Examples of the light emitting device include, but are not limited to, a light source module device used as lighting (for example, a planar light emitting body module) and a display device having pixels formed therein.
<粘着型光学フィルムの構成例>
 この明細書により開示される粘着型光学フィルムの一構成例を図1に示す。この粘着型光学フィルム1は、第1の表面10Aが被着体への貼付面(粘着面)となっている粘着剤層10と、粘着剤層10の第2の表面10Bに積層された光透過性部材20と、を含む片面接着性の粘着型光学フィルム(片面粘着シート)として構成されている。粘着剤層10の第2の表面10Bは、光透過性部材20の第1面(非剥離性の表面)20Aに接合している。光透過性部材20は、例えば光学用の樹脂フィルムであり得る。光透過性部材20は、偏光板等の光学フィルムであってもよい。使用前(被着体への貼付け前)の粘着型光学フィルム1は、例えば図1に示すように、粘着面10Aが、少なくとも該粘着剤層側が剥離性表面(剥離面)となっている剥離ライナー30で保護された、剥離ライナー付き粘着型光学フィルム50の形態であり得る。あるいは、光透過性部材20の第2面20B(第1面20Aとは反対側の表面であり、背面ともいう。)が剥離面となっており、この第2面20Bに粘着面10Aが当接するように巻回または積層されることで粘着面10Aが保護された形態であってもよい。粘着剤層10は、単層構造であってもよく、組成の異なる2以上のサブ粘着剤層が直接接して(すなわち、非粘着性材料の層によって隔てられることなく)積層した積層構造であってもよい。
<Structure example of adhesive optical film>
An example of the configuration of the adhesive optical film disclosed by this specification is shown in FIG. In this adhesive type optical film 1, the light laminated on the pressure-sensitive adhesive layer 10 in which the first surface 10A is the surface to be attached to the adherend (adhesive surface) and the second surface 10B of the pressure-sensitive adhesive layer 10. It is configured as a single-sided adhesive adhesive optical film (single-sided adhesive sheet) including a transparent member 20. The second surface 10B of the pressure-sensitive adhesive layer 10 is bonded to the first surface (non-peelable surface) 20A of the light-transmitting member 20. The light transmissive member 20 can be, for example, a resin film for optics. The light transmissive member 20 may be an optical film such as a polarizing plate. In the adhesive optical film 1 before use (before sticking to the adherend), for example, as shown in FIG. 1, the adhesive surface 10A is peeled off so that at least the adhesive layer side is a peelable surface (peeling surface). It may be in the form of an adhesive optical film 50 with a release liner protected by a liner 30. Alternatively, the second surface 20B of the light transmissive member 20 (the surface opposite to the first surface 20A, also referred to as the back surface) is a peeling surface, and the adhesive surface 10A hits the second surface 20B. The adhesive surface 10A may be protected by being wound or laminated so as to be in contact with each other. The pressure-sensitive adhesive layer 10 may have a single-layer structure, and is a laminated structure in which two or more sub- pressure-sensitive adhesive layers having different compositions are directly in contact with each other (that is, without being separated by a layer of a non-adhesive material). You may.
 ここに開示される粘着型光学フィルムは、粘着剤層の少なくとも一方の表面に光学部材が接合された光学積層体の構成要素であり得る。例えば、図1に示す粘着型光学フィルム1は、図2に示すように、粘着剤層10の第1の表面10Aに光学部材70が接合された光学積層体100の構成要素であり得る。上記光学部材は、例えば、ガラス板、樹脂フィルム、金属板等であり得る。また、図1に示す粘着型光学フィルム1において、光透過性部材20が光学フィルム等の光学部材である場合、該粘着型光学フィルム1は、粘着剤層10の第2の表面10Bに光学部材が接合された光学積層体として把握され得る。 The adhesive optical film disclosed herein can be a component of an optical laminate in which an optical member is bonded to at least one surface of an adhesive layer. For example, the adhesive optical film 1 shown in FIG. 1 can be a component of the optical laminate 100 in which the optical member 70 is bonded to the first surface 10A of the adhesive layer 10, as shown in FIG. The optical member may be, for example, a glass plate, a resin film, a metal plate, or the like. Further, in the adhesive type optical film 1 shown in FIG. 1, when the light transmitting member 20 is an optical member such as an optical film, the adhesive type optical film 1 is formed on the second surface 10B of the adhesive layer 10 by the optical member. Can be grasped as a bonded optical laminate.
 また、ここに開示される粘着型光学フィルムは、特に図示しないが、非剥離性の第1面および第2面を有する光透過性部材を備え、上記第1面に第1粘着剤層が固定的に積層され、上記第2面に第2粘着剤層が固定的に積層された、両面接着性の粘着型光学フィルムの形態であってもよい。このような両面接着性の粘着型光学フィルム(以下、両面粘着型光学フィルムともいう。)の構成例として、図1に示す粘着型光学フィルム(片面粘着シート)1において、光透過性部材20の第2面20Bが非剥離性の表面であって該第2面20B上に第2粘着剤層が設けられ、上記第2粘着剤層の第2の表面が光透過性部材20の第2面20Bに接合し、上記第2粘着剤層の第1の表面(第2の表面とは反対側の表面)が両面粘着型光学フィルムの第2粘着面となっている形態が挙げられる。第2粘着剤層を構成する粘着剤の組成は、第1粘着剤層を構成する粘着剤の組成と同様であってもよく、異なっていてもよい。使用前の両面粘着型光学フィルムは、第1粘着面および第2粘着面が剥離ライナーによって保護された形態であり得る。 Further, although not particularly shown, the adhesive optical film disclosed herein includes a light-transmitting member having a non-peelable first surface and a second surface, and a first adhesive layer is fixed to the first surface. It may be in the form of a double-sided adhesive adhesive optical film in which the second pressure-sensitive adhesive layer is fixedly laminated on the second surface. As a configuration example of such a double-sided adhesive adhesive optical film (hereinafter, also referred to as a double-sided adhesive optical film), in the adhesive optical film (single-sided adhesive sheet) 1 shown in FIG. The second surface 20B is a non-peelable surface, a second pressure-sensitive adhesive layer is provided on the second surface 20B, and the second surface of the second pressure-sensitive adhesive layer is the second surface of the light-transmitting member 20. Examples thereof include a form in which the first surface (the surface opposite to the second surface) of the second pressure-sensitive adhesive layer is bonded to 20B and is the second pressure-sensitive surface of the double-sided pressure-sensitive optical film. The composition of the pressure-sensitive adhesive constituting the second pressure-sensitive adhesive layer may be the same as or different from the composition of the pressure-sensitive adhesive constituting the first pressure-sensitive adhesive layer. The double-sided adhesive optical film before use may be in a form in which the first adhesive surface and the second adhesive surface are protected by a release liner.
 なお、ここに開示され粘着型光学フィルムは、ロール状であってもよく、枚葉状であってもよい。あるいは、さらに種々の形状に加工された形態の粘着型光学フィルムであってもよい。 The adhesive optical film disclosed herein may be in the form of a roll or in the form of a single leaf. Alternatively, it may be an adhesive optical film in a form further processed into various shapes.
<粘着剤層の特性>
 (屈折率)
 ここに開示される粘着型光学フィルムは、屈折率が1.570超の粘着剤層を有する。このような粘着剤層は、屈折率が1.570超の粘着剤によって該粘着剤層の少なくとも一方の表面(粘着面)を構成することにより実現することができる。ここに開示される技術によると、屈折率が1.570超である粘着剤、該粘着剤を形成することのできる粘着剤組成物、および上記粘着剤を含む粘着型光学フィルムが提供され得る。
<Characteristics of adhesive layer>
(Refractive index)
The pressure-sensitive optical film disclosed herein has a pressure-sensitive adhesive layer having a refractive index of more than 1.570. Such an adhesive layer can be realized by forming at least one surface (adhesive surface) of the adhesive layer with an adhesive having a refractive index of more than 1.570. According to the technique disclosed herein, a pressure-sensitive adhesive having a refractive index of more than 1.570, a pressure-sensitive adhesive composition capable of forming the pressure-sensitive adhesive, and a pressure-sensitive optical film containing the pressure-sensitive adhesive can be provided.
 なお、本明細書において粘着剤の屈折率とは、該粘着剤の表面(粘着面)の屈折率をいう。粘着剤の屈折率は、市販の屈折率測定装置(アッベ屈折率計)を用いて、測定波長589nm、測定温度25℃の条件で測定することができる。アッベ屈折率計としては、例えばATAGO社製の型式「DR-M4」またはその相当品が用いられる。測定サンプルとしては、評価対象の粘着剤からなる粘着剤層を用いることができる。粘着剤の屈折率は、具体的には、後述の実施例に記載の方法で測定することができる。粘着剤の屈折率は、例えば、該粘着剤の組成(例えば、ベースポリマーを構成するモノマー成分の組成、必要に応じて用いられ得る添加剤等)によって調節することができる。 In the present specification, the refractive index of the pressure-sensitive adhesive means the refractive index of the surface (adhesive surface) of the pressure-sensitive adhesive. The refractive index of the pressure-sensitive adhesive can be measured using a commercially available refractive index measuring device (Abbe refractive index meter) under the conditions of a measurement wavelength of 589 nm and a measurement temperature of 25 ° C. As the Abbe refractive index meter, for example, a model "DR-M4" manufactured by ATAGO or an equivalent product thereof is used. As the measurement sample, a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive to be evaluated can be used. Specifically, the refractive index of the pressure-sensitive adhesive can be measured by the method described in Examples described later. The refractive index of the pressure-sensitive adhesive can be adjusted, for example, by the composition of the pressure-sensitive adhesive (for example, the composition of the monomer components constituting the base polymer, additives that can be used if necessary, etc.).
 いくつかの態様において、上記粘着剤の屈折率は、好ましくは1.580以上であり、より好ましくは1.585以上であり、さらに好ましくは1.590以上(例えば1.595以上)であり得る。かかる屈折率を有する粘着剤によると、該粘着剤と被着体との相対的な屈折率の関係を利用して、該粘着剤を透過する光の挙動を効果的に制御することができる。ここに開示される粘着剤のいくつかの態様において、該粘着剤の屈折率は、例えば1.600以上または1.600超、1.605以上または1.605超、あるいは1.610以上または1.610超であり得る。粘着剤の屈折率の好ましい上限は、被着体の屈折率等に応じて異なり得るので特定の範囲に限定されない。いくつかの態様において、粘着特性や透明性とのバランスを考慮して、粘着剤の屈折率は、例えば1.700以下であってよく、1.670以下でもよく、1.650以下でもよい。 In some embodiments, the refractive index of the pressure-sensitive adhesive may be preferably 1.580 or higher, more preferably 1.585 or higher, and even more preferably 1.590 or higher (eg 1.595 or higher). .. According to the pressure-sensitive adhesive having such a refractive index, the behavior of light transmitted through the pressure-sensitive adhesive can be effectively controlled by utilizing the relationship of the relative refractive index between the pressure-sensitive adhesive and the adherend. In some aspects of the pressure-sensitive adhesives disclosed herein, the index of refraction of the pressure-sensitive adhesive is, for example, 1.600 or greater or greater than 1.600, 1.605 or greater or greater than 1.605, or 1.610 or greater or 1 It can be over 610. The preferable upper limit of the refractive index of the pressure-sensitive adhesive is not limited to a specific range because it may differ depending on the refractive index of the adherend and the like. In some embodiments, the refractive index of the pressure-sensitive adhesive may be, for example, 1.700 or less, 1.670 or less, or 1.650 or less in consideration of the balance with the adhesive properties and transparency.
 ここに開示される粘着型光学フィルムが、一方の面が第1粘着面となっており、他方の面が第2粘着面となっている両面粘着型光学フィルムの形態である場合、少なくも第1粘着面が上述したいずれかの屈折率を満たせばよく、第2粘着面の屈折率は特に制限されない。
 いくつかの態様において、第2粘着面の屈折率nは、第1粘着面の屈折率nと概ね同程度であり得る。より具体的には、両粘着面の屈折率の差の絶対値、すなわち|n-n|は、例えば0.05未満、または0.03未満、または0.01未満であり得る。|n-n|の下限は、0.00でもよく、0.00より大でもよい。両粘着面の屈折率の相対関係は、n>nでもよく、n<nでもよく、n=nでもよい。
 他のいくつかの態様において、両面粘着型光学フィルムの第1粘着面の屈折率nと第2粘着面の屈折率nとの差、すなわちn-nは、例えば0.00より大であってよく、0.01以上でもよく、0.03以上でもよく、0.05以上でもよく、0.10以上でもよく、0.15以上でもよく、0.20以上でもよく、0.25以上でもよい。nとnとの大小関係は逆でもよい。第1粘着面と第2粘着面とで屈折率が異なる両面粘着型光学フィルムは、例えば、光透過性部材の第1面および第2面に互いに屈折率の異なる第1、第2粘着剤層を積層することによって実現し得る。
When the adhesive optical film disclosed herein is in the form of a double-sided adhesive optical film in which one surface is a first adhesive surface and the other surface is a second adhesive surface, at least the first. The refractive index of the first adhesive surface may satisfy any of the above-mentioned refractive coefficients, and the refractive index of the second adhesive surface is not particularly limited.
In some embodiments, the refractive index n 2 of the second adhesive surface can be approximately comparable to the refractive index n 1 of the first adhesive surface. More specifically, the absolute value of the difference in refractive index between the two adhesive surfaces, that is, | n 1- n 2 |, can be, for example, less than 0.05, less than 0.03, or less than 0.01. The lower limit of | n 1 − n 2 | may be 0.00 or greater than 0.00. The relative relationship between the refractive indexes of both adhesive surfaces may be n 1 > n 2 , n 1 <n 2 , or n 1 = n 2 .
In some other embodiments, the difference between the refractive index n 1 of the first adhesive surface and the refractive index n 2 of the second adhesive surface of the double-sided adhesive optical film, that is, n 1 to n 2, is, for example, greater than 0.00. It may be large, 0.01 or more, 0.03 or more, 0.05 or more, 0.10 or more, 0.15 or more, 0.20 or more, 0. It may be 25 or more. The magnitude relationship between n 1 and n 2 may be reversed. The double-sided adhesive optical film having different refractive indexes between the first adhesive surface and the second adhesive surface is, for example, a first and second adhesive layers having different refractive indexes on the first surface and the second surface of the light transmissive member. Can be realized by laminating.
 (全光線透過率)
 ここに開示される粘着型光学フィルムは、上記の高屈折率を有し、かつ全光線透過率が86%以上である粘着剤層を備える。いくつかの態様において、上記粘着剤層の全光線透過率は、88%以上であることが好ましく、90%以上(例えば90.0%超)であることがより好ましく、90.5%以上でもよく、93%以上でもよく、95%以上でもよい。全光線透過率の上限は、理論的には、100%から空気界面で生じる反射による光損失(フレネルロス)を除いた値となり、実用上、凡そ98%以下であってよく、凡そ96%以下でもよく、凡そ95%以下でもよい。いくつかの態様では、屈折率や粘着特性を考慮して、粘着剤層の全光線透過率は、凡そ94%以下でもよく、凡そ93%以下でもよく、凡そ92%以下でもよい。全光線透過率は、JIS K 7136:2000に準拠して、市販の透過率計を使用して測定される。透過率計としては、村上色彩技術研究所製の商品名「HAZEMETER HM-150」またはその相当品が用いられる。より具体的には、例えば後述の実施例に従って粘着剤層の全光線透過率を測定することができる。粘着剤層の全光線透過率は、例えば、該粘着剤層の組成や厚さ等の選択によって調節することができる。
(Total light transmittance)
The pressure-sensitive optical film disclosed herein includes a pressure-sensitive adhesive layer having the above-mentioned high refractive index and a total light transmittance of 86% or more. In some embodiments, the total light transmittance of the pressure-sensitive adhesive layer is preferably 88% or more, more preferably 90% or more (for example, more than 90.0%), and even 90.5% or more. It may be 93% or more, or 95% or more. Theoretically, the upper limit of the total light transmittance is a value obtained by subtracting the light loss (Frenel loss) due to reflection generated at the air interface from 100%, and practically, it may be about 98% or less, or even about 96% or less. Well, it may be about 95% or less. In some embodiments, the total light transmittance of the pressure-sensitive adhesive layer may be about 94% or less, about 93% or less, or about 92% or less in consideration of the refractive index and the adhesive property. Total light transmittance is measured using a commercially available transmittance meter in accordance with JIS K 7136: 2000. As the transmittance meter, the trade name "HAZEMETER HM-150" manufactured by Murakami Color Technology Research Institute or its equivalent is used. More specifically, for example, the total light transmittance of the pressure-sensitive adhesive layer can be measured according to the examples described later. The total light transmittance of the pressure-sensitive adhesive layer can be adjusted by selecting, for example, the composition and thickness of the pressure-sensitive adhesive layer.
 ここに開示される粘着型光学フィルムが、光透過性部材の第1面および第2面に第1粘着剤層および第2粘着剤層が固定的に積層された両面粘着型光学フィルムの形態である場合、少なくとも第1粘着剤層が上述したいずれかの全光線透過率を満たせばよく、第2粘着剤層の全光線透過率は特に特に制限されない。粘着型光学フィルムの厚み方向に光が通り抜ける使用態様では、第2粘着剤層の全光線透過率が、上述した第1粘着剤層の全光線透過率のいずれかを満たすことが好ましい。両粘着剤層の全光線透過率の相対関係は、第1粘着剤層>第2粘着剤層でもよく、第1粘着剤層<第2粘着剤層でもよく、第1粘着剤層=第2粘着剤層でもよい。 The pressure-sensitive optical film disclosed herein is in the form of a double-sided pressure-sensitive optical film in which a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer are fixedly laminated on the first and second surfaces of a light-transmitting member. In some cases, at least the first pressure-sensitive adhesive layer may satisfy any of the above-mentioned total light transmission rates, and the total light transmission rate of the second pressure-sensitive adhesive layer is not particularly limited. In the usage mode in which light passes through in the thickness direction of the adhesive optical film, it is preferable that the total light transmittance of the second pressure-sensitive adhesive layer satisfies any of the total light transmittances of the first pressure-sensitive adhesive layer described above. The relative relationship between the total light transmittances of both pressure-sensitive adhesive layers may be the first pressure-sensitive adhesive layer> the second pressure-sensitive adhesive layer, the first pressure-sensitive adhesive layer <the second pressure-sensitive adhesive layer, and the first pressure-sensitive adhesive layer = the second. It may be an adhesive layer.
 (ヘイズ値)
 ここに開示される粘着型光学フィルムは、上記の高屈折率を有し、かつヘイズ値が3.0%以下である粘着剤層を備える。いくつかの態様において、上記粘着剤層のヘイズ値は、2.0%以下であることが好ましく、1.0%以下であることがより好ましく、0.9%以下であることがさらに好ましく、0.8%以下でもよく、0.5%以下でもよく、0.3%以下でもよい。粘着剤層のヘイズ値の下限は特に制限されず、透明性向上の観点からはヘイズ値は小さいほど好ましい。一方、いくつかの態様では、屈折率や粘着特性を考慮して、ヘイズ値は、例えば0.05%以上であってよく、0.1%以上でもよく.0.2%以上でもよく、0.3%以上でもよく、0.4%以上でもよい。
(Haze value)
The pressure-sensitive optical film disclosed herein includes a pressure-sensitive adhesive layer having the above-mentioned high refractive index and a haze value of 3.0% or less. In some embodiments, the haze value of the pressure-sensitive adhesive layer is preferably 2.0% or less, more preferably 1.0% or less, still more preferably 0.9% or less. It may be 0.8% or less, 0.5% or less, or 0.3% or less. The lower limit of the haze value of the pressure-sensitive adhesive layer is not particularly limited, and a smaller haze value is preferable from the viewpoint of improving transparency. On the other hand, in some embodiments, the haze value may be, for example, 0.05% or more, or 0.1% or more, in consideration of the refractive index and the adhesive property. It may be 0.2% or more, 0.3% or more, or 0.4% or more.
 ここで「ヘイズ値」とは、測定対象に可視光を照射したときの、全透過光に対する拡散透過光の割合をいう。くもり価ともいう。ヘイズ値は、以下の式で表すことができる。
   Th(%)=Td/Tt×100
 上記式において、Thはヘイズ値(%)であり、Tdは散乱光透過率、Ttは全光透過率である。ヘイズ値の測定は、後述の実施例に記載の方法に従って行うことができる。粘着剤層のヘイズ値は、例えば、該粘着剤層の組成や厚さ等の選択によって調節することができる。
Here, the "haze value" refers to the ratio of diffuse transmitted light to total transmitted light when the measurement target is irradiated with visible light. Also called cloudy value. The haze value can be expressed by the following formula.
Th (%) = Td / Tt × 100
In the above formula, Th is a haze value (%), Td is a scattered light transmittance, and Tt is a total light transmittance. The haze value can be measured according to the method described in Examples described later. The haze value of the pressure-sensitive adhesive layer can be adjusted by selecting, for example, the composition and thickness of the pressure-sensitive adhesive layer.
 ここに開示される粘着型光学フィルムが、光透過性部材の第1面および第2面に第1粘着剤層および第2粘着剤層が固定的に積層された両面粘着型光学フィルムの形態である場合、少なくとも第1粘着剤層が上述したいずれかのヘイズ値を満たせばよく、第2粘着剤層のヘイズ値は特に制限されない。粘着型光学フィルムの厚み方向に光が通り抜ける使用態様では、第2粘着剤層のヘイズ値が、上述した第1粘着剤層のヘイズ値のいずれかを満たすことが好ましい。両粘着剤層のヘイズ値の相対関係は、第1粘着剤層>第2粘着剤層でもよく、第1粘着剤層<第2粘着剤層でもよく、第1粘着剤層=第2粘着剤層でもよい。 The pressure-sensitive optical film disclosed herein is in the form of a double-sided pressure-sensitive optical film in which a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer are fixedly laminated on the first and second surfaces of a light-transmitting member. In some cases, at least the first pressure-sensitive adhesive layer may satisfy any of the above-mentioned haze values, and the haze value of the second pressure-sensitive adhesive layer is not particularly limited. In the usage mode in which light passes through in the thickness direction of the adhesive type optical film, it is preferable that the haze value of the second pressure-sensitive adhesive layer satisfies any of the haze values of the first pressure-sensitive adhesive layer described above. The relative relationship between the haze values of both adhesive layers may be 1st adhesive layer> 2nd adhesive layer, 1st adhesive layer <2nd adhesive layer, and 1st adhesive layer = 2nd adhesive. It may be a layer.
 (粘着面の表面平滑性)
 ここに開示される粘着型光学フィルムのいくつかの態様において、該粘着型光学フィルムの粘着面は、高い表面平滑性を有することが好ましい。
(Surface smoothness of adhesive surface)
In some aspects of the adhesive optical film disclosed herein, the adhesive surface of the adhesive optical film preferably has high surface smoothness.
 例えば、上記粘着面は、その算術平均粗さRaが所定値以下に制限されていることが好ましい。算術平均粗さRaが低くなるように設計された粘着面を備える構成は、光学的均質性の観点から好ましい。算術平均粗さRaを制限することにより、例えば上記粘着面を通じて光が取り出される使用態様(発光装置において上記粘着剤層が自発光素子よりも視点側に配置される態様等)において、粘着剤層の表面状態に起因する輝度ムラの発生を抑制する効果を発揮することができる。粘着面の算術平均粗さRaが低いことは、光学歪の抑制にも有利であり、光学歪の抑制もまた光学的均質性の向上に寄与する。第1粘着面および第2粘着面を有する両面粘着型光学フィルムにおいては、少なくとも第1粘着面の算術平均粗さRaが所定値以下に制限されていることが好ましく、両粘着面の算術平均粗さRaがいずれも所定値以下に制限されていることがより好ましい。両面粘着型光学フィルムの各粘着面が高い表面平滑性を有することで、光学的均質性に優れた接着を好ましく実現し得る。 For example, it is preferable that the arithmetic average roughness Ra of the adhesive surface is limited to a predetermined value or less. A configuration having an adhesive surface designed to have a low arithmetic mean roughness Ra is preferable from the viewpoint of optical homogeneity. By limiting the arithmetic mean roughness Ra, for example, in a usage mode in which light is extracted through the pressure-sensitive adhesive surface (such as a mode in which the pressure-sensitive adhesive layer is arranged on the viewpoint side of the self-luminous element in a light emitting device), the pressure-sensitive adhesive layer. It is possible to exert the effect of suppressing the occurrence of brightness unevenness due to the surface condition of the above. The low arithmetic mean roughness Ra of the adhesive surface is also advantageous for suppressing optical strain, and the suppression of optical strain also contributes to the improvement of optical homogeneity. In the double-sided adhesive optical film having the first adhesive surface and the second adhesive surface, it is preferable that at least the arithmetic average roughness Ra of the first adhesive surface is limited to a predetermined value or less, and the arithmetic average roughness of both adhesive surfaces is preferable. It is more preferable that Ra is limited to a predetermined value or less. Since each adhesive surface of the double-sided adhesive optical film has high surface smoothness, it is possible to preferably realize adhesion having excellent optical homogeneity.
 いくつかの態様において、粘着面の算術平均粗さRaは、好ましくは凡そ70nm以下であり、より好ましくは凡そ65nm以下であり、さらに好ましくは凡そ55nm以下であり、50nm未満であってもよく、45nm未満でもよく、40nm未満でもよい。生産効率等の観点から、いくつかの態様において、粘着面の算術平均粗さRaは、例えば凡そ10nm以上であってよく、凡そ20nm以上でもよく、凡そ30nm以上(例えば凡そ40nm以上)でもよい。粘着型光学フィルムが第1粘着面および第2粘着面を有する態様において、第1粘着面の算術平均粗さRaと第2粘着面の算術平均粗さRaとは、同程度であってもよく、異なっていてもよい。 In some embodiments, the arithmetic mean roughness Ra of the adhesive surface is preferably about 70 nm or less, more preferably about 65 nm or less, still more preferably about 55 nm or less, and may be less than 50 nm. It may be less than 45 nm or less than 40 nm. From the viewpoint of production efficiency and the like, in some embodiments, the arithmetic mean roughness Ra of the adhesive surface may be, for example, about 10 nm or more, about 20 nm or more, or about 30 nm or more (for example, about 40 nm or more). In the embodiment in which the adhesive optical film has a first adhesive surface and a second adhesive surface, the arithmetic average roughness Ra of the first adhesive surface and the arithmetic average roughness Ra of the second adhesive surface may be about the same. , May be different.
 また、例えば、上記粘着面は、最大高さRzが所定値以下に制限されていることが好ましい。最大高さRzが低くなるように設計された粘着面を備える構成は、光学的均質性の観点から好ましい。最大高さRzを制限することにより、例えば上述のように上記粘着面を通じて光が取り出される使用態様において、粘着剤層の表面状態に起因する輝度ムラの発生を抑制する効果を発揮することができる。粘着面の最大高さRzが低いことは、光学歪の抑制にも有利である。第1粘着面および第2粘着面を有する両面粘着型光学フィルムにおいては、少なくとも第1粘着面の最大高さRzが所定値以下に制限されていることが好ましく、両粘着面の最大高さRzがいずれも所定値以下に制限されていることがより好ましい。両面粘着型光学フィルムの各粘着面が高い表面平滑性を有することで、光学的均質性に優れた接着を好ましく実現し得る。 Further, for example, it is preferable that the maximum height Rz of the adhesive surface is limited to a predetermined value or less. A configuration having an adhesive surface designed to have a low maximum height Rz is preferable from the viewpoint of optical homogeneity. By limiting the maximum height Rz, for example, in the usage mode in which light is extracted through the adhesive surface as described above, it is possible to exert the effect of suppressing the occurrence of luminance unevenness due to the surface state of the adhesive layer. .. The low maximum height Rz of the adhesive surface is also advantageous for suppressing optical distortion. In the double-sided adhesive optical film having the first adhesive surface and the second adhesive surface, it is preferable that at least the maximum height Rz of the first adhesive surface is limited to a predetermined value or less, and the maximum height Rz of both adhesive surfaces. Is more preferably limited to a predetermined value or less. Since each adhesive surface of the double-sided adhesive optical film has high surface smoothness, it is possible to preferably realize adhesion having excellent optical homogeneity.
 いくつかの態様において、粘着面の最大高さRzは、好ましくは凡そ600nm以下であり、より好ましくは凡そ500nm以下であり、さらに好ましくは凡そ450nm以下であり、特に好ましくは凡そ400nm以下であり、350nm未満であってもよく、300nm未満でもよく、250nm未満でもよい。生産効率等の観点から、いくつかの態様において、粘着面の最大高さRzは、例えば凡そ10nm以上であってよく、凡そ50nm以上でもよく、凡そ100nm以上でもよく、凡そ200nm以上でもよい。第1粘着面および第2粘着面を有する粘着型光学フィルムの形態において、第1粘着面の最大高さRzと第2粘着面の最大高さRzとは、同程度であってもよく、異なっていてもよい。 In some embodiments, the maximum height Rz of the adhesive surface is preferably about 600 nm or less, more preferably about 500 nm or less, still more preferably about 450 nm or less, and particularly preferably about 400 nm or less. It may be less than 350 nm, less than 300 nm, or less than 250 nm. From the viewpoint of production efficiency and the like, in some embodiments, the maximum height Rz of the adhesive surface may be, for example, about 10 nm or more, about 50 nm or more, about 100 nm or more, or about 200 nm or more. In the form of the adhesive type optical film having the first adhesive surface and the second adhesive surface, the maximum height Rz of the first adhesive surface and the maximum height Rz of the second adhesive surface may be the same or different. May be.
 粘着面の算術平均粗さRaおよび最大高さRzは、非接触式の表面粗さ測定装置を用いて測定される。非接触式の表面粗さ測定装置としては、光干渉方式の表面粗さ測定装置が用いられ、例えば3次元光学プロファイラー(商品名「NewView7300」、ZYGO社製)またはその相当品を使用することができる。具体的な測定操作および測定条件は、後述する実施例に記載の測定条件に従って、または該測定条件に従う場合と同等もしくは対応する結果が得られるように設定することができる。 The arithmetic mean roughness Ra and the maximum height Rz of the adhesive surface are measured using a non-contact type surface roughness measuring device. As the non-contact type surface roughness measuring device, a light interference type surface roughness measuring device is used, and for example, a three-dimensional optical profiler (trade name "NewView7300", manufactured by ZYGO) or an equivalent product thereof can be used. can. The specific measurement operation and measurement conditions can be set according to the measurement conditions described in Examples described later, or to obtain results equivalent to or corresponding to those according to the measurement conditions.
 粘着面の算術平均粗さRaおよび最大高さRzは、粘着剤層の形成に用いる粘着剤組成物の組成や性状(粘度、レベリング性等)、粘着面を保護する剥離ライナーの表面(剥離面)の性状等によって調節され得る。 The arithmetic mean roughness Ra and maximum height Rz of the adhesive surface are the composition and properties (viscosity, leveling property, etc.) of the adhesive composition used to form the adhesive layer, and the surface of the release liner that protects the adhesive surface (release surface). ) Can be adjusted according to the properties.
 (吸水率)
 ここに開示される粘着型光学フィルムのいくつかの態様において、該粘着型光学フィルムを構成する粘着剤層は、吸水率が所定値以下に制限されていることが好ましい。例えば、上述した屈折率、全光線透過率およびヘイズ値を満たし、かつ吸水率が所定値以下に制限されていることが好ましい。粘着剤層の吸水率を制限することにより、該粘着剤層中の水分量の変動(例えば、環境中の湿気等の水分の吸収および放出)による粘着剤層の寸法変化は抑制される傾向にある。これにより、粘着剤層とこれに隣接する層(光透過性部材、剥離ライナー、被着体等であり得る。)との寸法変化の不一致に起因する粘着型光学フィルムまたは該粘着型光学フィルムを含む光学積層体の反りを抑制することができる。粘着剤層中の水分量の変動を抑制し得ることは、粘着剤層の平坦性、透明性、屈折率等を一定に維持する観点からも好ましい。また、吸水率の低い粘着剤層は、水分を吸蔵しにくいため、例えば有機EL素子のように水分を嫌う要素を含む部材または製品に用いられる粘着型光学フィルムとして好適である。
(Water absorption rate)
In some aspects of the pressure-sensitive optical film disclosed herein, it is preferable that the pressure-sensitive adhesive layer constituting the pressure-sensitive optical film has a water absorption rate limited to a predetermined value or less. For example, it is preferable that the above-mentioned refractive index, total light transmittance and haze value are satisfied, and the water absorption rate is limited to a predetermined value or less. By limiting the water absorption rate of the pressure-sensitive adhesive layer, dimensional changes of the pressure-sensitive adhesive layer due to fluctuations in the amount of water in the pressure-sensitive adhesive layer (for example, absorption and release of water such as moisture in the environment) tend to be suppressed. be. As a result, the adhesive optical film or the adhesive optical film caused by the mismatch of the dimensional changes between the adhesive layer and the layer adjacent thereto (which may be a light transmitting member, a release liner, an adherend, etc.) It is possible to suppress the warp of the included optical laminate. It is preferable that the fluctuation of the water content in the pressure-sensitive adhesive layer can be suppressed from the viewpoint of maintaining the flatness, transparency, refractive index and the like of the pressure-sensitive adhesive layer constant. Further, since the pressure-sensitive adhesive layer having a low water absorption rate does not easily absorb water, it is suitable as an adhesive type optical film used for a member or product containing an element that dislikes water such as an organic EL element.
 いくつかの態様において、粘着剤層の吸水率は、凡そ1.0%以下であることが適当であり、0.7%以下であることが好ましく、0.5%以下(例えば0.5%未満)であることがより好ましく、0.4%以下でもよく、0.3%以下でもよく、0.2%以下でもよい。粘着剤層の吸水率の下限は特に制限されないが、粘着特性との両立等の実用上の観点から、例えば0.01%以上であってよく、0.05%以上でもよく、0.1%以上でもよく、0.15%以上でもよく、0.25%以上でもよい。第1粘着剤層および第2粘着剤層を有する両面粘着型光学フィルムの形態においては、少なくとも第1粘着剤層の吸水率が所定値以下に制限されていることが好ましい。より高い効果を得る観点から、第1、第2粘着剤層の吸水率がいずれも所定値以下に制限されていることがより好ましい。 In some embodiments, the water absorption of the pressure-sensitive adhesive layer is preferably about 1.0% or less, preferably 0.7% or less, and 0.5% or less (eg 0.5%). Less than), more preferably 0.4% or less, 0.3% or less, and 0.2% or less. The lower limit of the water absorption rate of the pressure-sensitive adhesive layer is not particularly limited, but from a practical point of view such as compatibility with the pressure-sensitive adhesive properties, for example, it may be 0.01% or more, 0.05% or more, or 0.1%. It may be more than or equal to, 0.15% or more, and 0.25% or more. In the form of the double-sided pressure-sensitive optical film having the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer, it is preferable that the water absorption rate of at least the first pressure-sensitive adhesive layer is limited to a predetermined value or less. From the viewpoint of obtaining a higher effect, it is more preferable that the water absorption rates of the first and second pressure-sensitive adhesive layers are all limited to a predetermined value or less.
 なお、粘着剤層の吸水率(水分率ともいう。)は、以下の方法により測定される。後述の実施例でも同様の方法が採用される。
  [水分率の測定]
 評価対象の粘着剤層を、その一方の面および他方の面上に配置された2枚の剥離ライナーとともに4cm×5cm(面積:20cm)のサイズに切り出し、一方の面上の剥離ライナーを除去して、あらかじめ秤量しておいたアルミニウム箔に貼り合わせる。次いで、粘着剤層の他方の面上の剥離ライナーを除去し、温度60℃、相対湿度90%の恒温恒湿槽に投入し、72時間後に取り出す。粘着剤層とアルミニウム箔とが積層された試験片を秤量した後、加熱気化装置(三菱化学アナリテック VA-200型)を備える水分計(三菱化学アナリテック CA-200型)を用い、カールフィッシャー電量滴定法により、以下の条件で水分率を測定する。 
  陽極液:アクアミクロンAKX(三菱化学製)
  陰極液:アクアミクロンCXU(三菱化学製)
  加熱気化温度:150℃
The water absorption rate (also referred to as water content) of the pressure-sensitive adhesive layer is measured by the following method. The same method is adopted in the examples described later.
[Measurement of moisture content]
The pressure-sensitive adhesive layer to be evaluated is cut into a size of 4 cm × 5 cm (area: 20 cm 2 ) together with two release liners arranged on one surface and the other surface, and the release liner on one surface is removed. Then, it is attached to the aluminum foil that has been weighed in advance. Next, the release liner on the other surface of the pressure-sensitive adhesive layer is removed, placed in a constant temperature and humidity chamber having a temperature of 60 ° C. and a relative humidity of 90%, and taken out after 72 hours. After weighing the test piece in which the pressure-sensitive adhesive layer and the aluminum foil are laminated, use a moisture meter (Mitsubishi Chemical Analytech CA-200 type) equipped with a heating vaporizer (Mitsubishi Chemical Analytech VA-200 type) to curl fisher. The water content is measured under the following conditions by the coulometric titration method.
Anode solution: Aquamicron AKX (manufactured by Mitsubishi Chemical Corporation)
Cathode solution: Aquamicron CXU (manufactured by Mitsubishi Chemical Corporation)
Heating vaporization temperature: 150 ° C
 (ゲル分率)
 粘着剤層のゲル分率は、使用目的や使用態様等に応じて適切に設定され、特定の範囲に限定されるものではない。上記ゲル分率は、例えば凡そ99%以下であり、凡そ97%以下が適当である。高屈折率と粘着特性とを好適に両立しやすくする観点から、いくつかの好ましい態様では、上記ゲル分率は凡そ95%以下、より好ましくは凡そ92%以下(例えば凡そ90%以下)であり得る。ゲル分率が高すぎないことは、被着体表面に存在し得る凹凸(例えば、発光装置において光取出し効率の向上等を目的として設けられた凹凸構造)に対して適切に追従し、良好に密着する観点からも好ましい。いくつかの態様において、ゲル分率は、凡そ88%以下であってもよく、凡そ75%以下でもよく、凡そ65%以下でもよい。また、粘着剤層のゲル分率は、粘着剤に適度な凝集性を付与し、粘着特性を適切に発現する観点から、例えば凡そ10%以上であり、凡そ20%以上とすることが適当であり、凡そ30%以上であってもよい。粘着剤層の耐変形性(圧力によるはみ出しや異物のかみ込みによる気泡の防止等)の観点から、上記ゲル分率は、好ましくは凡そ30%以上、より好ましくは凡そ40%以上であり、凡そ45%以上であってもよく、凡そ50%以上でもよく、凡そ65%以上でもよく、凡そ75%以上でもよい。ゲル分率は、ベースポリマーの分子量や分子構造、濃度、架橋度等により調節することができる。ゲル分率は下記の方法で測定される。
(Gel fraction)
The gel fraction of the pressure-sensitive adhesive layer is appropriately set according to the purpose of use, the mode of use, and the like, and is not limited to a specific range. The gel fraction is, for example, about 99% or less, and about 97% or less is appropriate. From the viewpoint of facilitating a good balance between high refractive index and adhesive properties, in some preferred embodiments, the gel fraction is about 95% or less, more preferably about 92% or less (for example, about 90% or less). obtain. The fact that the gel fraction is not too high appropriately follows the unevenness that may exist on the surface of the adherend (for example, the uneven structure provided for the purpose of improving the light extraction efficiency in the light emitting device), and satisfactorily follows. It is also preferable from the viewpoint of close contact. In some embodiments, the gel fraction may be approximately 88% or less, approximately 75% or less, or approximately 65% or less. Further, the gel fraction of the pressure-sensitive adhesive layer is, for example, about 10% or more, and preferably about 20% or more, from the viewpoint of imparting appropriate cohesiveness to the pressure-sensitive adhesive and appropriately expressing the pressure-sensitive adhesive properties. Yes, it may be about 30% or more. From the viewpoint of deformation resistance of the pressure-sensitive adhesive layer (prevention of air bubbles due to pressure squeeze out and foreign matter biting, etc.), the gel fraction is preferably about 30% or more, more preferably about 40% or more, and is about 40% or more. It may be 45% or more, about 50% or more, about 65% or more, or about 75% or more. The gel fraction can be adjusted by adjusting the molecular weight, molecular structure, concentration, degree of cross-linking, etc. of the base polymer. The gel fraction is measured by the following method.
  [ゲル分率の測定]
 所定量の粘着剤サンプル(重量Wg1)を平均孔径0.2μmの多孔質ポリテトラフルオロエチレン膜(重量Wg2)で巾着状に包み、口をタコ糸(重量Wg3)で縛る。上記多孔質ポリテトラフルオロエチレン(PTFE)膜としては、日東電工社から入手可能な商品名「ニトフロン(登録商標)NTF1122」(平均孔径0.2μm、気孔率75%、厚さ85μm)またはその相当品を使用する。
 この包みを十分量の酢酸エチルに浸し、室温(典型的には23℃)で7日間保持して粘着剤中のゾル分のみを上記膜外に溶出させた後、上記包みを取り出して外表面に付着している酢酸エチルを拭き取り、該包みを130℃で2時間乾燥させ、該包みの重量(Wg4)を測定する。粘着剤層のゲル分率は、各値を以下の式に代入することにより求められる。
    ゲル分率(%)=[(Wg4-Wg2-Wg3)/Wg1]×100
[Measurement of gel fraction]
A predetermined amount of the pressure-sensitive adhesive sample (weight Wg 1 ) is wrapped in a porous polytetrafluoroethylene film (weight Wg 2 ) having an average pore size of 0.2 μm in a purse-like shape, and the mouth is tied with an octopus thread (weight Wg 3 ). As the porous polytetrafluoroethylene (PTFE) film, the trade name "Nitoflon (registered trademark) NTF1122" (average pore diameter 0.2 μm, porosity 75%, thickness 85 μm) available from Nitto Denko Co., Ltd. or its equivalent Use the item.
After immersing this package in a sufficient amount of ethyl acetate and holding it at room temperature (typically 23 ° C.) for 7 days to elute only the sol component in the adhesive to the outside of the film, the package is taken out and the outer surface is removed. The ethyl acetate adhering to the package is wiped off, the package is dried at 130 ° C. for 2 hours, and the weight of the package (Wg 4 ) is measured. The gel fraction of the pressure-sensitive adhesive layer can be obtained by substituting each value into the following formula.
Gel fraction (%) = [(Wg 4- Wg 2- Wg 3 ) / Wg 1 ] x 100
 第1粘着面および第2粘着面を有する両面粘着型光学フィルムの形態において、上述したゲル分率は、少なくとも第1粘着面を構成する粘着剤層に適用され得、好ましくは第1粘着面を構成する粘着剤層および第2粘着面を構成する粘着剤層の両方に適用される。第1粘着面を構成する粘着剤層のゲル分率と第2粘着面を構成する粘着剤層のゲル分率とは、同程度であってもよく、異なっていてもよい。 In the form of a double-sided adhesive optical film having a first adhesive surface and a second adhesive surface, the gel fraction described above can be applied to at least the adhesive layer constituting the first adhesive surface, preferably the first adhesive surface. It is applied to both the constituent pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer constituting the second pressure-sensitive adhesive surface. The gel fraction of the pressure-sensitive adhesive layer constituting the first adhesive surface and the gel fraction of the pressure-sensitive adhesive layer constituting the second adhesive surface may be about the same or different.
 (貯蔵弾性率G’)
 ここに開示される粘着型光学フィルムにおいて、粘着剤層を構成する粘着剤の25℃における貯蔵弾性率G’(以下、「貯蔵弾性率G’(25)」ともいう。)は、使用目的や使用態様等に応じて適切に設定され、特定の範囲に限定されない。粘着剤の貯蔵弾性率G’(25)は、例えば凡そ700kPa以下であり得る。いくつかの態様において、被着体への貼付け容易性等の観点から、粘着剤の貯蔵弾性率G’(25)は、凡そ600kPa以下であることが有利であり、500kPa以下であることが好ましく、400kPa以下(例えば350kPa以下)であることがより好ましい。いくつかの態様において、室温域(例えば25℃)における粘着剤の柔軟性を高めて被着体に密着させやすくする観点から、粘着剤の貯蔵弾性率G’(25)は、凡そ330kPa以下であることが有利であり、300kPa以下であることが好ましい。室温域での貼付け性や柔軟性がより重視されるいくつかの態様において、粘着剤の貯蔵弾性率G’(25)は、例えば270kPa未満または250kPa未満であってよく、200kPa未満であることが有利であり、180kPa未満であることが好ましく、160kPa未満(例えば140kPa未満)であることがより好ましい。いくつかの態様において、粘着剤の貯蔵弾性率G’(25)は、100kPa未満であってもよく、90kPa未満であってもよい。粘着剤の貯蔵弾性率G’(25)の下限は特に制限されないが、加工性や取扱い性等の観点から、例えば30kPa以上であってよく、50kPa以上でもよく、70kPa以上でもよい。いくつかの態様において、高屈折率化を考慮して、貯蔵弾性率G’(25)は、100kPa以上でもよく、150kPa以上でもよく、200kPa以上でもよく、250kPa以上でもよく、300kPa以上でもよい。
(Storage modulus G')
In the pressure-sensitive optical film disclosed herein, the storage elastic modulus G'(hereinafter, also referred to as" storage elastic modulus G'(25) ") of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer at 25 ° C. It is appropriately set according to the usage mode and the like, and is not limited to a specific range. The storage elastic modulus G'(25) of the pressure-sensitive adhesive can be, for example, about 700 kPa or less. In some embodiments, the storage elastic modulus G'(25) of the pressure-sensitive adhesive is preferably about 600 kPa or less, preferably 500 kPa or less, from the viewpoint of ease of attachment to the adherend. , 400 kPa or less (for example, 350 kPa or less) is more preferable. In some embodiments, the storage elastic modulus G'(25) of the pressure-sensitive adhesive is approximately 330 kPa or less, from the viewpoint of increasing the flexibility of the pressure-sensitive adhesive in the room temperature range (for example, 25 ° C.) and facilitating adhesion to the adherend. It is advantageous to have it, and it is preferably 300 kPa or less. In some embodiments where stickability and flexibility at room temperature are more important, the storage elastic modulus G'(25) of the pressure-sensitive adhesive may be, for example, less than 270 kPa or less than 250 kPa, and may be less than 200 kPa. It is advantageous, preferably less than 180 kPa, more preferably less than 160 kPa (eg, less than 140 kPa). In some embodiments, the storage modulus G'(25) of the pressure-sensitive adhesive may be less than 100 kPa or less than 90 kPa. The lower limit of the storage elastic modulus G'(25) of the pressure-sensitive adhesive is not particularly limited, but may be, for example, 30 kPa or more, 50 kPa or more, or 70 kPa or more from the viewpoint of workability and handleability. In some embodiments, the storage elastic modulus G'(25) may be 100 kPa or higher, 150 kPa or higher, 200 kPa or higher, 250 kPa or higher, or 300 kPa or higher, in consideration of increasing the refractive index.
 ここに開示される粘着型光学フィルムにおいて、粘着剤層を構成する粘着剤の50℃における貯蔵弾性率G’(以下、「貯蔵弾性率G’(50)」ともいう。)は、特に限定されず、例えば100kPa未満であり得る。いくつかの態様において、貯蔵弾性率G’(50)は、60kPa未満であることが適当であり、40kPa未満であることが好ましく、38kPa未満(例えば36kPa未満)であることがより好ましい。このように貯蔵弾性率G’(50)が制限された粘着剤は、必要に応じて適度な加熱を行うことにより被着体への密着性を容易に高めることができ、これにより被着体への接着性を向上させ得る。粘着剤の貯蔵弾性率G’(50)の下限は特に制限されない。いくつかの態様において、粘着剤の耐熱特性の観点から、貯蔵弾性率G’(50)は、例えば10kPa以上であってよく、15kPa以上でもよく、20kPa以上でもよく、23kPa以上でもよい。 In the pressure-sensitive optical film disclosed herein, the storage elastic modulus G'(hereinafter, also referred to as "storage elastic modulus G'(50)") of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer at 50 ° C. is particularly limited. However, it can be less than 100 kPa, for example. In some embodiments, the storage modulus G'(50) is preferably less than 60 kPa, preferably less than 40 kPa, more preferably less than 38 kPa (eg, less than 36 kPa). As described above, the adhesive having a limited storage elastic modulus G'(50) can easily improve the adhesion to the adherend by appropriately heating it as necessary, whereby the adherend can be adhered to the adherend. It can improve the adhesiveness to. The lower limit of the storage elastic modulus G'(50) of the pressure-sensitive adhesive is not particularly limited. In some embodiments, the storage elastic modulus G'(50) may be, for example, 10 kPa or higher, 15 kPa or higher, 20 kPa or higher, or 23 kPa or higher, from the viewpoint of the heat resistant properties of the pressure-sensitive adhesive.
 ここに開示される粘着型光学フィルムのいくつかの態様において、粘着剤層を構成する粘着剤は、以下の条件:
 (a)25℃における貯蔵弾性率G’(25)が350kPa以下(好ましくは200kPa未満、例えば180kPa以下)である;および
 (b)50℃における貯蔵弾性率G’(50)が60kPa未満(好ましくは50kPa未満、より好ましくは40kPa未満、例えば38kPa未満)である;
の少なくとも一方を満たすことが好ましい。少なくとも上記条件(a)を満たす粘着剤は、室温域(例えば25℃)における被着体への密着性の観点から好ましい。少なくとも上記条件(b)を満たす粘着剤は、室温より少し高い程度の温度に加熱することで被着体への密着性(接着性)を容易に向上させ得るので好ましい。上記条件(a)を満たさずかつ上記(b)を満たす粘着剤は、室温域での貼付けの初期にはリワーク性(貼直し性)がよく、室温より少し高い程度への温度への加熱により被着体からの剥離強度を効果的に上昇させることのできる、熱活性化タイプの粘着剤として利用され得る。上記熱活性化は、被着体への貼付けに際して粘着剤を室温より少し高い程度の温度に加熱することにより行ってもよい。上記室温より少し高い程度の温度とは、例えば60℃程度またはそれ以下であり、好ましくは55℃程度またはそれ以下(例えば、50℃程度またはそれ以下)である。
In some aspects of the pressure-sensitive optical film disclosed herein, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer has the following conditions:
(A) The storage elastic modulus G'(25) at 25 ° C. is 350 kPa or less (preferably less than 200 kPa, for example 180 kPa or less); and (b) the storage elastic modulus G'(50) at 50 ° C. is less than 60 kPa (preferably less than 60 kPa). Is less than 50 kPa, more preferably less than 40 kPa, eg less than 38 kPa);
It is preferable to satisfy at least one of the above. A pressure-sensitive adhesive that satisfies at least the above condition (a) is preferable from the viewpoint of adhesion to an adherend in a room temperature range (for example, 25 ° C.). A pressure-sensitive adhesive that satisfies at least the above condition (b) is preferable because the adhesion (adhesiveness) to the adherend can be easily improved by heating to a temperature slightly higher than room temperature. The adhesive that does not satisfy the above condition (a) and satisfies the above (b) has good reworkability (reapplyability) at the initial stage of application in the room temperature range, and is heated to a temperature slightly higher than room temperature. It can be used as a heat-activated adhesive that can effectively increase the peel strength from the adherend. The thermal activation may be performed by heating the pressure-sensitive adhesive to a temperature slightly higher than room temperature when it is attached to the adherend. The temperature slightly higher than the room temperature is, for example, about 60 ° C. or lower, preferably about 55 ° C. or lower (for example, about 50 ° C. or lower).
 ここに開示される粘着型光学フィルムのいくつかの態様において、粘着剤層を構成する粘着剤の貯蔵弾性率G’(25)[kPa]に対する貯蔵弾性率G’(50)[kPa]の比、すなわち貯蔵弾性率比G’(50)/G’(25)は、例えば70%以下であり、40%以下でもよく、30%以下でもよく、20%以下でもよい。G’(50)/G’(25)が小さい粘着剤は、上記熱活性化タイプの粘着剤としての使用に適している。G’(50)/G’(25)の下限は特に制限されない。G’(50)/G’(25)は、例えば5%以上であり、粘着剤の耐熱特性の観点から10%以上であることが好ましく、12%以上でもよく、15%以上でもよい。 In some aspects of the pressure-sensitive optical film disclosed herein, the ratio of the storage elastic modulus G'(50) [kPa] to the storage elastic modulus G'(25) [kPa] of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer. That is, the storage elastic modulus ratio G'(50) / G'(25) is, for example, 70% or less, 40% or less, 30% or less, or 20% or less. A pressure-sensitive adhesive having a small G'(50) / G'(25) is suitable for use as the above-mentioned heat-activated type pressure-sensitive adhesive. The lower limit of G'(50) / G'(25) is not particularly limited. G'(50) / G'(25) is, for example, 5% or more, preferably 10% or more from the viewpoint of heat resistance characteristics of the pressure-sensitive adhesive, and may be 12% or more, or 15% or more.
 貯蔵弾性率G’(25)およびG’(50)は、動的粘弾性測定により求めることができ、その結果からG’(50)/G’(25)を算出することができる。動的粘弾性測定は、市販の動的粘弾性測定装置を用いて常法により行うことができ、例えばTA Instruments社製の「Advanced Rheometric Expansion System (ARES)」またはその相当品を使用して、以下の測定条件で行うことができる。測定用のサンプルとしては、評価対象の粘着剤層を必要に応じて積層する等して厚さ約1.5mmに調製したものを用いる。
  [測定条件]
 変形モード:ねじり
 測定周波数:1Hz
 昇温速度:5℃/分
 形状:パラレルプレート 7.9mmφ
The storage elastic moduli G'(25) and G'(50) can be obtained by dynamic viscoelasticity measurement, and G'(50) / G'(25) can be calculated from the results. Dynamic viscoelasticity measurement can be performed by a conventional method using a commercially available dynamic viscoelasticity measuring device, for example, using "Advanced Rheometric Expansion System (ARES)" manufactured by TA Instruments or an equivalent product thereof. It can be performed under the following measurement conditions. As the sample for measurement, a sample prepared to have a thickness of about 1.5 mm by laminating the pressure-sensitive adhesive layer to be evaluated as necessary is used.
[Measurement condition]
Deformation mode: Torsion measurement frequency: 1Hz
Temperature rise rate: 5 ° C / min Shape: Parallel plate 7.9 mmφ
 粘着剤層の貯蔵弾性率G’(25)、G’(50)および貯蔵弾性率比は、粘着剤のベースポリマーを構成するモノマー成分の組成の選択(例えば、モノマー(m1)の種類および含有量の選択)、架橋剤の使用有無、種類および使用量の選択、後述する屈折率向上剤や可塑化材料の使用有無、種類および使用量の選択、等により調節し得る。例えば、モノマー(m1)として、該モノマー(m1)の主成分である第1のモノマーに加えて、該第1のモノマーとは化学構造の異なる第2のモノマーを比較的少量、上記第1のモノマーと組み合わせて使用することにより、モノマー(m1)として第1のモノマーを単独で用いる場合に加えてG’(50)を小さくし、G’(50)/G’(25)を低下させ得る。 The storage modulus G'(25), G'(50) and storage modulus ratio of the pressure-sensitive adhesive layer are selected from the composition of the monomer components constituting the base polymer of the pressure-sensitive adhesive (for example, the type and content of the monomer (m1)). It can be adjusted by selecting the amount), the presence / absence of the cross-linking agent, the selection of the type and the amount used, the presence / absence of the refractive modulus improver and the thermoplastic material described later, the selection of the type and the amount used, and the like. For example, as the monomer (m1), in addition to the first monomer which is the main component of the monomer (m1), a relatively small amount of a second monomer having a chemical structure different from that of the first monomer is used in the first monomer. When used in combination with a monomer, G'(50) can be reduced and G'(50) / G'(25) can be lowered in addition to the case where the first monomer is used alone as the monomer (m1). ..
 第1粘着面および第2粘着面を有する両面粘着型光学フィルムの形態において、上述した貯蔵弾性率G’(25)、G’(50)および貯蔵弾性率比は、少なくとも第1粘着面を構成する粘着剤層に適用され、好ましくは第1粘着面を構成する粘着剤層および第2粘着面を構成する粘着剤層の両方に適用される。第1粘着面を構成する粘着剤層の貯蔵弾性率G’と第2粘着面を構成する粘着剤層の貯蔵弾性率G’とは、同程度であってもよく、異なっていてもよい。 In the form of a double-sided adhesive optical film having a first adhesive surface and a second adhesive surface, the above-mentioned storage elasticity G'(25), G'(50) and storage elasticity ratio constitute at least the first adhesive surface. It is applied to the pressure-sensitive adhesive layer, preferably applied to both the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive surface and the pressure-sensitive adhesive layer constituting the second pressure-sensitive adhesive surface. The storage elastic modulus G'of the pressure-sensitive adhesive layer constituting the first adhesive surface and the storage elastic modulus G'of the pressure-sensitive adhesive layer forming the second adhesive surface may be about the same or different.
 ここに開示される技術のいくつかの態様において、粘着剤層を構成する粘着剤のtanδのピーク温度は、凡そ-50℃以上であることが好ましく、また、凡そ50℃以下であることが好ましい。ここで、粘着剤のtanδ(損失正接)とは、該粘着剤の貯蔵弾性率G’に対する損失弾性率G”の比をいう。すなわち、tanδ=G”/G’である。粘着剤のtanδは、厚さ約2mm、直径7.9mmの円盤状の粘着剤サンプルをパラレルプレートで挟み込み、粘弾性試験装置を用いて周波数1Hzのせん断歪みを与えながら、測定温度範囲-60℃~60℃、昇温速度5℃/分の条件で、せん断モードにより該粘着剤の温度分散試験を行い、その際の貯蔵弾性率G’(Pa)および損失弾性率G”(Pa)から次式:tanδ=G”/G’;により求められる。上記温度範囲におけるtanδの推移から、粘着剤のtanδのピーク温度(以下、Tpeakと表記することがある。)が求められる。粘弾性試験装置としては、TA Instruments社製のARESまたはその相当品を用いることができる。 In some aspects of the techniques disclosed herein, the peak temperature of the tan δ of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is preferably about −50 ° C. or higher, and more preferably about 50 ° C. or lower. .. Here, the tan δ (tangent loss) of the pressure-sensitive adhesive means the ratio of the loss elastic modulus G'to the storage elastic modulus G'of the pressure-sensitive adhesive, that is, tan δ = G'/ G'. The pressure-sensitive adhesive tan δ has a measurement temperature range of -60 ° C while sandwiching a disk-shaped pressure-sensitive adhesive sample with a thickness of about 2 mm and a diameter of 7.9 mm between parallel plates and applying shear strain at a frequency of 1 Hz using a viscoelasticity tester. A temperature dispersion test of the pressure-sensitive adhesive was carried out in a shear mode under the conditions of ~ 60 ° C. and a heating rate of 5 ° C./min. It is calculated by the formula: tan δ = G "/ G';. From the transition of tan δ in the above temperature range, the peak temperature of tan δ of the pressure-sensitive adhesive (hereinafter, may be referred to as Tpeak) can be obtained. As the viscoelasticity test apparatus, ARES manufactured by TA Instruments or an equivalent product thereof can be used.
 いくつかの態様において、粘着剤のTpeakは、45℃以下または35℃以下であることが有利であり、30℃以下(例えば25℃以下)であることが好ましく、20℃以下でもよく、15℃以下でもよい。よりTpeakの低い粘着剤によると、室温域において良好な初期接着性や密着性が得られやすくなる傾向にある。一方、粘着剤のTpeakが低すぎないことは、粘着剤に適度な凝集性を付与する観点から好ましく、高屈折率化との両立にも適する傾向にある。かかる観点から、いくつかの態様において、粘着剤のTpeakは、例えば-40℃以上であってよく、-30℃以上でもよく、-20℃以上でもよく、-5℃以上でもよく、5℃以上でもよく、15℃以上でもよく、さらには25℃以上でもよい。Tpeakが比較的高い粘着剤は、被着体への貼付けに際し、必要に応じて粘着剤と被着体の一方または両方を室温より少し高い程度の温度に加熱する態様で好ましく用いられ得る。粘着剤のTpeakは、該粘着剤の組成の選択(例えば、ベースポリマーを構成するモノマー成分の組成、屈折率向上剤や可塑化材料の使用有無、種類および使用量の選択)等により調節し得る。
 第1粘着面および第2粘着面を有する両面粘着型光学フィルムの形態において、上述した粘着剤のTpeakは、少なくとも第1粘着面を構成する粘着剤層に適用されることが好ましく、より好ましくは第1粘着面を構成する粘着剤層および第2粘着面を構成する粘着剤層の両方に適用される。第1粘着面を構成する粘着剤層のTpeakと第2粘着面を構成する粘着剤層のTpeakとは、同程度であってもよく、異なっていてもよい。
In some embodiments, the Tpeak of the pressure-sensitive adhesive is preferably 45 ° C. or lower or 35 ° C. or lower, preferably 30 ° C. or lower (for example, 25 ° C. or lower), 20 ° C. or lower, and 15 ° C. or lower. It may be as follows. Adhesives with a lower Tpeak tend to provide good initial adhesiveness and adhesion in the room temperature range. On the other hand, it is preferable that the Tpeak of the pressure-sensitive adhesive is not too low from the viewpoint of imparting appropriate cohesiveness to the pressure-sensitive adhesive, and it tends to be suitable for both high refractive index and high refractive index. From this point of view, in some embodiments, the Tpeak of the pressure-sensitive adhesive may be, for example, −40 ° C. or higher, −30 ° C. or higher, −20 ° C. or higher, −5 ° C. or higher, 5 ° C. or higher. However, it may be 15 ° C. or higher, and further may be 25 ° C. or higher. A pressure-sensitive adhesive having a relatively high Tpeak can be preferably used in an embodiment in which one or both of the pressure-sensitive adhesive and the adherend are heated to a temperature slightly higher than room temperature, if necessary, when the pressure-sensitive adhesive is attached to the adherend. The Tpeak of the pressure-sensitive adhesive can be adjusted by selecting the composition of the pressure-sensitive adhesive (for example, the composition of the monomer components constituting the base polymer, the presence or absence of a refractive index improver or a thermoplastic material, the type and the amount used), and the like. ..
In the form of a double-sided adhesive optical film having a first adhesive surface and a second adhesive surface, the Tpeak of the above-mentioned adhesive is preferably applied to at least the adhesive layer constituting the first adhesive surface, and more preferably. It is applied to both the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive surface and the pressure-sensitive adhesive layer constituting the second pressure-sensitive adhesive surface. The Tpeak of the pressure-sensitive adhesive layer forming the first adhesive surface and the Tpeak of the pressure-sensitive adhesive layer forming the second adhesive surface may be the same or different.
<粘着剤層>
 (ベースポリマー)
 ここに開示される技術において、粘着剤層を構成する粘着剤の種類は特に限定されない。上記粘着剤は、粘着剤の分野において用いられ得るアクリル系ポリマー、ゴム系ポリマー(例えば天然ゴム、合成ゴム、これらの混合物等)、ポリエステル系ポリマー、ウレタン系ポリマー、ポリエーテル系ポリマー、シリコーン系ポリマー、ポリアミド系ポリマー、フッ素系ポリマー等の各種ゴム状ポリマーの1種または2種以上を粘着性ポリマー(粘着剤を形づくる構造ポリマーという意味で、以下「ベースポリマー」ともいう。)として含むものであり得る。粘着性能やコスト等の観点から、アクリル系ポリマーまたはゴム系ポリマーをベースポリマーとして含む粘着剤を好ましく採用し得る。なかでもアクリル系ポリマーをベースポリマーとする粘着剤(アクリル系粘着剤)が好ましい。ここに開示される技術は、アクリル系粘着剤を用いる態様で好ましく実施される。
<Adhesive layer>
(Base polymer)
In the technique disclosed herein, the type of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited. The pressure-sensitive adhesive may be an acrylic polymer, a rubber-based polymer (for example, natural rubber, synthetic rubber, a mixture thereof, etc.), a polyester-based polymer, a urethane-based polymer, a polyether polymer, or a silicone-based polymer that can be used in the field of pressure-sensitive adhesives. , One or more of various rubber-like polymers such as polyamide polymers and fluoropolymers are included as adhesive polymers (hereinafter, also referred to as "base polymers" in the sense of structural polymers forming adhesives). obtain. From the viewpoint of adhesive performance, cost, and the like, a pressure-sensitive adhesive containing an acrylic polymer or a rubber-based polymer as a base polymer can be preferably adopted. Of these, a pressure-sensitive adhesive (acrylic pressure-sensitive adhesive) using an acrylic polymer as a base polymer is preferable. The technique disclosed herein is preferably carried out in an embodiment using an acrylic pressure-sensitive adhesive.
 以下、アクリル系粘着剤により構成された粘着剤層、すなわちアクリル系粘着剤層を有する粘着型光学フィルムについて主に説明するが、ここに開示される粘着型光学フィルムの粘着剤層をアクリル系粘着剤により構成されたものに限定する意図ではない。 Hereinafter, a pressure-sensitive adhesive layer composed of an acrylic pressure-sensitive adhesive, that is, a pressure-sensitive adhesive film having an acrylic-based pressure-sensitive adhesive layer will be mainly described. It is not intended to be limited to those composed of agents.
 なお、この明細書において、粘着剤の「ベースポリマー」とは、該粘着剤に含まれるゴム状ポリマーの主成分をいい、このこと以外、何ら限定的に解釈されるものではない。上記ゴム状ポリマーとは、室温付近の温度域においてゴム弾性を示すポリマーをいう。また、この明細書において「主成分」とは、特記しない場合、50重量%を超えて含まれる成分を指す。
 また、この明細書において「アクリル系ポリマー」とは、該ポリマーを構成するモノマー単位として、1分子中に少なくとも1つの(メタ)アクリロイル基を有するモノマーに由来するモノマー単位を含む重合物をいう。以下、1分子中に少なくとも1つの(メタ)アクリロイル基を有するモノマーを「アクリル系モノマー」ともいう。したがって、この明細書におけるアクリル系ポリマーは、アクリル系モノマーに由来するモノマー単位を含むポリマーとして定義される。アクリル系ポリマーの典型例として、該アクリル系ポリマーの合成に用いられる全モノマーのうちアクリル系モノマーの割合が50重量%超(好ましくは70重量%超、例えば90重量%超)であるポリマーが挙げられる。
 また、この明細書において「(メタ)アクリロイル」とは、アクリロイルおよびメタクリロイルを包括的に指す意味である。同様に、「(メタ)アクリレート」とはアクリレートおよびメタクリレートを、「(メタ)アクリル」とはアクリルおよびメタクリルを、それぞれ包括的に指す意味である。したがって、ここでいうアクリル系モノマーの概念には、アクリロイル基を有するモノマー(アクリル系モノマー)とメタクリロイル基を有するモノマー(メタクリル系モノマー)との両方が包含され得る。
In this specification, the "base polymer" of the pressure-sensitive adhesive refers to the main component of the rubber-like polymer contained in the pressure-sensitive adhesive, and is not interpreted in any limitation other than this. The rubber-like polymer refers to a polymer that exhibits rubber elasticity in a temperature range near room temperature. Further, in this specification, the “main component” refers to a component contained in an amount of more than 50% by weight unless otherwise specified.
Further, in the present specification, the "acrylic polymer" refers to a polymer containing a monomer unit derived from a monomer having at least one (meth) acryloyl group in one molecule as a monomer unit constituting the polymer. Hereinafter, a monomer having at least one (meth) acryloyl group in one molecule is also referred to as an “acrylic monomer”. Therefore, the acrylic polymer in this specification is defined as a polymer containing a monomer unit derived from an acrylic monomer. A typical example of the acrylic polymer is a polymer in which the proportion of the acrylic monomer in the total monomers used in the synthesis of the acrylic polymer is more than 50% by weight (preferably more than 70% by weight, for example, more than 90% by weight). Be done.
Further, in this specification, "(meth) acryloyl" means a comprehensive reference to acryloyl and methacryloyl. Similarly, "(meth) acrylate" means acrylate and methacrylate, and "(meth) acrylic" means acrylic and methacrylic, respectively. Therefore, the concept of the acrylic monomer here may include both a monomer having an acryloyl group (acrylic monomer) and a monomer having a methacryloyl group (methacryl monomer).
 (アクリル系ポリマー(A))
 ここに開示される粘着型光学フィルムは、屈折率が1.570超であり、全光線透過率が86%以上であり、かつヘイズ値が3.0%以下(好ましくは2.0%以下、より好ましくは1.0%以下)であるアクリル系粘着剤層を含む態様で好ましく実施し得る。上記アクリル系粘着剤層のベースポリマーであるアクリル系ポリマーとしては、該アクリル系ポリマーを構成するモノマー成分として芳香環含有モノマー(m1)を含むものが好ましい。すなわち、芳香環含有モノマー(m1)をモノマー単位として含むアクリル系ポリマーが好ましい。以下、かかるアクリル系ポリマーを「アクリル系ポリマー(A)」ともいう。ここで、本明細書において「アクリル系ポリマーを構成するモノマー成分」とは、あらかじめ形成された重合物(オリゴマーであり得る。)の形態で粘着剤組成物に含まれるか、未重合のモノマーの形態で粘着剤組成物に含まれるかを問わず、該粘着剤組成物から形成される粘着剤中においてアクリル系ポリマーの繰返し単位を構成するモノマーを意味する。すなわち、アクリル系ポリマーを構成するモノマー成分は、重合物、未重合物、部分重合物のいずれの形態で上記粘着剤組成物に含まれていてもよい。粘着剤組成物の調製容易性等の観点から、いくつかの態様において、モノマー成分の実質的に全部(例えば95重量%以上、好ましくは99重量%以上)を重合物の形態で含む粘着剤組成物が好ましい。モノマー成分の実質的に全部を重合物の形態で含む粘着剤組成物は、歪みや反りの少ない粘着型光学フィルムを形成しやすいという観点からも好ましい。
(Acrylic polymer (A))
The adhesive optical film disclosed herein has a refractive index of more than 1.570, a total light transmittance of 86% or more, and a haze value of 3.0% or less (preferably 2.0% or less, More preferably, it can be carried out in an embodiment including an acrylic pressure-sensitive adhesive layer (1.0% or less). As the acrylic polymer that is the base polymer of the acrylic pressure-sensitive adhesive layer, those containing an aromatic ring-containing monomer (m1) as a monomer component constituting the acrylic polymer are preferable. That is, an acrylic polymer containing an aromatic ring-containing monomer (m1) as a monomer unit is preferable. Hereinafter, such an acrylic polymer is also referred to as an "acrylic polymer (A)". Here, in the present specification, the "monomer component constituting the acrylic polymer" is a monomer contained in the pressure-sensitive adhesive composition in the form of a preformed polymer (which may be an oligomer) or a non-polymerized monomer. Regardless of whether it is contained in the pressure-sensitive adhesive composition in its form, it means a monomer constituting a repeating unit of an acrylic polymer in a pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition. That is, the monomer component constituting the acrylic polymer may be contained in the pressure-sensitive adhesive composition in any form of a polymer, a non-polymer, or a partial polymer. From the viewpoint of ease of preparation of the pressure-sensitive adhesive composition, in some embodiments, a pressure-sensitive adhesive composition containing substantially all of the monomer components (for example, 95% by weight or more, preferably 99% by weight or more) in the form of a polymer. The thing is preferable. A pressure-sensitive adhesive composition containing substantially all of the monomer components in the form of a polymer is preferable from the viewpoint of easily forming a pressure-sensitive optical film with less distortion and warpage.
 (モノマー(m1))
 モノマー(m1)としては、1分子中に少なくとも1つの芳香環と少なくとも1つのエチレン性不飽和基とを含む化合物が用いられる。モノマー(m1)としては、かかる化合物の1種を単独でまたは2種以上を組み合わせて用いることができる。
(Monomer (m1))
As the monomer (m1), a compound containing at least one aromatic ring and at least one ethylenically unsaturated group in one molecule is used. As the monomer (m1), one of the compounds may be used alone or in combination of two or more.
 上記エチレン性不飽和基の例としては、(メタ)アクリロイル基、ビニル基、(メタ)アリル基等が挙げられる。重合反応性の観点から(メタ)アクリロイル基が好ましく、柔軟性や粘着性の観点からアクリロイル基がより好ましい。粘着剤の柔軟性低下を抑制する観点から、モノマー(m1)としては、1分子中に含まれるエチレン性不飽和基の数が1である化合物(すなわち、単官能モノマー)が好ましく用いられる。 Examples of the ethylenically unsaturated group include (meth) acryloyl group, vinyl group, (meth) allyl group and the like. A (meth) acryloyl group is preferable from the viewpoint of polymerization reactivity, and an acryloyl group is more preferable from the viewpoint of flexibility and adhesiveness. From the viewpoint of suppressing a decrease in the flexibility of the pressure-sensitive adhesive, a compound (that is, a monofunctional monomer) in which the number of ethylenically unsaturated groups contained in one molecule is 1 is preferably used as the monomer (m1).
 モノマー(m1)として用いられる化合物1分子に含まれる芳香環の数は、1でもよく、2以上でもよい。モノマー(m1)に含まれる芳香環の数の上限は特に制限されず、例えば16以下であり得る。いくつかの態様において、アクリル系ポリマー(A)の調製容易性や粘着剤の透明性の観点から、上記芳香環の数は、例えば12以下であってよく、8以下であることが好ましく、6以下であることがより好ましく、5以下でもよく、4以下でもよく、3以下でもよく、2以下でもよい。 The number of aromatic rings contained in one molecule of the compound used as the monomer (m1) may be 1 or 2 or more. The upper limit of the number of aromatic rings contained in the monomer (m1) is not particularly limited, and may be 16 or less, for example. In some embodiments, the number of aromatic rings may be, for example, 12 or less, preferably 8 or less, from the viewpoint of ease of preparation of the acrylic polymer (A) and transparency of the pressure-sensitive adhesive. More preferably, it may be 5 or less, 4 or less, 3 or less, or 2 or less.
 モノマー(m1)として用いられる化合物の有する芳香環は、例えばベンゼン環(ビフェニル構造やフルオレン構造の一部を構成するベンゼン環であり得る。);ナフタレン環、インデン環、アズレン環、アントラセン環、フェナントレン環の縮合環;等の炭素環であってもよく、例えばピリジン環、ピリミジン環、ピリダジン環、ピラジン環、トリアジン環、ピロール環、ピラゾール環、イミダゾール環、トリアゾール環、オキサゾール環、イソオキサゾール環、チアゾール環、チオフェン環;等の複素環であってもよい。上記複素環において環構成原子として含まれるヘテロ原子は、例えば窒素、硫黄および酸素からなる群から選択される1または2以上であり得る。いくつかの態様において、上記複素環を構成するヘテロ原子は、窒素および硫黄の一方または両方であり得る。モノマー(m1)は、例えばジナフトチオフェン構造のように、1または2以上の炭素環と1または2以上の複素環とが縮合した構造を有していてもよい。 The aromatic ring of the compound used as the monomer (m1) is, for example, a benzene ring (which may be a benzene ring forming a part of a biphenyl structure or a fluorene structure); a naphthalene ring, an inden ring, an azulene ring, an anthracene ring, and a phenanthrene. It may be a carbon ring such as a fused ring of a ring; for example, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, an isooxazole ring, and the like. It may be a heterocycle such as a thiazole ring or a thiophene ring. The heteroatom contained as a ring-constituting atom in the heterocycle may be one or more selected from the group consisting of, for example, nitrogen, sulfur and oxygen. In some embodiments, the heteroatom constituting the heterocycle can be one or both of nitrogen and sulfur. The monomer (m1) may have a structure in which one or more carbon rings and one or more heterocycles are condensed, for example, a dinaphthothiophene structure.
 上記芳香環(好ましくは炭素環)は、環構成原子上に1または2以上の置換基を有していてもよく、置換基を有していなくてもよい。置換基を有する場合、該置換基としては、アルキル基、アルコキシ基、アリールオキシ基、水酸基、ハロゲン原子(フッ素原子、塩素原子、臭素原子等)、ヒドロキシアルキル基、ヒドロキシアルキルオキシ基、グリシジルオキシ基等が例示されるが、これらに限定されない。炭素原子を含む置換基において、該置換基に含まれる炭素原子の数は、好ましくは1~4であり、より好ましくは1~3であり、例えば1または2であり得る。いくつかの態様において、上記芳香環は、環構成原子上に置換基を有しないか、アルキル基、アルコキシ基およびハロゲン原子(例えば臭素原子)からなる群から選択される1または2以上の置換基を有する芳香環であり得る。なお、モノマー(m1)の有する芳香環がその環構成原子上に置換基を有するとは、該芳香環が、エチレン性不飽和基を有する置換基以外の置換基を有することをいう。 The aromatic ring (preferably a carbon ring) may have one or more substituents on the ring-constituting atom, and may not have a substituent. When it has a substituent, the substituent includes an alkyl group, an alkoxy group, an aryloxy group, a hydroxyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydroxyalkyl group, a hydroxyalkyloxy group, and a glycidyloxy group. Etc., but are not limited thereto. In the substituent containing a carbon atom, the number of carbon atoms contained in the substituent is preferably 1 to 4, more preferably 1 to 3, and may be, for example, 1 or 2. In some embodiments, the aromatic ring has one or more substituents that do not have a substituent on the ring-constituting atom or are selected from the group consisting of an alkyl group, an alkoxy group and a halogen atom (eg, a bromine atom). It can be an aromatic ring having. The fact that the aromatic ring of the monomer (m1) has a substituent on its ring-constituting atom means that the aromatic ring has a substituent other than the substituent having an ethylenically unsaturated group.
 芳香環とエチレン性不飽和基とは、直接結合していてもよく、リンキング基を介して結合していてもよい。上記リンキング基は、例えば、アルキレン基、オキシアルキレン基、ポリ(オキシアルキレン)基、フェニル基、アルキルフェニル基、アルコキシフェニル基、これらの基において1または2以上の水素原子が水酸基で置換された構造の基(例えば、ヒドロキシアルキレン基)、オキシ基(-O-基)、チオオキシ基(-S-基)、等から選択される1または2以上の構造を含む基であり得る。いくつかの態様において、芳香環とエチレン性不飽和基とが、直接結合しているか、またはアルキレン基、オキシアルキレン基およびポリ(オキシアルキレン)基からなる群から選択されるリンキング基を介して結合している構造の芳香環含有モノマーを好ましく採用し得る。上記アルキレン基および上記オキシアルキレン基における炭素原子数は、好ましくは1~4であり、より好ましくは1~3であり、例えば1または2であり得る。上記ポリ(オキシアルキレン)基におけるオキシアルキレン単位の繰り返し数は、例えば2~3であり得る。 The aromatic ring and the ethylenically unsaturated group may be directly bonded or may be bonded via a linking group. The linking group is, for example, an alkylene group, an oxyalkylene group, a poly (oxyalkylene) group, a phenyl group, an alkylphenyl group, an alkoxyphenyl group, and a structure in which one or more hydrogen atoms are substituted with hydroxyl groups in these groups. It can be a group containing one or more structures selected from the group (eg, hydroxyalkylene group), oxy group (—O— group), thiooxy group (—S— group), and the like. In some embodiments, the aromatic ring and the ethylenically unsaturated group are directly bonded or bonded via a linking group selected from the group consisting of alkylene groups, oxyalkylene groups and poly (oxyalkylene) groups. An aromatic ring-containing monomer having a structure having a structure can be preferably adopted. The number of carbon atoms in the alkylene group and the oxyalkylene group is preferably 1 to 4, more preferably 1 to 3, and may be, for example, 1 or 2. The number of repetitions of the oxyalkylene unit in the poly (oxyalkylene) group can be, for example, 2 to 3.
 モノマー(m1)として好ましく採用し得る化合物の例として、芳香環含有(メタ)アクリレートおよび芳香環含有ビニル化合物が挙げられる。芳香環含有(メタ)アクリレートおよび芳香環含有ビニル化合物は、それぞれ、1種を単独でまたは2種以上を組み合わせて用いることができる。1種または2種以上の芳香環含有(メタ)アクリレートと、1種または2種以上の芳香環含有ビニル化合物とを組み合わせて用いてもよい。 Examples of compounds that can be preferably used as the monomer (m1) include aromatic ring-containing (meth) acrylates and aromatic ring-containing vinyl compounds. The aromatic ring-containing (meth) acrylate and the aromatic ring-containing vinyl compound can be used individually by 1 type or in combination of 2 or more types, respectively. One or more aromatic ring-containing (meth) acrylates may be used in combination with one or more aromatic ring-containing vinyl compounds.
 アクリル系ポリマー(A)を構成するモノマー成分におけるモノマー(m1)の含有量は、特に制限されず、所望の屈折率と粘着特性(例えば剥離強度、柔軟性等)および/または光学特性(例えば全光線透過性、ヘイズ値等)とを両立する粘着剤層を実現し得るように設定することができる。いくつかの態様において、上記モノマー成分におけるモノマー(m1)の含有量は、例えば30重量%以上であってよく、好ましくは50重量%以上であり、60重量%以上でもよく、70重量%以上でもよい。より高い屈折率を得やすくする観点から、いくつかの好ましい態様において、上記モノマー(m1)の含有量は、例えば70重量%超であってよく、75重量%以上でもよく、80重量%以上でもよく、85重量%以上でもよく、90重量%以上でもよく、95重量%以上でもよい。上記モノマー成分におけるモノマー(m1)の含有量の上限は100重量%である。高屈折率と粘着特性および/または光学特性とをバランスよく両立する観点から、上記モノマー(m1)の含有量は、100重量%未満とすることが有利であり、例えば凡そ99重量%以下であることが好ましく、98重量%以下であることがより好ましく、97重量%以下でもよく、96重量%以下でもよい。いくつかの態様において、上記モノマー(m1)の含有量は、93重量%以下でもよく、90重量%以下でもよく、80重量%以下でもよく、75重量%以下でもよい。より粘着特性および/または光学特性を重視するいくつかの態様において、上記モノマー成分における上記モノマー(m1)の含有量は、70重量%以下でもよく、60重量%以下でもよく、45重量%以下でもよい。 The content of the monomer (m1) in the monomer component constituting the acrylic polymer (A) is not particularly limited, and the desired refractive index and adhesive properties (for example, peel strength, flexibility, etc.) and / or optical properties (for example, all) are not particularly limited. It can be set so as to realize a pressure-sensitive adhesive layer that has both light transmittance, haze value, etc.). In some embodiments, the content of the monomer (m1) in the monomer component may be, for example, 30% by weight or more, preferably 50% by weight or more, 60% by weight or more, or 70% by weight or more. good. From the viewpoint of facilitating the acquisition of a higher refractive index, in some preferred embodiments, the content of the monomer (m1) may be, for example, more than 70% by weight, 75% by weight or more, or 80% by weight or more. It may be 85% by weight or more, 90% by weight or more, or 95% by weight or more. The upper limit of the content of the monomer (m1) in the above-mentioned monomer component is 100% by weight. From the viewpoint of achieving both high refractive index and adhesive properties and / or optical properties in a well-balanced manner, it is advantageous that the content of the monomer (m1) is less than 100% by weight, for example, about 99% by weight or less. It is preferably 98% by weight or less, 97% by weight or less, and 96% by weight or less. In some embodiments, the content of the monomer (m1) may be 93% by weight or less, 90% by weight or less, 80% by weight or less, or 75% by weight or less. In some embodiments where more adhesive and / or optical properties are emphasized, the content of the monomer (m1) in the monomer component may be 70% by weight or less, 60% by weight or less, or 45% by weight or less. good.
 ここに開示される技術のいくつかの態様において、モノマー(m1)としては、高い高屈折率化効果が得られやすいことから、1分子中に2以上の芳香環(好ましくは炭素環)を有するモノマーを好ましく採用し得る。1分子内に2以上の芳香環を有するモノマー(以下、「芳香環複数含有モノマー」ともいう。)の例としては、2以上の非縮合芳香環がリンキング基を介して結合した構造を有するモノマー、2以上の非縮合芳香環が直接(すなわち、他の原子を介さずに)化学結合した構造を有するモノマー、縮合芳香環構造を有するモノマー、フルオレン構造を有するモノマー、ジナフトチオフェン構造を有するモノマー、ジベンゾチオフェン構造を有するモノマー、等が挙げられる。芳香環複数含有モノマーは、1種を単独でまたは2種以上を組み合わせて用いることができる。 In some aspects of the technique disclosed herein, the monomer (m1) has two or more aromatic rings (preferably carbon rings) in one molecule because a high refractive index increasing effect can be easily obtained. Monomers can be preferably used. As an example of a monomer having two or more aromatic rings in one molecule (hereinafter, also referred to as “monomer containing a plurality of aromatic rings”), a monomer having a structure in which two or more non-condensed aromatic rings are bonded via a linking group. A monomer having a structure in which two or more non-condensed aromatic rings are chemically bonded directly (that is, without interposing other atoms), a monomer having a condensed aromatic ring structure, a monomer having a fluorene structure, and a monomer having a dinaphthothiophene structure. , Monomers having a dibenzothiophene structure, and the like. The monomer containing a plurality of aromatic rings may be used alone or in combination of two or more.
 上記リンキング基は、例えばオキシ基(-O-)、チオオキシ基(-S-)、オキシアルキレン基(例えば-O-(CH-基、ここでnは1~3、好ましくは1)、チオオキシアルキレン基(例えば-S-(CH-基、ここでnは1~3、好ましくは1)、直鎖アルキレン基(すなわち-(CH-基、ここでnは1~6、好ましくは1~3)、上記オキシアルキレン基、上記チオオキシアルキレン基および上記直鎖アルキレン基におけるアルキレン基が部分ハロゲン化または完全ハロゲン化された基、等であり得る。粘着剤の柔軟性等の観点から、上記リンキング基の好適例として、オキシ基、チオオキシ基、オキシアルキレン基および直鎖アルキレン基が挙げられる。2以上の非縮合芳香環がリンキング基を介して結合した構造を有するモノマーの具体例としては、フェノキシベンジル(メタ)アクリレート(例えば、m-フェノキシベンジル(メタ)アクリレート)、チオフェノキシベンジル(メタ)アクリレート、ベンジルベンジル(メタ)アクリレート、等が挙げられる。 The linking group is, for example, an oxy group (-O-), a thiooxy group (-S-), an oxyalkylene group (for example, -O- (CH 2 ) n- group, where n is 1 to 3, preferably 1). , Thiooxyalkylene groups (eg-S- (CH 2 ) n -groups, where n is 1-3, preferably 1), linear alkylene groups (ie-(CH 2 ) n -groups, where n is 1 to 6, preferably 1 to 3), the oxyalkylene group, the thiooxyalkylene group, and the group in which the alkylene group in the linear alkylene group is partially halogenated or completely halogenated, and the like can be used. From the viewpoint of the flexibility of the pressure-sensitive adhesive, preferred examples of the linking group include an oxy group, a thiooxy group, an oxyalkylene group and a linear alkylene group. Specific examples of the monomer having a structure in which two or more non-condensed aromatic rings are bonded via a linking group include phenoxybenzyl (meth) acrylate (for example, m-phenoxybenzyl (meth) acrylate) and thiophenoxybenzyl (meth). Examples thereof include acrylate, benzylbenzyl (meth) acrylate, and the like.
 上記2以上の非縮合芳香環が直接化学結合した構造を有するモノマーは、例えばビフェニル構造含有(メタ)アクリレート、トリフェニル構造含有(メタ)アクリレート、ビニル基含有ビフェニル等であり得る。具体例としては、o-フェニルフェノール(メタ)アクリレート、ビフェニルメチル(メタ)アクリレート等が挙げられる。 The monomer having a structure in which the above two or more non-condensed aromatic rings are directly chemically bonded may be, for example, a biphenyl structure-containing (meth) acrylate, a triphenyl structure-containing (meth) acrylate, a vinyl group-containing biphenyl, or the like. Specific examples include o-phenylphenol (meth) acrylate and biphenylmethyl (meth) acrylate.
 上記縮合芳香環構造を有するモノマーの例としては、ナフタレン環含有(メタ)アクリレート、アントラセン環含有(メタ)アクリレート、ビニル基含有ナフタレン、ビニル基含有アントラセン、等が挙げられる。具体例としては、1-ナフチルメチル(メタ)アクリレート(別名:1-ナフタレンメチル(メタ)アクリレート)、ヒドロキシエチル化β-ナフトールアクリレート、2-ナフトエチル(メタ)アクリレート、2-ナフトキシエチルアクリレート、2-(4-メトキシ-1-ナフトキシ)エチル(メタ)アクリレート、等が挙げられる。 Examples of the monomer having a condensed aromatic ring structure include naphthalene ring-containing (meth) acrylate, anthracene ring-containing (meth) acrylate, vinyl group-containing naphthalene, and vinyl group-containing anthracene. Specific examples include 1-naphthylmethyl (meth) acrylate (also known as 1-naphthalenemethyl (meth) acrylate), hydroxyethylated β-naphthol acrylate, 2-naphthoethyl (meth) acrylate, 2-naphthoxyethyl acrylate, 2 -(4-Methoxy-1-naphthoxy) ethyl (meth) acrylate, etc. may be mentioned.
 上記フルオレン構造を有するモノマーの具体例としては、9,9-ビス(4-ヒドロキシフェニル)フルオレン(メタ)アクリレート、9,9-ビス[4-(2-ヒドロキシエトキシ)フェニル]フルオレン(メタ)アクリレート等が挙げられる。なお、フルオレン構造を有するモノマーは、2つのベンゼン環が直接化学結合した構造部分を含むため、上記2以上の非縮合芳香環が直接化学結合した構造を有するモノマーの概念に包含される。 Specific examples of the monomer having a fluorene structure include 9,9-bis (4-hydroxyphenyl) fluorene (meth) acrylate and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (meth) acrylate. And so on. Since the monomer having a fluorene structure contains a structural portion in which two benzene rings are directly chemically bonded, it is included in the concept of a monomer having a structure in which two or more non-condensed aromatic rings are directly chemically bonded.
 上記ジナフトチオフェン構造を有するモノマーとしては、(メタ)アクリロイル基含有ジナフトチオフェン、ビニル基含有ジナフトチオフェン、(メタ)アリル基含有ジナフトチオフェン、等が挙げられる。具体例としては、(メタ)アクリロイルオキシメチルジナフトチオフェン(例えば、ジナフトチオフェン環の5位または6位にCHCH(R)C(O)OCH-が結合した構造の化合物。ここで、Rは水素原子またはメチル基である。)、(メタ)アクリロイルオキシエチルジナフトチオフェン(例えば、ジナフトチオフェン環の5位または6位に、CHCH(R)C(O)OCH(CH)-またはCHCH(R)C(O)OCHCH-が結合した構造の化合物。ここで、Rは水素原子またはメチル基である。)、ビニルジナフトチオフェン(例えば、ナフトチオフェン環の5位または6位にビニル基が結合した構造の化合物)、(メタ)アリルオキシジナフトチオフェン、等が挙げられる。なお、ジナフトチオフェン構造を有するモノマーは、ナフタレン構造を含むことにより、またチオフェン環と2つのナフタレン構造とが縮合した構造を有することによっても、上記縮合芳香環構造を有するモノマーの概念に包含される。 Examples of the monomer having a dinaphthophene structure include (meth) acryloyl group-containing dinaphthophene, vinyl group-containing dinaphthophene, and (meth) allyl group-containing dinaphthothiophene. As a specific example, a compound having a structure in which CH 2 CH (R 1 ) C (O) OCH 2- is bound to the 5- or 6-position of the (meth) acryloyloxymethyldinaphthophene ring (for example, the dinaphthophene ring). R 1 is a hydrogen atom or a methyl group), (meth) acryloyloxyethyl dinaphthophene (eg, CH 2 CH (R 1 ) C (O) at the 5th or 6th position of the dinaphthophene ring. A compound having a structure in which OCH (CH 3 ) -or CH 2 CH (R 1 ) C (O) OCH 2 CH 2 -are bound. Here, R 1 is a hydrogen atom or a methyl group), vinyl dinaphthophene. (For example, a compound having a structure in which a vinyl group is bonded to the 5- or 6-position of the naphthophene ring), (meth) allyloxydinaphthophene, and the like. The monomer having a dinaphthophene structure is included in the concept of a monomer having a condensed aromatic ring structure because it contains a naphthalene structure and also has a structure in which a thiophene ring and two naphthalene structures are condensed. NS.
 上記ジベンゾチオフェン構造を有するモノマーとしては、(メタ)アクリロイル基含有ジベンゾチオフェン、ビニル基含有ジベンゾチオフェン、等が挙げられる。なお、ジベンゾチオフェン構造を有するモノマーは、チオフェン環と2つのベンゼン環とが縮合した構造を有することから、上記縮合芳香環構造を有するモノマーの概念に包含される。
 なお、ジナフトチオフェン構造およびジベンゾチオフェン構造は、いずれも、2以上の非縮合芳香環が直接化学結合した構造には該当しない。
Examples of the monomer having a dibenzothiophene structure include (meth) acryloyl group-containing dibenzothiophene, vinyl group-containing dibenzothiophene, and the like. A monomer having a dibenzothiophene structure is included in the concept of a monomer having a condensed aromatic ring structure because it has a structure in which a thiophene ring and two benzene rings are condensed.
Neither the dinaphthothiophene structure nor the dibenzothiophene structure corresponds to a structure in which two or more uncondensed aromatic rings are directly chemically bonded.
 ここに開示される技術におけるモノマー(m1)として、1分子中に1つの芳香環(好ましくは炭素環)を有するモノマーを使用してもよい。1分子中に1つの芳香環を有するモノマーは、例えば、粘着剤の柔軟性の向上や粘着特性の調整、透明性の向上等に役立ち得る。いくつかの態様において、1分子中に1つの芳香環を有するモノマーは、粘着剤の屈折率向上の観点から、芳香環複数含有モノマーと組み合わせて用いることが好ましい。 As the monomer (m1) in the technique disclosed herein, a monomer having one aromatic ring (preferably a carbon ring) in one molecule may be used. A monomer having one aromatic ring in one molecule can be useful for improving the flexibility of the pressure-sensitive adhesive, adjusting the pressure-sensitive adhesive properties, improving the transparency, and the like. In some embodiments, the monomer having one aromatic ring in one molecule is preferably used in combination with a monomer containing a plurality of aromatic rings from the viewpoint of improving the refractive index of the pressure-sensitive adhesive.
 1分子中に1つの芳香環を有するモノマーの例としては、べンジル(メタ)アクリレート、メトキシベンジル(メタ)アクリレート、フェニル(メタ)アクリレート、エトキシ化フェノール(メタ)アクリレート、フェノキシプロピル(メタ)アクリレート、フェノキシブチル(メタ)アクリレート、クレジル(メタ)アクリレート、2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート、クロロベンジル(メタ)アクリレート等の、炭素芳香環含有(メタ)アクリレート;2-(4,6-ジブロモ-2-s-ブチルフェノキシ)エチル(メタ)アクリレート、2-(4,6-ジブロモ-2-イソプロピルフェノキシ)エチル(メタ)アクリレート、6-(4,6-ジブロモ-2-s-ブチルフェノキシ)ヘキシル(メタ)アクリレート、6-(4,6-ジブロモ-2-イソプロピルフェノキシ)ヘキシル(メタ)アクリレート、2,6-ジブロモ-4-ノニルフェニルアクリレート、2,6-ジブロモ-4-ドデシルフェニルアクリレート等の、臭素置換芳香環含有(メタ)アクリレート;スチレン、α-メチルスチレン、ビニルトルエン、tert-ブチルスチレン等の、炭素芳香環含有ビニル化合物;N-ビニルピリジン、N-ビニルピリミジン、N-ビニルピラジン、N-ビニルピロール、N-ビニルイミダゾール、N-ビニルオキサゾール等の、複素芳香環上にビニル置換基を有する化合物;等が挙げられる。 Examples of monomers having one aromatic ring in one molecule include benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, phenyl (meth) acrylate, ethoxylated phenol (meth) acrylate, and phenoxypropyl (meth) acrylate. , Phenoxybutyl (meth) acrylate, cresyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, chlorobenzyl (meth) acrylate, and other carbon aromatic ring-containing (meth) acrylates; 2- (4, 6-Dibromo-2-s-butylphenoxy) ethyl (meth) acrylate, 2- (4,6-dibromo-2-isopropylphenoxy) ethyl (meth) acrylate, 6- (4,6-dibromo-2-s-) Butylphenoxy) hexyl (meth) acrylate, 6- (4,6-dibromo-2-isopropylphenoxy) hexyl (meth) acrylate, 2,6-dibromo-4-nonylphenyl acrylate, 2,6-dibromo-4-dodecyl Bromine-substituted aromatic ring-containing (meth) acrylates such as phenyl acrylates; carbon aromatic ring-containing vinyl compounds such as styrene, α-methylstyrene, vinyltoluene and tert-butylstyrene; N-vinylpyridine, N-vinylpyrimidine, N. -Compounds having a vinyl substituent on the heteroaromatic ring such as vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole; and the like can be mentioned.
 モノマー(m1)としては、上述のような各種芳香環含有モノマーにおけるエチレン性不飽和基と芳香環との間にオキシエチレン鎖を介在させた構造のモノマーを使用してもよい。このようにエチレン性不飽和基と芳香環との間にオキシエチレン鎖を介在させたモノマーは、元のモノマーのエトキシ化物として把握され得る。上記オキシエチレン鎖におけるオキシエチレン単位(-CHCHO-)の繰返し数は、典型的には1~4、好ましくは1~3、より好ましくは1~2であり、例えば1である。エトキシ化された芳香環含有モノマーの具体例としては、エトキシ化o-フェニルフェノール(メタ)アクリレート、エトキシ化ノニルフェノール(メタ)アクリレート、エトキシ化クレゾール(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、フェノキシジエチレングリコールジ(メタ)アクリレート等が挙げられる。 As the monomer (m1), a monomer having a structure in which an oxyethylene chain is interposed between an ethylenically unsaturated group and an aromatic ring in various aromatic ring-containing monomers as described above may be used. A monomer having an oxyethylene chain interposed between an ethylenically unsaturated group and an aromatic ring in this way can be grasped as an ethoxylated product of the original monomer. The number of repetitions of the oxyethylene unit (-CH 2 CH 2 O-) in the oxyethylene chain is typically 1 to 4, preferably 1 to 3, more preferably 1 to 2, and is, for example, 1. Specific examples of the ethoxylated aromatic ring-containing monomer include ethoxylated o-phenylphenol (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, ethoxylated cresol (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol. Di (meth) acrylate and the like can be mentioned.
 モノマー(m1)における芳香環複数含有モノマーの含有量は、特に制限されず、例えば5重量%以上であってよく、25重量%以上でもよく、40重量%以上でもよい。いくつかの態様において、より高い屈折率を有する粘着剤を実現しやすくする観点から、モノマー(m1)における芳香環複数含有モノマーの含有量は、例えば50重量%以上であってよく、70重量%以上であることが好ましく、85重量%以上でもよく、90重量%以上でもよく、95重量%以上でもよい。モノマー(m1)の実質的に100重量%が芳香環複数含有モノマーであってもよい。すなわち、モノマー(m1)として1種または2種以上の芳香環複数含有モノマーのみを使用してもよい。また、いくつかの態様において、例えば高屈折率と粘着特性および/または光学特性とのバランスを考慮して、モノマー(m1)における芳香環複数含有モノマーの含有量は、100重量%未満であってもよく、98重量%以下でもよく、90重量%以下でもよく、80重量%以下でもよく、65重量%以下でもよい。いくつかの態様において、粘着特性および/または光学特性を考慮して、モノマー(m1)における芳香環複数含有モノマーの含有量は、70重量%以下でもよく、50重量%以下でもよく、25重量%以下でもよく、10重量%以下でもよい。ここに開示される技術は、モノマー(m1)における芳香環複数含有モノマーの含有量が5重量%未満である態様でも実施し得る。芳香環複数含有モノマーを使用しなくてもよい。 The content of the monomer containing a plurality of aromatic rings in the monomer (m1) is not particularly limited, and may be, for example, 5% by weight or more, 25% by weight or more, or 40% by weight or more. In some embodiments, the content of the aromatic ring plurality-containing monomer in the monomer (m1) may be, for example, 50% by weight or more, 70% by weight, from the viewpoint of facilitating the realization of a pressure-sensitive adhesive having a higher refractive index. The above is preferable, and it may be 85% by weight or more, 90% by weight or more, or 95% by weight or more. Substantially 100% by weight of the monomer (m1) may be a monomer containing a plurality of aromatic rings. That is, only one type or two or more types of aromatic ring-containing plurality-containing monomers may be used as the monomer (m1). Further, in some embodiments, the content of the aromatic ring plurality-containing monomer in the monomer (m1) is less than 100% by weight, for example, in consideration of the balance between the high refractive index and the adhesive property and / or the optical property. It may be 98% by weight or less, 90% by weight or less, 80% by weight or less, or 65% by weight or less. In some embodiments, the content of the aromatic ring multiple-containing monomer in the monomer (m1) may be 70% by weight or less, 50% by weight or less, or 25% by weight in consideration of adhesive properties and / or optical properties. It may be less than or equal to 10% by weight or less. The technique disclosed herein can also be carried out in an embodiment in which the content of the monomer containing a plurality of aromatic rings in the monomer (m1) is less than 5% by weight. It is not necessary to use a monomer containing a plurality of aromatic rings.
 アクリル系ポリマーを構成するモノマー成分における芳香環複数含有モノマーの含有量は、特に制限されず、所望の屈折率と粘着特性(例えば剥離強度、柔軟性等)および/または光学特性(例えば全光線透過性、ヘイズ値等)とを両立する粘着剤層を実現し得るように設定することができる。上記モノマー成分における芳香環複数含有モノマーの含有量は、例えば3重量%以上であってよく、10重量%以上でもよく、25重量%以上でもよい。いくつかの態様において、より高い屈折率を有する粘着剤を実現しやすくする観点から、上記モノマー成分における芳香環複数含有モノマーの含有量は、例えば35重量%超であってよく、50重量%超であることが好ましく、70重量%超でもよく、75重量%以上でもよく、85重量%以上でもよく、90重量%以上でもよく、95重量%以上でもよい。上記モノマー成分における芳香環複数含有モノマーの含有量は、100重量%であり得るが、高屈折率と粘着特性および/または光学特性とをバランスよく両立する観点から、100重量%未満とすることが有利であり、凡そ99重量%以下とすることが好ましく、98重量%以下とすることがより好ましく、96重量%以下でもよく、93重量%以下でもよく、90重量%以下でもよく、85重量%以下でもよく、80重量%以下でもよく、75重量%以下でもよい。いくつかの態様において、粘着特性および/または光学特性を考慮して、上記モノマー成分における芳香環複数含有モノマーの含有量は、70重量%以下でもよく、50重量%以下でもよく、25重量%以下でもよく、15重量%以下でもよく、5重量%以下でもよい。ここに開示される技術は、上記モノマー成分における芳香環複数含有モノマーの含有量が3重量%未満である態様でも実施し得る。 The content of the aromatic ring-containing monomer in the monomer component constituting the acrylic polymer is not particularly limited, and the desired refractive index and adhesive properties (for example, peel strength, flexibility, etc.) and / or optical properties (for example, total light transmission) are not particularly limited. It can be set so as to realize a pressure-sensitive adhesive layer that is compatible with (property, haze value, etc.). The content of the monomer containing a plurality of aromatic rings in the above-mentioned monomer component may be, for example, 3% by weight or more, 10% by weight or more, or 25% by weight or more. In some embodiments, the content of the aromatic ring plurality-containing monomer in the above-mentioned monomer component may be, for example, more than 35% by weight, more than 50% by weight, from the viewpoint of facilitating the realization of a pressure-sensitive adhesive having a higher refractive index. It may be more than 70% by weight, 75% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more. The content of the monomer containing a plurality of aromatic rings in the above-mentioned monomer component may be 100% by weight, but may be less than 100% by weight from the viewpoint of achieving both high refractive index and adhesive properties and / or optical properties in a well-balanced manner. It is advantageous, preferably about 99% by weight or less, more preferably 98% by weight or less, 96% by weight or less, 93% by weight or less, 90% by weight or less, 85% by weight. It may be less than or equal to 80% by weight, and may be 75% by weight or less. In some embodiments, the content of the aromatic ring plurality-containing monomer in the above-mentioned monomer component may be 70% by weight or less, 50% by weight or less, and 25% by weight or less in consideration of adhesive properties and / or optical properties. However, it may be 15% by weight or less, or 5% by weight or less. The technique disclosed herein can also be carried out in an embodiment in which the content of the monomer containing a plurality of aromatic rings in the above-mentioned monomer component is less than 3% by weight.
 ここに開示される技術のいくつかの態様において、モノマー(m1)の少なくとも一部として、高屈折率モノマーを好ましく採用し得る。ここで「高屈折率モノマー」とは、その屈折率が、例えば凡そ1.510以上、好ましくは凡そ1.530以上、より好ましくは凡そ1.550以上であるモノマーのことを指す。高屈折率モノマーの屈折率の上限は特に制限されないが、粘着剤組成物の調製容易性や、粘着剤として適した柔軟性との両立容易性の観点から、例えば3.000以下であり、2.500以下でもよく、2.000以下でもよく、1.900以下でもよく、1.800以下でもよく、1.700以下でもよい。高屈折率モノマーは、1種を単独でまたは2種以上を組み合わせて用いることができる。
 なお、モノマーの屈折率は、アッベ屈折率計を用いて、測定波長589nm、測定温度25℃の条件で測定される。アッベ屈折率計としては、ATAGO社製の型式「DR-M4」またはその相当品を用いることができる。メーカー等から25℃における屈折率の公称値が提供されている場合は、その公称値を採用することができる。
In some aspects of the techniques disclosed herein, a high refractive index monomer may be preferably employed as at least a portion of the monomer (m1). Here, the "high refractive index monomer" refers to a monomer having a refractive index of, for example, about 1.510 or more, preferably about 1.530 or more, and more preferably about 1.550 or more. The upper limit of the refractive index of the high-refractive index monomer is not particularly limited, but is, for example, 3.000 or less from the viewpoint of ease of preparation of the pressure-sensitive adhesive composition and ease of compatibility with flexibility suitable as a pressure-sensitive adhesive. It may be .500 or less, 2.000 or less, 1.900 or less, 1.800 or less, or 1.700 or less. The high refractive index monomer may be used alone or in combination of two or more.
The refractive index of the monomer is measured using an Abbe refractive index meter under the conditions of a measurement wavelength of 589 nm and a measurement temperature of 25 ° C. As the Abbe refractive index meter, a model "DR-M4" manufactured by ATAGO or an equivalent product thereof can be used. If the manufacturer or the like provides a nominal value of the refractive index at 25 ° C., the nominal value can be adopted.
 上記高屈折率モノマーとしては、ここに開示される芳香環含有モノマー(m1)の概念に包含される化合物(例えば、上記で例示した化合物および化合物群)のなかから、該当する屈折率を有するものを適宜採用することができる。具体例としては、m-フェノキシベンジルアクリレート(屈折率:1.566、ホモポリマーのTg:-35℃)、1-ナフチルメチルアクリレート(屈折率:1.595、ホモポリマーのTg:31℃)、エトキシ化o-フェニルフェノールアクリレート(オキシエチレン単位の繰返し数:1、屈折率:1.578)、ベンジルアクリレート(屈折率(nD20):1.519、ホモポリマーのTg:6℃)、フェノキシエチルアクリレート(屈折率(nD20):1.517、ホモポリマーのTg:2℃)、フェノキシジエチレングリコールアクリレート(屈折率:1.510、ホモポリマーのTg:-35℃)、6-アクリロイルオキシメチルジナフトチオフェン(6MDNTA、屈折率:1.75)、6-メタアクリロイルオキシメチルジナフトチオフェン(6MDNTMA、屈折率:1.726)、5-アクリロイルオキシエチルジナフトチオフェン(5EDNTA、屈折率:1.786)、6-アクリロイルオキシエチルジナフトチオフェン(6EDNTA、屈折率:1.722)、6-ビニルジナフトチオフェン(6VDNT、屈折率:1.802)、5-ビニルジナフトチオフェン(略号:5VDNT、屈折率:1.793)、等が挙げられるが、これらに限定されない。 The high-refractive index monomer has a refractive index among the compounds included in the concept of the aromatic ring-containing monomer (m1) disclosed herein (for example, the compounds and compound groups exemplified above). Can be adopted as appropriate. Specific examples include m-phenoxybenzyl acrylate (refraction: 1.566, homopolymer Tg: −35 ° C.), 1-naphthylmethyl acrylate (refraction: 1.595, homopolymer Tg: 31 ° C.), O-phenylphenol acrylate ethoxylated (number of repetitions of oxyethylene unit: 1, refraction: 1.578), benzyl acrylate (refraction (nD20): 1.519, homopolymer Tg: 6 ° C), phenoxyethyl acrylate (Refraction (nD20): 1.517, homopolymer Tg: 2 ° C.), phenoxydiethylene glycol acrylate (refraction: 1.510, homopolymer Tg: -35 ° C.), 6-acryloyloxymethyldinaphthophen ( 6MDNTA, Refraction: 1.75), 6-Metaacryloyloxymethyldinaphthophen (6MDNTMA, Refraction: 1.726), 5-Acryloyloxyethyldinaphthophen (5EDNTA, Refraction: 1.786), 6 -Acryloyloxyethyl dinaphthophene (6EDNTA, refraction: 1.722), 6-vinyldinaphthophene (6VDNT, refraction: 1.802), 5-vinyldinaphthophen (abbreviation: 5VDNT, refraction: 1) .793), etc., but are not limited to these.
 モノマー(m1)における高屈折率モノマー(すなわち、屈折率が凡そ1.510以上、好ましくは凡そ1.530以上、より好ましくは凡そ1.550以上である芳香環含有モノマー)の含有量は、特に制限されず、例えば5重量%以上であってよく、25重量%以上でもよく、35重量%以上でもよく、40重量%以上でもよい。いくつかの態様において、より高い屈折率を得やすくする観点から、モノマー(m1)における高屈折率モノマーの含有量は、例えば50重量%以上であってよく、70重量%以上であることが好ましく、85重量%以上でもよく、90重量%以上でもよく、95重量%以上でもよい。モノマー(m1)の実質的に100重量%が高屈折率モノマーであってもよい。また、いくつかの態様において、例えば高屈折率と粘着特性および/または光学特性とをバランスよく両立する観点から、モノマー(m1)における高屈折率モノマーの含有量は、100重量%未満であってもよく、98重量%以下でもよく、90重量%以下でもよく、80重量%以下でもよく、65重量%以下でもよい。いくつかの態様において、粘着特性および/または光学特性を考慮して、モノマー(m1)における高屈折率モノマーの含有量は、70重量%以下でもよく、50重量%以下でもよく、25重量%以下でもよく、15重量%以下でもよく、10重量%以下でもよい。ここに開示される技術は、モノマー成分(m1)における高屈折率モノマーの含有量が5重量%未満である態様でも実施し得る。高屈折率モノマーを使用しなくてもよい。 The content of the high refractive index monomer (that is, the aromatic ring-containing monomer having a refractive index of about 1.510 or more, preferably about 1.530 or more, more preferably about 1.550 or more) in the monomer (m1) is particularly high. It is not limited, and may be, for example, 5% by weight or more, 25% by weight or more, 35% by weight or more, or 40% by weight or more. In some embodiments, the content of the high refractive index monomer in the monomer (m1) may be, for example, 50% by weight or more, preferably 70% by weight or more, from the viewpoint of facilitating the acquisition of a higher refractive index. , 85% by weight or more, 90% by weight or more, 95% by weight or more. Substantially 100% by weight of the monomer (m1) may be a high refractive index monomer. Further, in some embodiments, the content of the high refractive index monomer in the monomer (m1) is less than 100% by weight, for example, from the viewpoint of achieving both high refractive index and adhesive properties and / or optical properties in a well-balanced manner. It may be 98% by weight or less, 90% by weight or less, 80% by weight or less, or 65% by weight or less. In some embodiments, the content of the high refractive index monomer in the monomer (m1) may be 70% by weight or less, 50% by weight or less, and 25% by weight or less in consideration of adhesive properties and / or optical properties. However, it may be 15% by weight or less, or 10% by weight or less. The technique disclosed herein can also be carried out in an embodiment in which the content of the high refractive index monomer in the monomer component (m1) is less than 5% by weight. It is not necessary to use a high refractive index monomer.
 アクリル系ポリマーを構成するモノマー成分における高屈折率モノマーの含有量は、特に制限されず、所望の屈折率と粘着特性(例えば剥離強度、柔軟性等)および/または光学特性(例えば全光線透過性、ヘイズ値等)とを両立する粘着剤層を実現し得るように設定することができる。上記モノマー成分における高屈折率モノマーの含有量は、例えば3重量%以上であってよく、10重量%以上でもよく、25重量%以上でもよい。いくつかの態様において、より高い屈折率を有する粘着剤を実現しやすくする観点から、上記モノマー成分における高屈折率モノマーの含有量は、例えば35重量%超であってよく、50重量%超であることが好ましく、70重量%超でもよく、75重量%以上でもよく、85重量%以上でもよく、90重量%以上でもよく、95重量%以上でもよい。上記モノマー成分における高屈折率モノマーの含有量は、100重量%であり得るが、高屈折率と粘着特性および/または光学特性とをバランスよく両立する観点から、100重量%未満とすることが有利であり、99重量%以下とすることが好ましく、98重量%以下とすることがより好ましく、96重量%以下でもよく、93重量%以下でもよく、90重量%以下でもよく、85重量%以下でもよく、80重量%以下でもよく、75重量%以下でもよい。いくつかの態様において、粘着特性および/または光学特性を考慮して、上記モノマー成分における高屈折率モノマーの含有量は、70重量%以下でもよく、50重量%以下でもよく、25重量%以下でもよく、15重量%以下でもよく、5重量%以下でもよい。ここに開示される技術は、上記モノマー成分における高屈折率モノマーの含有量が3重量%未満である態様でも実施し得る。 The content of the high refractive index monomer in the monomer component constituting the acrylic polymer is not particularly limited, and the desired refractive index and adhesive properties (for example, peel strength, flexibility, etc.) and / or optical properties (for example, total light transmittance) are not particularly limited. , Haze value, etc.) can be set so as to realize a pressure-sensitive adhesive layer. The content of the high refractive index monomer in the monomer component may be, for example, 3% by weight or more, 10% by weight or more, or 25% by weight or more. In some embodiments, from the viewpoint of facilitating the realization of a pressure-sensitive adhesive having a higher refractive index, the content of the high refractive index monomer in the above-mentioned monomer component may be, for example, more than 35% by weight, and more than 50% by weight. It may be more than 70% by weight, 75% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more. The content of the high refractive index monomer in the above-mentioned monomer component can be 100% by weight, but it is advantageous to make it less than 100% by weight from the viewpoint of achieving a good balance between the high refractive index and the adhesive property and / or the optical property. It is preferably 99% by weight or less, more preferably 98% by weight or less, 96% by weight or less, 93% by weight or less, 90% by weight or less, and 85% by weight or less. It may be 80% by weight or less, or 75% by weight or less. In some embodiments, the content of the high refractive index monomer in the monomer component may be 70% by weight or less, 50% by weight or less, or 25% by weight or less in consideration of adhesive properties and / or optical properties. It may be 15% by weight or less, or 5% by weight or less. The technique disclosed herein can also be carried out in an embodiment in which the content of the high refractive index monomer in the monomer component is less than 3% by weight.
 ここに開示される技術のいくつかの好ましい態様では、モノマー(m1)の少なくとも一部として、ホモポリマーのTgが10℃以下(好ましくは5℃以下または0℃以下、より好ましくは-10℃以下、さらに好ましくは-20℃以下、例えば-25℃以下)である芳香環含有モノマー(以下、「モノマーL」と表記することがある。)を採用する。モノマー成分における芳香環含有モノマー(m1)(特に、上述した芳香環複数含有モノマーおよび高屈折率モノマーの一方または両方に該当する芳香環含有モノマー(m1))の含有量を多くすると、粘着剤の貯蔵弾性率G’は概して上昇する傾向にあるところ、該モノマー(m1)の一部または全部としてモノマーLを採用することにより、貯蔵弾性率G’の上昇を抑制することができる。これにより、粘着剤として適した柔軟性をよりよく維持しつつ、屈折率を向上させることができる。モノマーLのTgの下限は特に制限されない。屈折率向上効果とのバランスを考慮して、いくつかの態様において、モノマーLのTgは、例えば-70℃以上であってよく、-55℃以上でもよく、-45℃以上でもよい。モノマーLは、1種を単独でまたは2種以上を組み合わせて用いることができる。 In some preferred embodiments of the techniques disclosed herein, the Tg of the homopolymer as at least a portion of the monomer (m1) is 10 ° C. or lower (preferably 5 ° C. or lower or 0 ° C. or lower, more preferably −10 ° C. or lower). , More preferably −20 ° C. or lower, for example −25 ° C. or lower), an aromatic ring-containing monomer (hereinafter, may be referred to as “monomer L”) is adopted. Increasing the content of the aromatic ring-containing monomer (m1) in the monomer component (particularly, the aromatic ring-containing monomer (m1) corresponding to one or both of the above-mentioned aromatic ring plural-containing monomer and high refractive index monomer) increases the content of the pressure-sensitive adhesive. Where the storage elasticity G'geners generally tends to increase, the increase in the storage elasticity G'can be suppressed by adopting the monomer L as a part or all of the monomer (m1). This makes it possible to improve the refractive index while better maintaining the flexibility suitable as a pressure-sensitive adhesive. The lower limit of Tg of the monomer L is not particularly limited. In consideration of the balance with the effect of improving the refractive index, in some embodiments, the Tg of the monomer L may be, for example, −70 ° C. or higher, −55 ° C. or higher, or −45 ° C. or higher. As the monomer L, one type can be used alone or two or more types can be used in combination.
 モノマーLとしては、ここに開示される芳香環含有モノマー(m1)の概念に包含される化合物(例えば、上記で例示した化合物および化合物群)のなかから、該当するTgを有するものを適宜採用することができる。モノマーLとして使用し得る芳香環含有モノマーの一好適例として、m-フェノキシベンジルアクリレート(ホモポリマーのTg:-35℃)が挙げられる。他の一好適例として、フェノキシジエチレングリコールアクリレート(ホモポリマーのTg:-35℃)が挙げられる。 As the monomer L, among the compounds included in the concept of the aromatic ring-containing monomer (m1) disclosed herein (for example, the compounds and compound groups exemplified above), those having the corresponding Tg are appropriately adopted. be able to. As a preferable example of the aromatic ring-containing monomer that can be used as the monomer L, m-phenoxybenzyl acrylate (Tg of homopolymer: −35 ° C.) can be mentioned. Another preferred example is phenoxydiethylene glycol acrylate (homopolymer Tg: −35 ° C.).
 モノマー(m1)におけるモノマーLの含有量は、特に制限されず、例えば5重量%以上であってよく、25重量%以上でもよく、40重量%以上でもよい。いくつかの態様において、高屈折率と柔軟性とをより高レベルで両立する粘着剤を得やすくする観点から、モノマー(m1)におけるモノマーLの含有量は、例えば50重量%以上であってよく、60重量%以上でもよく、70重量%以上でもよく、75重量%以上でもよく、85重量%以上でもよく、90重量%以上でもよく、95重量%以上でもよい。モノマー(A1)の実質的に100重量%がモノマーLであってもよい。また、いくつかの態様において、例えば粘着剤として適した柔軟性と高屈折率とをバランスよく両立する観点から、モノマー(m1)におけるモノマーLの含有量は、100重量%未満であってもよく、98重量%以下でもよく、90重量%以下でもよく、80重量%以下でもよく、70重量%以下でもよく、50重量%以下でもよく、25重量%以下でもよく、10重量%以下でもよい。ここに開示される技術は、モノマー(m1)におけるモノマーLの含有量が5重量%未満である態様でも実施し得る。モノマーLを使用しなくてもよい。 The content of the monomer L in the monomer (m1) is not particularly limited, and may be, for example, 5% by weight or more, 25% by weight or more, or 40% by weight or more. In some embodiments, the content of the monomer L in the monomer (m1) may be, for example, 50% by weight or more, from the viewpoint of facilitating the acquisition of a pressure-sensitive adhesive having both high refractive index and flexibility at a higher level. , 60% by weight or more, 70% by weight or more, 75% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more. Substantially 100% by weight of the monomer (A1) may be the monomer L. Further, in some embodiments, the content of the monomer L in the monomer (m1) may be less than 100% by weight from the viewpoint of achieving both flexibility suitable as a pressure-sensitive adhesive and high refractive index in a well-balanced manner. , 98% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 50% by weight or less, 25% by weight or less, or 10% by weight or less. The technique disclosed herein can also be carried out in an embodiment in which the content of the monomer L in the monomer (m1) is less than 5% by weight. It is not necessary to use the monomer L.
 アクリル系ポリマーを構成するモノマー成分におけるモノマーLの含有量は、例えば3重量%以上であってよく、10重量%以上でもよく、25重量%以上でもよい。いくつかの態様において、高屈折率と柔軟性とをより高レベルで両立する粘着剤を得やすくする観点から、モノマー成分におけるモノマーLの含有量は、例えば35重量%超であってよく、50重量%超であることが好ましく、70重量%超でもよく、75重量%以上でもよく、85重量%以上でもよく、90重量%以上でもよく、95重量%以上でもよい。上記モノマー成分におけるモノマーLの含有量は、100重量%であり得るが、高屈折率と粘着特性および/または光学特性とのバランスを考慮して、100重量%未満とすることが有利であり、凡そ99重量%以下であることが好ましく、98重量%以下であることがより好ましく、96重量%以下でもよく、95重量%以下でもよく、93重量%以下でもよく、90重量%以下でもよく、85重量%以下でもよく、80重量%以下でもよく、75重量%以下でもよい。いくつかの態様において、上記モノマー成分におけるモノマーLの含有量は、70重量%以下でもよく、50重量%以下でもよく、25重量%以下でもよく、15重量%以下でもよく、5重量%以下でもよい。ここに開示される技術は、上記モノマー成分におけるモノマーLの含有量が3重量%未満である態様でも実施し得る。 The content of the monomer L in the monomer component constituting the acrylic polymer may be, for example, 3% by weight or more, 10% by weight or more, or 25% by weight or more. In some embodiments, the content of the monomer L in the monomer component may be, for example,> 35% by weight, 50 It is preferably more than 70% by weight, more than 70% by weight, more than 75% by weight, more than 85% by weight, more than 90% by weight, and more than 95% by weight. The content of the monomer L in the above-mentioned monomer component can be 100% by weight, but it is advantageous that the content is less than 100% by weight in consideration of the balance between the high refractive index and the adhesive property and / or the optical property. It is preferably about 99% by weight or less, more preferably 98% by weight or less, 96% by weight or less, 95% by weight or less, 93% by weight or less, 90% by weight or less. It may be 85% by weight or less, 80% by weight or less, or 75% by weight or less. In some embodiments, the content of the monomer L in the monomer component may be 70% by weight or less, 50% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less. good. The technique disclosed herein can also be carried out in an embodiment in which the content of the monomer L in the monomer component is less than 3% by weight.
 いくつかの態様において、モノマー(m1)の組成に基づくガラス転移温度Tgm1は、粘着剤の柔軟性の観点から、凡そ20℃以下であることが有利であり、好ましくは10℃以下(例えば5℃以下)、より好ましくは0℃以下であり、さらに好ましくは-10℃以下であり、-20℃以下でもよく、-25℃以下でもよい。ガラス転移温度Tgm1の下限は特に制限されない。屈折率向上効果とのバランスを考慮して、いくつかの態様において、ガラス転移温度Tgm1は、例えば-70℃以上であってよく、-55℃以上でもよく、-45℃以上でもよい。ここに開示される技術は、ガラス転移温度Tgm1が例えば-40℃以上、-35℃以上、-33℃以上、-30℃以上、または-25℃以上である態様でも好適に実施され得る。 In some embodiments, the glass transition temperature Tg m1 based on the composition of the monomer (m1) is preferably about 20 ° C. or lower, preferably 10 ° C. or lower (eg 5) from the viewpoint of adhesive flexibility. (° C. or lower), more preferably 0 ° C. or lower, still more preferably −10 ° C. or lower, −20 ° C. or lower, or −25 ° C. or lower. The lower limit of the glass transition temperature Tg m1 is not particularly limited. In consideration of the balance with the effect of improving the refractive index, the glass transition temperature Tg m1 may be, for example, −70 ° C. or higher, −55 ° C. or higher, or −45 ° C. or higher in some embodiments. The technique disclosed herein can also be preferably carried out in an embodiment in which the glass transition temperature Tg m1 is, for example, −40 ° C. or higher, −35 ° C. or higher, −33 ° C. or higher, −30 ° C. or higher, or −25 ° C. or higher.
 ここで、モノマー(m1)の組成に基づくガラス転移温度Tgm1とは、アクリル系ポリマーを構成するモノマー成分のうちモノマー(m1)のみの組成に基づいて、後述するFoxの式により求められるTgをいう。ガラス転移温度Tgm1は、アクリル系ポリマーを構成するモノマー成分のうちモノマー(m1)のみを対象として後述するFoxの式を適用し、モノマー(m1)として用いられる各芳香環含有モノマーのホモポリマーのガラス転移温度と、モノマー(m1)の合計量に占める各芳香環含有モノマーの重量分率とから算出することができる。モノマー(m1)として1種類のモノマーのみを使用する態様では、該モノマーのホモポリマーのTgとガラス転移温度Tgm1とは一致する。 Here, the glass transition temperature Tg m1 based on the composition of the monomer (m1) is a Tg obtained by the Fox formula described later based on the composition of only the monomer (m1) among the monomer components constituting the acrylic polymer. say. The glass transition temperature Tg m1 is a homopolymer of each aromatic ring-containing monomer used as the monomer (m1) by applying the Fox formula described later for only the monomer (m1) among the monomer components constituting the acrylic polymer. It can be calculated from the glass transition temperature and the weight fraction of each aromatic ring-containing monomer in the total amount of the monomers (m1). In the embodiment in which only one kind of monomer is used as the monomer (m1), the Tg of the homopolymer of the monomer and the glass transition temperature Tg m1 are the same.
 いくつかの態様において、芳香環含有モノマー(m1)としては、モノマーL(すなわち、ホモポリマーのTgが10℃以下、好ましくは5℃以下または0℃以下、より好ましくは-10℃以下、さらに好ましくは-20℃以下、例えば-25℃以下である芳香環含有モノマー)と、Tgが10℃よりも高いモノマーHとを組み合わせて用いることができる。モノマーHのTgは、例えば10℃超であってよく、15℃超であってもよく、20℃超であってもよい。モノマーLとモノマーHとを組み合わせて用いることにより、例えばモノマー成分における芳香環含有モノマー(m1)の含有量が比較的多い構成において、粘着剤の高屈折率と柔軟性とをより高レベルで両立させることができる。モノマーLとモノマーHとの使用量比は、かかる効果が好適に発現するように設定することができ、特に限定されない。例えば、上述したいずれかのガラス転移温度Tgm1を満たすようにモノマーLとモノマーHとの使用量比を設定することが好ましい。 In some embodiments, the aromatic ring-containing monomer (m1) includes monomer L (ie, homopolymer Tg of 10 ° C. or lower, preferably 5 ° C. or lower or 0 ° C. or lower, more preferably −10 ° C. or lower, even more preferably. (Aromatic ring-containing monomer having a temperature of −20 ° C. or lower, for example, −25 ° C. or lower) and a monomer H having a Tg higher than 10 ° C. can be used in combination. The Tg of the monomer H may be, for example, more than 10 ° C., more than 15 ° C., or more than 20 ° C. By using the monomer L and the monomer H in combination, for example, in a configuration in which the content of the aromatic ring-containing monomer (m1) in the monomer component is relatively large, the high refractive index and flexibility of the pressure-sensitive adhesive are compatible at a higher level. Can be made to. The usage amount ratio of the monomer L and the monomer H can be set so as to preferably exhibit such an effect, and is not particularly limited. For example, it is preferable to set the usage amount ratio of the monomer L and the monomer H so as to satisfy any of the above-mentioned glass transition temperatures Tg m1.
 いくつかの態様において、芳香環含有モノマー(m1)は、2以上の非縮合芳香環が直接化学結合した構造(例えばビフェニル構造)を含まない化合物から好ましく選択され得る。例えば、2以上の非縮合芳香環が直接化学結合した構造を含む化合物の含有量が5重量%未満(より好ましくは3重量%未満であり、0重量%でもよい。)である組成のモノマー成分により構成されたアクリル系ポリマーが好ましい。このように2以上の非縮合芳香環が直接化学結合した構造を含む化合物の使用量を制限することは、柔軟性や粘着性と高屈折率とをバランスよく両立させた粘着剤を実現する観点から有利となり得る。 In some embodiments, the aromatic ring-containing monomer (m1) can be preferably selected from compounds that do not contain a structure in which two or more uncondensed aromatic rings are directly chemically bonded (eg, a biphenyl structure). For example, a monomer component having a composition in which the content of the compound containing a structure in which two or more non-condensed aromatic rings are directly chemically bonded is less than 5% by weight (more preferably less than 3% by weight and may be 0% by weight). The acrylic polymer composed of is preferable. Limiting the amount of a compound containing a structure in which two or more non-condensed aromatic rings are directly chemically bonded in this way is a viewpoint of realizing a pressure-sensitive adhesive having a good balance of flexibility, tackiness and high refractive index. Can be advantageous from.
 (モノマー(m2))
 ここに開示される技術のいくつかの態様において、アクリル系ポリマーを構成するモノマー成分は、上記モノマー(m1)に加えて、モノマー(m2)をさらに含有し得る。上記モノマー(m2)は、水酸基を有するモノマー(水酸基含有モノマー)およびカルボキシ基を有するモノマー(カルボキシ基含有モノマー)の少なくとも一方に該当するモノマーである。上記水酸基含有モノマーは、1分子内に少なくとも1つの水酸基と少なくとも1つのエチレン性不飽和基とを有する化合物である。上記カルボキシ基含有モノマーは、1分子内に少なくとも1つのカルボキシ基と少なくとも1つのエチレン性不飽和基とを含む化合物である。モノマー(m2)は、アクリル系ポリマーに架橋点を導入したり、粘着剤に適度な凝集性を付与したりするために役立ち得る。モノマー(m2)は、1種を単独でまたは2種以上を組み合わせて用いることができる。モノマー(m2)は、典型的には芳香環を含有しないモノマーである。
(Monomer (m2))
In some aspects of the techniques disclosed herein, the monomer component constituting the acrylic polymer may further contain a monomer (m2) in addition to the above-mentioned monomer (m1). The monomer (m2) is a monomer corresponding to at least one of a monomer having a hydroxyl group (hydroxyl group-containing monomer) and a monomer having a carboxy group (carboxy group-containing monomer). The hydroxyl group-containing monomer is a compound having at least one hydroxyl group and at least one ethylenically unsaturated group in one molecule. The carboxy group-containing monomer is a compound containing at least one carboxy group and at least one ethylenically unsaturated group in one molecule. The monomer (m2) can be useful for introducing cross-linking points into the acrylic polymer and imparting appropriate cohesiveness to the pressure-sensitive adhesive. The monomer (m2) may be used alone or in combination of two or more. The monomer (m2) is typically a monomer that does not contain an aromatic ring.
 モノマー(m2)の有するエチレン性不飽和基の例としては、(メタ)アクリロイル基、ビニル基、(メタ)アリル基等が挙げられる。重合反応性の観点から(メタ)アクリロイル基が好ましく、柔軟性や粘着性の観点からアクリロイル基がより好ましい。粘着剤の柔軟性低下を抑制する観点から、モノマー(m2)としては、1分子中に含まれるエチレン性不飽和基の数が1である化合物(すなわち、単官能モノマー)が好ましく用いられる。 Examples of the ethylenically unsaturated group contained in the monomer (m2) include a (meth) acryloyl group, a vinyl group, a (meth) allyl group and the like. A (meth) acryloyl group is preferable from the viewpoint of polymerization reactivity, and an acryloyl group is more preferable from the viewpoint of flexibility and adhesiveness. From the viewpoint of suppressing a decrease in the flexibility of the pressure-sensitive adhesive, a compound (that is, a monofunctional monomer) in which the number of ethylenically unsaturated groups contained in one molecule is 1 is preferably used as the monomer (m2).
 水酸基含有モノマーの例としては、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸4-ヒドロキシブチル、(メタ)アクリル酸6-ヒドロキシヘキシル、(メタ)アクリル酸8-ヒドロキシオクチル、(メタ)アクリル酸10-ヒドロキシデシル、(メタ)アクリル酸12-ヒドロキシラウリル、(4-ヒドロキシメチルシクロへキシル)メチル(メタ)アクリレート等の(メタ)アクリル酸ヒドロキシアルキルが挙げられるが、これらに限定されない。好ましく使用し得る水酸基含有モノマーの例として、アクリル酸4-ヒドロキシブチル(Tg:-40℃)およびアクリル酸2-ヒドロキシエチル(Tg:-15℃)が挙げられる。室温域における柔軟性向上の観点から、よりTgの低いアクリル酸4-ヒドロキシブチルがより好ましい。好ましい一態様では、モノマー(m2)の50重量%以上(例えば50重量%超、70重量%超または85重量%超)がアクリル酸4-ヒドロキシブチルであり得る。水酸基含有モノマーは、1種を単独でまたは2種以上を組み合わせて用いることができる。 Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and (meth). ) Hydroxy (meth) acrylate such as 8-hydroxyoctyl acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate Alkyl includes, but is not limited to. Examples of hydroxyl group-containing monomers that can be preferably used include 4-hydroxybutyl acrylate (Tg: −40 ° C.) and 2-hydroxyethyl acrylate (Tg: −15 ° C.). From the viewpoint of improving flexibility in the room temperature range, 4-hydroxybutyl acrylate having a lower Tg is more preferable. In a preferred embodiment, more than 50% by weight (eg, more than 50% by weight, more than 70% by weight or more than 85% by weight) of the monomer (m2) can be 4-hydroxybutyl acrylate. The hydroxyl group-containing monomer may be used alone or in combination of two or more.
 モノマー(m2)として水酸基含有モノマーを使用するいくつかの態様において、上記水酸基含有モノマーは、メタクリロイル基を有しない化合物から選択される1種または2種以上であり得る。メタクリロイル基を有しない水酸基含有モノマーの好適例として、上述した各種のアクリル酸ヒドロキシアルキルが挙げられる。例えば、モノマー(m2)として使用する水酸基含有モノマーのうち50重量%超、70重量%超または85重量%超がアクリル酸ヒドロキシアルキルであることが好ましい。アクリル酸ヒドロキシアルキルの使用により、架橋点の提供や適度な凝集性の付与に役立つヒドロキシ基をアクリル系ポリマーに導入することができ、かつ対応するメタクリル酸ヒドロキシアルキルのみを使用する場合に比べて室温域における柔軟性や粘着性の良い粘着剤が得られやすい。 In some embodiments where a hydroxyl group-containing monomer is used as the monomer (m2), the hydroxyl group-containing monomer may be one or more selected from compounds having no methacryloyl group. Preferable examples of the hydroxyl group-containing monomer having no methacryloyl group include the above-mentioned various hydroxyalkyl acrylates. For example, it is preferable that more than 50% by weight, more than 70% by weight, or more than 85% by weight of the hydroxyl group-containing monomers used as the monomer (m2) is hydroxyalkyl acrylate. By using hydroxyalkyl acrylate, hydroxy groups that help provide cross-linking points and impart appropriate cohesiveness can be introduced into the acrylic polymer, and the room temperature is higher than when only the corresponding hydroxyalkyl methacrylate is used. It is easy to obtain an adhesive with good flexibility and adhesiveness in the region.
 カルボキシ基含有モノマーの例としては、(メタ)アクリル酸、(メタ)アクリル酸カルボキシエチル、(メタ)アクリル酸カルボキシペンチル等のアクリル系モノマーのほか、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸等が挙げられるが、これらに限定されない。好ましく使用し得るカルボキシ基含有モノマーの例として、アクリル酸、メタクリル酸が挙げられる。カルボキシ基含有モノマーは、1種を単独でまたは2種以上を組み合わせて用いることができる。水酸基含有モノマーとカルボキシ基含有モノマーとを併用してもよい。 Examples of carboxy group-containing monomers include acrylic monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate, as well as itaconic acid, maleic acid, fumaric acid, and crotonic acid. Examples thereof include, but are not limited to, isocrotonic acid. Examples of carboxy group-containing monomers that can be preferably used include acrylic acid and methacrylic acid. The carboxy group-containing monomer may be used alone or in combination of two or more. A hydroxyl group-containing monomer and a carboxy group-containing monomer may be used in combination.
 アクリル系ポリマーを構成するモノマー成分におけるモノマー(m2)の含有量は、特に制限されず、目的に応じて設定し得る。いくつかの態様において、上記モノマー(m2)の含有量は、例えば0.01重量%以上、0.1重量%以上または0.5重量%以上であり得る。より高い使用効果を得る観点から、いくつかの態様において、上記モノマー(A2)の含有量は、1重量%以上とすることが好ましく、2重量%以上としてもよく、4重量%以上としてもよい。モノマー成分におけるモノマー(m2)の含有量の上限は、他のモノマーの含有量との合計が100重量%を超えないように設定される。いくつかの態様において、上記モノマー(m2)の含有量は、例えば30重量%以下または25重量%以下とすることが適当であり、モノマー(m1)の含有量を相対的に多くして高屈折率化を容易とする観点から、20重量%以下とすることが好ましく、15重量%以下とすることがより好ましく、12重量%未満でもよく、10重量%未満でもよく、7重量%未満でもよい。 The content of the monomer (m2) in the monomer component constituting the acrylic polymer is not particularly limited and can be set according to the purpose. In some embodiments, the content of the monomer (m2) can be, for example, 0.01% by weight or more, 0.1% by weight or more, or 0.5% by weight or more. From the viewpoint of obtaining a higher effect of use, in some embodiments, the content of the monomer (A2) is preferably 1% by weight or more, preferably 2% by weight or more, or 4% by weight or more. .. The upper limit of the content of the monomer (m2) in the monomer component is set so that the total content with the content of other monomers does not exceed 100% by weight. In some embodiments, it is appropriate that the content of the monomer (m2) is, for example, 30% by weight or less or 25% by weight or less, and the content of the monomer (m1) is relatively increased to achieve high refraction. From the viewpoint of facilitating rate, it is preferably 20% by weight or less, more preferably 15% by weight or less, less than 12% by weight, less than 10% by weight, or less than 7% by weight. ..
 モノマー(m2)として水酸基含有モノマーを用いる態様において、モノマー成分における水酸基含有モノマーの含有量は、特に制限されず、例えば0.01重量%以上(好ましくは0.1重量%以上、より好ましくは0.5重量%以上)であり得る。いくつかの態様において、上記水酸基含有モノマーの含有量は、上記モノマー成分の1重量%以上とすることが好ましく、2重量%以上としてもよく、4重量%以上としてもよい。モノマー成分における水酸基含有モノマーの含有量の上限は、他のモノマーの含有量との合計が100重量%を超えないように設定され、例えば30重量%以下または25重量%以下とすることが適当であり、モノマー(m1)の含有量を相対的に多くして高屈折率化を容易とする観点から20重量%以下とすることが好ましく、15重量%以下とすることがより好ましく、12重量%未満でもよく、10重量%未満でもよく、7重量%未満でもよい。 In the embodiment in which the hydroxyl group-containing monomer is used as the monomer (m2), the content of the hydroxyl group-containing monomer in the monomer component is not particularly limited, and is, for example, 0.01% by weight or more (preferably 0.1% by weight or more, more preferably 0). It can be 5.5% by weight or more). In some embodiments, the content of the hydroxyl group-containing monomer is preferably 1% by weight or more, preferably 2% by weight or more, or 4% by weight or more of the monomer component. The upper limit of the content of the hydroxyl group-containing monomer in the monomer component is set so that the total content with the content of other monomers does not exceed 100% by weight, and it is appropriate to set it to, for example, 30% by weight or less or 25% by weight or less. From the viewpoint of facilitating high refractive index by relatively increasing the content of the monomer (m1), it is preferably 20% by weight or less, more preferably 15% by weight or less, and 12% by weight. It may be less than 10% by weight, less than 7% by weight, or less than 7% by weight.
 モノマー(m2)としてカルボキシ基含有モノマーを用いる態様において、モノマー成分におけるカルボキシ基含有モノマーの含有量は、特に制限されず、例えば0.01重量%以上(好ましくは0.1重量%以上、より好ましくは0.3重量%以上)であり得る。いくつかの態様において、上記カルボキシ基含有モノマーの含有量は、1重量%以上としてもよく、2重量%以上としてもよく、4重量%以上としてもよい。モノマー成分におけるカルボキシ基含有モノマーの含有量の上限は、他のモノマーの使用量との合計が100重量%を超えないように設定され、例えば30重量%以下または25重量%以下とすることが適当であり、モノマー(m1)の含有量を相対的に多くして高屈折率化を容易とする観点から、20重量%以下とすることが好ましく、15重量%以下とすることがより好ましく、12重量%未満でもよく、10重量%未満でもよい。いくつかの態様において、粘着剤の柔軟性向上の観点から、上記カルボキシ基含有モノマーの含有量は、7重量%未満とすることが有利であり、5重量%未満とすることが好ましく、3重量%未満としてもよく、1重量%未満としてもよく、0.5重量%未満としてもよい。ここに開示される技術は、例えば、モノマー(m2)として水酸基含有モノマーのみを用いる態様、すなわちカルボキシ基含有モノマーを使用しない態様で好ましく実施され得る。 In the embodiment in which the carboxy group-containing monomer is used as the monomer (m2), the content of the carboxy group-containing monomer in the monomer component is not particularly limited, and is, for example, 0.01% by weight or more (preferably 0.1% by weight or more, more preferably 0.1% by weight or more). Can be 0.3% by weight or more). In some embodiments, the content of the carboxy group-containing monomer may be 1% by weight or more, 2% by weight or more, or 4% by weight or more. The upper limit of the content of the carboxy group-containing monomer in the monomer component is set so that the total with the amount of other monomers used does not exceed 100% by weight, and it is appropriate to set it to, for example, 30% by weight or less or 25% by weight or less. From the viewpoint of facilitating a high refractive index by relatively increasing the content of the monomer (m1), the content is preferably 20% by weight or less, more preferably 15% by weight or less, and 12 It may be less than 10% by weight, or less than 10% by weight. In some embodiments, from the viewpoint of improving the flexibility of the pressure-sensitive adhesive, the content of the carboxy group-containing monomer is preferably less than 7% by weight, preferably less than 5% by weight, and 3% by weight. It may be less than%, less than 1% by weight, or less than 0.5% by weight. The technique disclosed herein can be preferably carried out, for example, in a mode in which only a hydroxyl group-containing monomer is used as the monomer (m2), that is, a mode in which a carboxy group-containing monomer is not used.
 アクリル系ポリマーを構成するモノマー成分におけるモノマー(m1)とモノマー(m2)との合計含有量は、例えば31重量%以上であってよく、好ましくは51重量%以上であり、61重量%以上でもよく、71重量%以上でもよい。いくつかの態様において、アクリル系ポリマーを構成するモノマー成分におけるモノマー(m1)とモノマー(m2)との合計含有量は、これらのモノマーの効果を好適に発揮しやすくする観点から、例えば76重量%以上であってよく、81重量%以上であることが好ましく、86重量%以上でもよく、91重量%以上でもよく、96重量%以上でもよく、99重量%以上でもよく、実質的に100重量%でもよい。 The total content of the monomer (m1) and the monomer (m2) in the monomer component constituting the acrylic polymer may be, for example, 31% by weight or more, preferably 51% by weight or more, or 61% by weight or more. , 71% by weight or more. In some embodiments, the total content of the monomer (m1) and the monomer (m2) in the monomer component constituting the acrylic polymer is, for example, 76% by weight from the viewpoint of facilitating the effect of these monomers. It may be more than 81% by weight, preferably 86% by weight or more, 91% by weight or more, 96% by weight or more, 99% by weight or more, substantially 100% by weight. But it may be.
 (モノマーm3)
 アクリル系ポリマーを構成するモノマー成分は、必要に応じて、上記モノマー(m1)および上記モノマー(m2)以外のモノマーを含んでいてもよい。そのような任意成分の一例として、アルキル(メタ)アクリレート(以下、「モノマー(m3)」ともいう。)が挙げられる。モノマー(m3)は、粘着剤の柔軟性の調整や、粘着剤内における相溶性の改善に役立ち得る。
(Monomer m3)
The monomer component constituting the acrylic polymer may contain a monomer other than the above-mentioned monomer (m1) and the above-mentioned monomer (m2), if necessary. An example of such an optional component is an alkyl (meth) acrylate (hereinafter, also referred to as “monomer (m3)”). The monomer (m3) can be useful for adjusting the flexibility of the pressure-sensitive adhesive and improving the compatibility in the pressure-sensitive adhesive.
 モノマー(m3)としては、炭素原子数1~20の(すなわち、C1-20の)直鎖または分岐鎖状のアルキル基をエステル末端に有するアルキル(メタ)アクリレートが好ましく用いられ得る。C1-20アルキル(メタ)アクリレートの具体例としては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸s-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸イソペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸ウンデシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸トリデシル、(メタ)アクリル酸テトラデシル、(メタ)アクリル酸ペンタデシル、(メタ)アクリル酸ヘキサデシル、(メタ)アクリル酸ヘプタデシル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸イソステアリル、(メタ)アクリル酸ノナデシル、(メタ)アクリル酸エイコシル等が挙げられるが、これらに限定されない。 As the monomer (m3), an alkyl (meth) acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms (that is, C 1-20) at the ester terminal can be preferably used. Specific examples of C 1-20 alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, (meth) ) Heptyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) Isodecyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, (meth) ) Heptadecyl acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, nonadecil (meth) acrylate, eikosyl (meth) acrylate and the like, but are not limited thereto.
 いくつかの態様において、モノマー(m3)の少なくとも一部として、ホモポリマーのTgが-20℃以下(より好ましくは-40℃以下、例えば-50℃以下)であるアルキル(メタ)アクリレートを好ましく採用し得る。このような低Tgのアルキル(メタ)アクリレートは、粘着剤の柔軟性の向上に役立ち得る。上記アルキル(メタ)アクリレートのTgの下限は特に制限されず、例えば-85℃以上であってよく、-75℃以上でもよく、-65℃以上でもよく、-60℃以上でもよい。上記低Tgアルキル(メタ)アクリレートの具体例としては、アクリル酸n-ブチル(BA)、アクリル酸2-エチルヘキシル(2EHA)、アクリル酸イソノニル(iNA)等が挙げられる。 In some embodiments, alkyl (meth) acrylates having a homopolymer Tg of −20 ° C. or lower (more preferably −40 ° C. or lower, eg, −50 ° C. or lower) are preferably employed as at least a portion of the monomer (m3). Can be done. Such low Tg alkyl (meth) acrylates can help improve the flexibility of the adhesive. The lower limit of Tg of the alkyl (meth) acrylate is not particularly limited, and may be, for example, −85 ° C. or higher, −75 ° C. or higher, −65 ° C. or higher, or −60 ° C. or higher. Specific examples of the low Tg alkyl (meth) acrylate include n-butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), and isononyl acrylate (iNA).
 モノマー(m3)を使用するいくつかの態様において、柔軟性や粘着性等の観点から、上記モノマー(m3)の少なくとも一部はアルキルアクリレートであることが好ましい。例えば、モノマー(m3)のうち50重量%以上(より好ましくは75重量%以上、さらに好ましくは90重量%以上)がアルキルアクリレートであることが好ましい。モノマー(m3)として1種または2種以上のアルキルアクリレートのみを使用し、アルキルメタクリレートを使用しない態様であってもよい。 In some embodiments where the monomer (m3) is used, it is preferable that at least a part of the monomer (m3) is an alkyl acrylate from the viewpoint of flexibility, adhesiveness and the like. For example, it is preferable that 50% by weight or more (more preferably 75% by weight or more, still more preferably 90% by weight or more) of the monomer (m3) is an alkyl acrylate. It may be an embodiment in which only one kind or two or more kinds of alkyl acrylates are used as the monomer (m3) and no alkyl methacrylate is used.
 モノマー成分がアルキル(メタ)アクリレートを含む態様において、モノマー成分におけるアルキル(メタ)アクリレートの含有量は、その使用効果が適切に発揮されるように設定することができる。いくつかの態様において、上記アルキル(メタ)アクリレートの含有量は、例えば1重量%以上であってよく、3重量%以上でもよく、5重量%以上でもよく、8重量%以上でもよい。いくつかの態様において、上記アルキル(メタ)アクリレートの含有量は、15重量%以上でもよく、30重量%以上でもよく、45重量%以上でもよい。モノマー成分におけるモノマー(m3)の含有量の上限は、他のモノマーの含有量との合計が100重量%を超えないように設定され、例えば50重量%未満であり得る。いくつかの態様において、上記モノマー(m3)の含有量は、例えば35重量%未満であり得る。一般にアルキル(メタ)アクリレートの屈折率は比較的低いため、高屈折率化のためには、モノマー成分におけるモノマー(m3)の含有量を制限し、モノマー(m1)の含有量を相対的に多くすることが有利である。かかる観点から、モノマー(m3)の含有量は、モノマー成分の24重量%以下であることが有利であり、23重量%未満であることが好ましく、20重量%未満であることがより好ましく、17重量%未満でもよく、12重量%未満でもよく、7重量%未満でもよく、3重量%未満でもよく、1重量%未満でもよい。モノマー(m3)を実質的に使用しなくてもよい。 In the embodiment in which the monomer component contains an alkyl (meth) acrylate, the content of the alkyl (meth) acrylate in the monomer component can be set so that the effect of use thereof is appropriately exhibited. In some embodiments, the content of the alkyl (meth) acrylate may be, for example, 1% by weight or more, 3% by weight or more, 5% by weight or more, or 8% by weight or more. In some embodiments, the content of the alkyl (meth) acrylate may be 15% by weight or more, 30% by weight or more, or 45% by weight or more. The upper limit of the content of the monomer (m3) in the monomer component is set so that the total content with the content of other monomers does not exceed 100% by weight, and can be, for example, less than 50% by weight. In some embodiments, the content of the monomer (m3) can be, for example, less than 35% by weight. In general, the refractive index of alkyl (meth) acrylate is relatively low. Therefore, in order to increase the refractive index, the content of the monomer (m3) in the monomer component is limited, and the content of the monomer (m1) is relatively large. It is advantageous to do. From this point of view, the content of the monomer (m3) is preferably 24% by weight or less, preferably less than 23% by weight, more preferably less than 20% by weight, 17% by weight of the monomer component. It may be less than% by weight, less than 12% by weight, less than 7% by weight, less than 3% by weight, or less than 1% by weight. It is not necessary to use the monomer (m3) substantially.
 (その他のモノマー)
 アクリル系ポリマーを構成するモノマー成分は、必要に応じて、上記モノマー(m1)、(m2)、(m3)以外のモノマー(以下、「その他モノマー」という。)を含んでいてもよい。上記その他モノマーは、例えば、アクリル系ポリマーのTg調整、粘着性能の調整、粘着剤層内における相溶性の改善等の目的で使用することができる。上記その他モノマーは、1種を単独でまたは2種以上を組み合わせて用いることができる。
(Other monomers)
The monomer component constituting the acrylic polymer may contain a monomer other than the above-mentioned monomers (m1), (m2), and (m3) (hereinafter, referred to as "other monomer"), if necessary. The above-mentioned other monomers can be used, for example, for the purpose of adjusting Tg of an acrylic polymer, adjusting the adhesive performance, improving the compatibility in the pressure-sensitive adhesive layer, and the like. The above-mentioned other monomers may be used alone or in combination of two or more.
 上記その他モノマーの例として、水酸基およびカルボキシ基以外の官能基を有するモノマー(官能基含有モノマー)が挙げられる。例えば、粘着剤の凝集力や耐熱性を向上させ得るその他モノマーとして、スルホン酸基含有モノマー、リン酸基含有モノマー、シアノ基含有モノマー等が挙げられる。また、アクリル系ポリマーに架橋基点となり得る官能基を導入することができ、あるいは剥離強度の向上や粘着剤層内における相溶性の改善に寄与し得るモノマーとして、アミド基含有モノマー(例えば、(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド等)、アミノ基含有モノマー(例えば、アミノエチル(メタ)アクリレート、N,N-ジメチルアミノエチル(メタ)アクリレート等)、窒素原子含有環を有するモノマー(例えば、N-ビニル-2-ピロリドン、N-(メタ)アクリロイルモルホリン等)、イミド基含有モノマー、エポキシ基含有モノマー、ケト基含有モノマー、イソシアネート基含有モノマー、アルコキシシリル基含有モノマー等が挙げられる。なお、窒素原子含有環を有するモノマーのなかには、例えばN-ビニル-2-ピロリドンのように、アミド基含有モノマーにも該当するものがある。上記窒素原子含有環を有するモノマーとアミノ基含有モノマーとの関係についても同様である。 Examples of the above-mentioned other monomers include monomers having functional groups other than hydroxyl groups and carboxy groups (functional group-containing monomers). For example, other monomers that can improve the cohesive force and heat resistance of the pressure-sensitive adhesive include sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, and cyano group-containing monomers. Further, as a monomer capable of introducing a functional group that can serve as a cross-linking base point into the acrylic polymer, or contributing to improvement of peel strength and compatibility in the pressure-sensitive adhesive layer, an amide group-containing monomer (for example, (meth). ) Acrylamide, N-methylol (meth) acrylamide, etc.), amino group-containing monomer (for example, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, etc.), monomer having a nitrogen atom-containing ring (for example, , N-vinyl-2-pyrrolidone, N- (meth) acryloylmorpholine, etc.), imide group-containing monomer, epoxy group-containing monomer, keto group-containing monomer, isocyanate group-containing monomer, alkoxysilyl group-containing monomer, and the like. In addition, among the monomers having a nitrogen atom-containing ring, there is also a monomer corresponding to an amide group-containing monomer such as N-vinyl-2-pyrrolidone. The same applies to the relationship between the monomer having a nitrogen atom-containing ring and the amino group-containing monomer.
 上記官能基含有モノマー以外で使用し得るその他モノマーとしては、酢酸ビニル等のビニルエステル系モノマー;シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート等の非芳香族性環含有(メタ)アクリレート;エチレン、ブタジエン、イソブチレン等のオレフィン系モノマー;塩化ビニル等の塩素含有モノマー;メトキシエチル(メタ)アクリレート、エトキシエチル(メタ)アクリレート、エトキシエトキシエチル(メタ)アクリレート等のアルコキシ基含有モノマー;メチルビニルエーテル等のビニルエーテル系モノマー;等が挙げられる。粘着剤の柔軟性向上等の目的で使用し得るその他モノマーの一好適例として、エトキシエトキシエチルアクリレート(別名:エチルカルビトールアクリレート、ホモポリマーのTg:-67℃)が挙げられる。 Other monomers that can be used other than the above functional group-containing monomers include vinyl ester-based monomers such as vinyl acetate; non-aromatic ring-containing (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; ethylene, Olefin-based monomers such as butadiene and isobutylene; Chlorine-containing monomers such as vinyl chloride; alkoxy group-containing monomers such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and ethoxyethoxyethyl (meth) acrylate; Vinyl ether such as methyl vinyl ether System monomers; and the like. As one preferable example of other monomers that can be used for the purpose of improving the flexibility of the pressure-sensitive adhesive, ethoxyethoxyethyl acrylate (also known as ethyl carbitol acrylate, homopolymer Tg: −67 ° C.) can be mentioned.
 上記その他モノマーを使用する場合、その使用量は特に制限されず、モノマー成分の合計量が100重量%を超えない範囲で適宜設定し得る。いくつかの態様において、モノマー(m1)の使用による屈折率向上効果を発揮しやすくする観点から、モノマー成分における上記その他モノマーの含有量は、例えば凡そ35重量%以下とすることができ、凡そ25重量%以下(例えば0~25重量%)とすることが適当であり、凡そ20重量%以下(例えば0~20重量%)でもよく、凡そ10重量%以下でもよく、凡そ5重量%以下でもよく、例えば凡そ1重量%以下でもよい。ここに開示される技術は、モノマー成分が上記その他のモノマーを実質的に含まない態様で好ましく実施され得る。 When the above-mentioned other monomers are used, the amount used is not particularly limited, and can be appropriately set within a range in which the total amount of the monomer components does not exceed 100% by weight. In some embodiments, the content of the other monomer in the monomer component can be, for example, about 35% by weight or less, and is about 25, from the viewpoint of facilitating the effect of improving the refractive index by using the monomer (m1). It is appropriate to set it to about 20% by weight or less (for example, 0 to 25% by weight), and it may be about 20% by weight or less (for example, 0 to 20% by weight), about 10% by weight or less, or about 5% by weight or less. For example, it may be about 1% by weight or less. The technique disclosed herein can be preferably carried out in a manner in which the monomer component is substantially free of the other monomers.
 いくつかの態様において、アクリル系ポリマーを構成するモノマー成分は、メタクリロイル基含有モノマーの使用量が所定以下に抑えられた組成であり得る。モノマー成分におけるメタクリロイル基含有モノマーの使用量は、例えば5重量%未満であってよく、3重量%未満でもよく、1重量%未満でもよく、0.5重量%未満でもよい。このようにメタクリロイル基含有モノマーの使用量を制限することは、柔軟性や粘着性と高屈折率とをバランスよく両立させた粘着剤を実現する観点から有利となり得る。アクリル系ポリマーを構成するモノマー成分は、メタクリロイル基含有モノマーを含まない組成(例えば、アクリロイル基含有モノマーのみからなる組成)であってもよい。 In some embodiments, the monomer component constituting the acrylic polymer may have a composition in which the amount of the methacryloyl group-containing monomer used is suppressed to a predetermined value or less. The amount of the methacryloyl group-containing monomer used in the monomer component may be, for example, less than 5% by weight, less than 3% by weight, less than 1% by weight, or less than 0.5% by weight. Limiting the amount of the methacryloyl group-containing monomer used in this way can be advantageous from the viewpoint of realizing a pressure-sensitive adhesive having both flexibility and adhesiveness and a high refractive index in a well-balanced manner. The monomer component constituting the acrylic polymer may have a composition that does not contain a methacryloyl group-containing monomer (for example, a composition consisting of only an acryloyl group-containing monomer).
 いくつかの態様において、粘着剤層のベースポリマー(例えば、アクリル系ポリマー)を構成するモノマー成分は、粘着剤の着色または変色(例えば黄変)を抑制する観点から、カルボキシ基含有モノマーの使用量が制限されていることが好ましい。モノマー成分におけるカルボキシ基含有モノマーの使用量は、例えば1重量%未満であってよく、0.5重量%未満であることが好ましく、0.3重量%未満であることがより好ましく、0.1重量%未満でもよく、0.05重量%未満でもよい。このようにカルボキシ基含有モノマーの使用量が制限されていることは、ここに開示される粘着剤に接触または近接して配置され得る金属材料(例えば、被着体上に存在し得る金属配線や金属膜等)の腐食を抑制する観点からも有利である。ここに開示される技術は、上記モノマー成分がカルボキシ基含有モノマーを含有しない態様で好ましく実施され得る。
 同様の理由から、いくつかの態様において、粘着剤層のベースポリマーを構成するモノマー成分は、酸性官能基(カルボキシ基の他、スルホン酸基、リン酸基等を包含する。)を有するモノマーの使用量が制限されていることが好ましい。かかる態様のモノマー成分における酸性官能基含有モノマーの使用量としては、上述したカルボキシ基含有モノマーの好ましい使用量を適用することができる。ここに開示される技術は、上記モノマー成分が酸性基含有モノマーを含有しない態様(すなわち、粘着剤層のベースポリマーが酸フリーである態様)で好ましく実施され得る。
In some embodiments, the monomer component constituting the base polymer (for example, an acrylic polymer) of the pressure-sensitive adhesive layer uses an amount of a carboxy group-containing monomer from the viewpoint of suppressing coloring or discoloration (for example, yellowing) of the pressure-sensitive adhesive. Is preferably restricted. The amount of the carboxy group-containing monomer used in the monomer component may be, for example, less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.3% by weight, and 0.1. It may be less than% by weight or less than 0.05% by weight. This limitation of the amount of carboxy group-containing monomer used means that metal materials that can be placed in contact with or in close proximity to the adhesives disclosed herein (eg, metal wiring that may be present on the adherend). It is also advantageous from the viewpoint of suppressing corrosion of metal films, etc.). The technique disclosed herein can be preferably carried out in a manner in which the above-mentioned monomer component does not contain a carboxy group-containing monomer.
For the same reason, in some embodiments, the monomer component constituting the base polymer of the pressure-sensitive adhesive layer is a monomer having an acidic functional group (including a sulfonic acid group, a phosphoric acid group, etc. in addition to a carboxy group). It is preferable that the amount used is limited. As the amount of the acidic functional group-containing monomer used in the monomer component of such an embodiment, the above-mentioned preferable amount of the carboxy group-containing monomer can be applied. The technique disclosed herein can be preferably carried out in a mode in which the monomer component does not contain an acidic group-containing monomer (that is, a mode in which the base polymer of the pressure-sensitive adhesive layer is acid-free).
 (ベースポリマーのガラス転移温度Tg
 いくつかの態様において、粘着剤層のベースポリマー(例えば、アクリル系ポリマー)は、該ポリマーを構成するモノマー成分の組成に基づくガラス転移温度Tgが、凡そ20℃以下であることが適当であり、凡そ10℃以下であることが好ましく、0℃以下であることがより好ましく、-10℃以下でもよく、-20℃以下でもよく、-25℃以下でもよく、-28℃以下でもよく、-30℃以下でもよい。ガラス転移温度Tgが低いことは、粘着剤の柔軟性向上の観点から有利となり得る。また、ガラス転移温度Tgは、例えば-60℃以上であってよく、粘着剤の高屈折率化を容易とする観点から、好ましくは-50℃以上であり、より好ましくは-45℃超であり、-40℃超であってもよく、-35℃超であってもよく、-25℃超であってもよく、-15℃以上であってもよく、-5℃以上であってもよい。
(Glass transition temperature of base polymer Tg T )
In some embodiments, the base polymer of the pressure-sensitive adhesive layer (eg, an acrylic polymer) preferably has a glass transition temperature Tg T based on the composition of the monomer components constituting the polymer, which is approximately 20 ° C. or lower. , Approximately 10 ° C or lower, more preferably 0 ° C or lower, -10 ° C or lower, -20 ° C or lower, -25 ° C or lower, −28 ° C or lower, −28 ° C or lower, − It may be 30 ° C. or lower. A low glass transition temperature Tg T can be advantageous from the viewpoint of improving the flexibility of the pressure-sensitive adhesive. The glass transition temperature Tg T may be, for example, −60 ° C. or higher, preferably −50 ° C. or higher, and more preferably −45 ° C. or higher, from the viewpoint of facilitating high refractive index of the pressure-sensitive adhesive. Yes, it may be above -40 ° C, above -35 ° C, above -25 ° C, above -15 ° C, or above -5 ° C. good.
 ここで、ポリマーのガラス転移温度Tgとは、特記しない場合、該ポリマーを構成するモノマー成分の組成に基づいて、Foxの式により求められるガラス転移温度をいう。Foxの式とは、以下に示すように、共重合体のTgと、該共重合体を構成するモノマーのそれぞれを単独重合したホモポリマーのガラス転移温度Tgiとの関係式である。
   1/Tg=Σ(Wi/Tgi)
 上記Foxの式において、Tgは共重合体のガラス転移温度(単位:K)、Wiは該共重合体におけるモノマーiの重量分率(重量基準の共重合割合)、Tgiはモノマーiのホモポリマーのガラス転移温度(単位:K)を表す。
 Tgの算出に使用するホモポリマーのガラス転移温度としては、「Polymer Handbook」(第3版、John Wiley & Sons, Inc., 1989年)等の公知資料に記載の値を用いるものとする。上記Polymer Handbookに複数種類の値が記載されているモノマーについては、最も高い値を採用する。公知資料にホモポリマーのTgが記載されていない場合は、日本国特許出願公開2007-51271号公報に記載の測定方法により得られる値を用いるものとする。
Here, the glass transition temperature Tg T of the polymer means the glass transition temperature obtained by the Fox formula based on the composition of the monomer components constituting the polymer, unless otherwise specified. As shown below, the Fox formula is a relational expression between the Tg of the copolymer and the glass transition temperature Tgi of the homopolymer in which each of the monomers constituting the copolymer is homopolymerized.
1 / Tg = Σ (Wi / Tgi)
In the Fox formula, Tg is the glass transition temperature (unit: K) of the copolymer, Wi is the weight fraction of the monomer i in the copolymer (copolymerization ratio based on the weight), and Tgi is the homopolymer of the monomer i. Represents the glass transition temperature (unit: K) of.
As the glass transition temperature of the homopolymer used for calculating Tg, the values described in publicly known materials such as "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989) shall be used. For the monomers whose multiple types of values are described in the Polymer Handbook, the highest value is adopted. When the Tg of the homopolymer is not described in the publicly known material, the value obtained by the measuring method described in Japanese Patent Application Publication No. 2007-51271 shall be used.
 (ベースポリマーの調製方法)
 ここに開示される技術において、粘着剤層のベースポリマー(例えば、上述のようなモノマー成分により構成されたアクリル系ポリマー(A))を得る方法は特に限定されず、溶液重合法、エマルション重合法、バルク重合法、懸濁重合法、光重合法等の公知の重合方法を適宜採用することができる。いくつかの態様において、溶液重合法を好ましく採用し得る。溶液重合を行う際の重合温度は、使用するモノマーおよび溶媒の種類、重合開始剤の種類等に応じて適宜選択することができ、例えば20℃~170℃程度(典型的には40℃~140℃程度)とすることができる。
(Preparation method of base polymer)
In the technique disclosed herein, the method for obtaining the base polymer of the pressure-sensitive adhesive layer (for example, the acrylic polymer (A) composed of the above-mentioned monomer components) is not particularly limited, and is a solution polymerization method or an emulsion polymerization method. , A known polymerization method such as a bulk polymerization method, a suspension polymerization method, and a photopolymerization method can be appropriately adopted. In some embodiments, the solution polymerization method may be preferably employed. The polymerization temperature at the time of solution polymerization can be appropriately selected depending on the type of monomer and solvent used, the type of polymerization initiator, etc., and is, for example, about 20 ° C. to 170 ° C. (typically 40 ° C. to 140 ° C.). ℃).
 溶液重合に用いる溶媒(重合溶媒)は、従来公知の有機溶媒から適宜選択することができる。例えば、トルエン等の芳香族化合物類(典型的には芳香族炭化水素類);酢酸エチル等の酢酸エステル類;ヘキサンやシクロヘキサン等の脂肪族または脂環式炭化水素類;1,2-ジクロロエタン等のハロゲン化アルカン類;イソプロピルアルコール等の低級アルコール類(例えば、炭素原子数1~4の一価アルコール類);tert-ブチルメチルエーテル等のエーテル類;メチルエチルケトン等のケトン類;等から選択されるいずれか1種の溶媒、または2種以上の混合溶媒を用いることができる。 The solvent (polymerization solvent) used for solution polymerization can be appropriately selected from conventionally known organic solvents. For example, aromatic compounds such as toluene (typically aromatic hydrocarbons); acetate esters such as ethyl acetate; aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane; 1,2-dichloroethane and the like. Alkanes halogenated; lower alcohols such as isopropyl alcohol (for example, monohydric alcohols having 1 to 4 carbon atoms); ethers such as tert-butyl methyl ether; ketones such as methyl ethyl ketone; etc. Any one kind of solvent or two or more kinds of mixed solvents can be used.
 重合に用いる開始剤は、重合方法の種類に応じて、従来公知の重合開始剤から適宜選択することができる。例えば、2,2’-アゾビスイソブチロニトリル(AIBN)等のアゾ系重合開始剤の1種または2種以上を好ましく使用し得る。重合開始剤の他の例としては、過硫酸カリウム等の過硫酸塩;ベンゾイルパーオキサイド、過酸化水素等の過酸化物系開始剤;フェニル置換エタン等の置換エタン系開始剤;芳香族カルボニル化合物;等が挙げられる。重合開始剤のさらに他の例として、過酸化物と還元剤との組み合わせによるレドックス系開始剤が挙げられる。重合開始剤は、1種を単独でまたは2種以上を組み合わせて使用することができる。重合開始剤の使用量は、通常の使用量であればよく、例えば、モノマー成分100重量部に対して凡そ0.005~1重量部程度(典型的には凡そ0.01~1重量部程度)の範囲から選択することができる。 The initiator used for polymerization can be appropriately selected from conventionally known polymerization initiators according to the type of polymerization method. For example, one or more azo-based polymerization initiators such as 2,2'-azobisisobutyronitrile (AIBN) can be preferably used. Other examples of polymerization initiators include persulfates such as potassium persulfate; peroxide-based initiators such as benzoyl peroxide and hydrogen peroxide; substituted ethane-based initiators such as phenyl-substituted ethane; aromatic carbonyl compounds. ; Etc. can be mentioned. Yet another example of the polymerization initiator is a redox-based initiator that is a combination of a peroxide and a reducing agent. The polymerization initiator may be used alone or in combination of two or more. The amount of the polymerization initiator used may be a normal amount, for example, about 0.005 to 1 part by weight (typically about 0.01 to 1 part by weight) with respect to 100 parts by weight of the monomer component. ) Can be selected.
 上記重合には、必要に応じて、従来公知の各種の連鎖移動剤を使用することができる。例えば、n-ドデシルメルカプタン、t-ドデシルメルカプタン、チオグリコール酸、α-チオグリセロール等のメルカプタン類を用いることができる。あるいは、硫黄原子を含まない連鎖移動剤(非硫黄系連鎖移動剤)を用いてもよい。非硫黄系連鎖移動剤の例としては、N,N-ジメチルアニリン、N,N-ジエチルアニリン等のアニリン類;α-ピネン、ターピノーレン等のテルペノイド類;α-メチルスチレン、α-メチルスチレンダイマー等のスチレン類;等が挙げられる。連鎖移動剤は、1種を単独でまたは2種以上を組み合わせて用いることができる。連鎖移動剤を使用する場合における使用量は、モノマー原料100重量部に対して、例えば凡そ0.01~1重量部程度とすることができる。 Various conventionally known chain transfer agents can be used for the above polymerization, if necessary. For example, mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid, and α-thioglycerol can be used. Alternatively, a chain transfer agent containing no sulfur atom (non-sulfur chain transfer agent) may be used. Examples of non-sulfur chain transfer agents include anilines such as N, N-dimethylaniline and N, N-diethylaniline; terpenoids such as α-pinene and turpinolene; α-methylstyrene, α-methylstyrene dimer and the like. Styrenes; etc. The chain transfer agent may be used alone or in combination of two or more. When the chain transfer agent is used, the amount used can be, for example, about 0.01 to 1 part by weight with respect to 100 parts by weight of the monomer raw material.
 ベースポリマーの重量平均分子量(Mw)は、特に限定されず、例えば凡そ10×10~500×10の範囲であり得る。粘着性能の観点から、ベースポリマーのMwは、凡そ20×10~400×10(より好ましくは凡そ30×10~150×10、例えば凡そ50×10~130×10)の範囲にあることが好ましい。 The weight average molecular weight (Mw) of the base polymer is not particularly limited, and may be in the range of , for example, approximately 10 × 10 4 to 500 × 10 4. From the viewpoint of adhesive performance, the Mw of the base polymer is about 20 × 10 4 to 400 × 10 4 (more preferably about 30 × 10 4 to 150 × 10 4 , for example, about 50 × 10 4 to 130 × 10 4 ). It is preferably in the range.
 ここで、ポリマーのMwは、ゲルパーミエーションクロマトグラフィー(GPC)によりポリスチレン換算して求めることができる。具体的には、GPC測定装置として商品名「HLC-8220GPC」(東ソー社製)を用いて、下記の条件で測定して求めることができる。
  [GPCの測定条件]
 サンプル濃度:0.2重量%(テトラヒドロフラン溶液)
 サンプル注入量:10μL
 溶離液:テトラヒドロフラン(THF)
 流量(流速):0.6mL/分
 カラム温度(測定温度):40℃
 カラム:
  サンプルカラム:商品名「TSKguardcolumn SuperHZ-H」1本+商品名「TSKgel SuperHZM-H」2本」(東ソー社製)
  リファレンスカラム:商品名「TSKgel SuperH-RC」1本(東ソー社製)
 検出器:示差屈折計(RI)
 標準試料:ポリスチレン
Here, the Mw of the polymer can be determined by gel permeation chromatography (GPC) in terms of polystyrene. Specifically, it can be obtained by measuring under the following conditions using the trade name "HLC-8220 GPC" (manufactured by Tosoh Corporation) as the GPC measuring device.
[GPC measurement conditions]
Sample concentration: 0.2% by weight (tetrahydrofuran solution)
Sample injection volume: 10 μL
Eluent: tetrahydrofuran (THF)
Flow rate (flow velocity): 0.6 mL / min Column temperature (measurement temperature): 40 ° C
column:
Sample column: 1 product name "TSKguardcolum SuperHZ-H" + 2 product name "TSKgel SuperHZM-H" (manufactured by Tosoh Corporation)
Reference column: 1 product name "TSKgel SuperH-RC" (manufactured by Tosoh Corporation)
Detector: Differential Refractometer (RI)
Standard sample: polystyrene
 (屈折率向上剤)
 ここに開示される技術のいくつかの態様において、上述の粘着剤層(例えば、アクリル系粘着剤層)には、ベースポリマーに加えて、必要に応じて屈折率向上剤を含有させ得る。ここで、本明細書において屈折率向上剤とは、その使用により粘着剤層の屈折率を高めることのできる材料をいう。屈折率向上剤としては、該屈折率向上剤を含む粘着剤層の屈折率よりも高屈折率の材料が好ましく用いられ得る。また、屈折率向上剤としては、該屈折率向上剤を含む粘着剤層のベースポリマー(例えば、アクリル系ポリマー(A))よりも高屈折率の材料が好ましく用いられ得る。屈折率向上剤の適切な使用により、より高い屈折率と、実用的な粘着性能とを好適に両立し得る。いくつかの態様において、屈折率向上剤は有機材料であることが好ましい。屈折率向上剤として用いられる有機材料は、重合体であってもよく、非重合体であってもよい。また、重合性官能基を有していてもよく、有していなくてもよい。屈折率向上剤は、1種を単独でまたは2種以上を組み合わせて用いることができる。
(Refractive index improver)
In some aspects of the techniques disclosed herein, the above-mentioned pressure-sensitive adhesive layer (for example, an acrylic pressure-sensitive adhesive layer) may contain a refractive index improver, if necessary, in addition to the base polymer. Here, the refractive index improving agent in the present specification means a material capable of increasing the refractive index of the pressure-sensitive adhesive layer by its use. As the refractive index improver, a material having a refractive index higher than that of the pressure-sensitive adhesive layer containing the refractive index improver can be preferably used. Further, as the refractive index improving agent, a material having a higher refractive index than the base polymer (for example, the acrylic polymer (A)) of the pressure-sensitive adhesive layer containing the refractive index improving agent can be preferably used. With proper use of the refractive index improver, a higher refractive index and practical adhesive performance can be suitably compatible. In some embodiments, the refractive index improver is preferably an organic material. The organic material used as the refractive index improver may be a polymer or a non-polymer. Further, it may or may not have a polymerizable functional group. The refractive index improver may be used alone or in combination of two or more.
 屈折率向上剤(例えば、後述する添加剤(HRO))の屈折率は、ベースポリマーの屈折率との相対関係で適当な範囲に設定し得るので、特定の範囲に限定されない。屈折率向上剤の屈折率は、例えば1.55超、1.56超または1.57超であって、かつベースポリマーの屈折率より高い範囲から選択し得る。粘着剤の高屈折率化の観点から、いくつかの態様において、屈折率向上剤の屈折率は、1.58以上であることが有利であり、1.60以上であることが好ましく、1.63以上であることがより好ましく、1.65以上でもよく、1.70以上でもよく、1.75以上でもよい。より屈折率の高い屈折率向上剤によると、より少量の屈折率向上剤の使用によっても目的の屈折率を達成し得る。このことは粘着特性や光学特性の低下抑制の観点から好ましい。屈折率向上剤の屈折率の上限は特に制限されないが、粘着剤内における相溶性や、高屈折率化と粘着剤として適した柔軟性との両立容易性等の観点から、例えば3.000以下であり、2.500以下でもよく、2.000以下でもよく、1.950以下でもよく、1.900以下でもよく、1.850以下でもよい。 The refractive index of the refractive index improver (for example, the additive (H RO ) described later) can be set in an appropriate range in relation to the refractive index of the base polymer, and is not limited to a specific range. The refractive index of the refractive index improver can be selected from, for example, more than 1.55, more than 1.56 or more than 1.57, and higher than the refractive index of the base polymer. From the viewpoint of increasing the refractive index of the pressure-sensitive adhesive, in some embodiments, the refractive index of the refractive index improver is preferably 1.58 or more, preferably 1.60 or more. It is more preferably 63 or more, 1.65 or more, 1.70 or more, or 1.75 or more. According to the refractive index improver having a higher refractive index, the desired refractive index can be achieved by using a smaller amount of the refractive index improver. This is preferable from the viewpoint of suppressing deterioration of adhesive properties and optical properties. The upper limit of the refractive index of the refractive index improver is not particularly limited, but from the viewpoint of compatibility in the pressure-sensitive adhesive and the ease of compatibility between high refractive index and flexibility suitable as a pressure-sensitive adhesive, for example, 3.000 or less. It may be 2.500 or less, 2.000 or less, 1.950 or less, 1.900 or less, or 1.850 or less.
 いくつかの態様において、屈折率向上剤(例えば、後述する添加剤(HRO))の屈折率nとベースポリマーの屈折率nとの差、すなわちn-n(以下、「Δn」ともいう。)は、0より大きくなるように設定される。いくつかの態様において、Δnは、例えば0.02以上であり、0.05以上でもよく、0.07以上でもよく、0.10以上でもよく、0.15以上でもよく、0.20以上または0.25以上でもよい。Δnがより大きくなるようにベースポリマーおよび屈折率向上剤を選択することにより、屈折率向上剤の使用による屈折率向上効果は高くなる傾向にある。また、粘着剤層内における相溶性や、粘着剤層の透明性等の観点から、いくつかの態様において、Δnは、例えば0.70以下であってよく、0.60以下でもよく、0.50以下でもよく、0.40以下または0.35以下でもよい。 In some embodiments, the refractive index improvers (e.g., later-described additives (H RO)) difference between the refractive index n a of the refractive index n b and the base polymer, i.e. n b -n a (hereinafter, "Δn A ”) is set to be greater than 0. In some embodiments, Δn A is, for example, 0.02 or greater, 0.05 or greater, 0.07 or higher, 0.10 or higher, 0.15 or higher, 0.20 or higher. Alternatively, it may be 0.25 or more. By selecting the base polymer and the refractive index improver so that Δn A becomes larger, the effect of improving the refractive index by using the refractive index improver tends to be higher. Further, from the viewpoint of compatibility in the pressure-sensitive adhesive layer, transparency of the pressure-sensitive adhesive layer, and the like, Δn A may be, for example, 0.70 or less, 0.60 or less, or 0 in some embodiments. It may be .50 or less, 0.40 or less, or 0.35 or less.
 いくつかの態様において、屈折率向上剤(例えば、後述する添加剤(HRO))の屈折率nと、該屈折率向上剤を含む粘着剤層の屈折率nとの差、すなわちn-n(以下、「Δn」ともいう。)は、0より大きくなるように設定される。いくつかの態様において、Δnは、例えば0.02以上であり、0.05以上でもよく、0.07以上でもよく、0.10以上でもよく、0.15以上でもよく、0.20以上または0.25以上でもよい。Δnがより大きくなるように粘着剤層の組成および屈折率向上剤を選択することにより、屈折率向上剤の使用による屈折率向上効果は高くなる傾向にある。また、粘着剤層内における相溶性や、粘着剤層の透明性等の観点から、いくつかの態様において、Δnは、例えば0.70以下であってよく、0.60以下でもよく、0.50以下でもよく、0.40以下または0.35以下でもよい。 In some embodiments, the difference between the refractive index n b of the refractive index improver (eg, additive (H RO ) described below) and the refractive index n T of the pressure-sensitive adhesive layer containing the refractive index improver, i.e. n b n T (hereinafter, also referred to as “Δn B ”) is set to be larger than 0. In some embodiments, Δn B is, for example, 0.02 or greater, 0.05 or greater, 0.07 or higher, 0.10 or higher, 0.15 or higher, 0.20 or higher. Alternatively, it may be 0.25 or more. By selecting the composition of the pressure-sensitive adhesive layer and the refractive index improver so that Δn B becomes larger, the effect of improving the refractive index by using the refractive index improver tends to be higher. Further, from the viewpoint of compatibility in the pressure-sensitive adhesive layer, transparency of the pressure-sensitive adhesive layer, and the like, Δn B may be, for example, 0.70 or less, 0.60 or less, or 0 in some embodiments. It may be .50 or less, 0.40 or less, or 0.35 or less.
 ベースポリマー100重量部に対する屈折率向上剤の使用量(複数種の屈折率向上剤を用いる場合は、それらの合計量)は、特に限定されず、目的に応じて設定することができる。粘着剤の高屈折率化の観点から、ベースポリマー100重量部に対する屈折率向上剤の使用量は、例えば1重量部以上とすることができ、3重量部以上とすることが有利であり、5重量部以上とすることが好ましく、7重量部以上でもよく、10重量部以上でもよく、15重量部以上でもよく、20重量部以上でもよい。また、いくつかの態様において、ベースポリマー100重量部に対する屈折率向上剤の使用量は、例えば80重量部以下とすることができ、粘着剤の高屈折率化と粘着特性や光学特性の低下抑制とをバランスよく両立する観点から、60重量部以下とすることが有利であり、45重量部以下とすることが好ましい。より粘着特性や光学特性を重視するいくつかの態様において、ベースポリマー100重量部に対する屈折率向上剤の使用量は、例えば30重量部以下であってよく、20重量部以下でもよく、15重量部以下でもよく、10重量部以下でもよく、5重量部以下でもよく、3重量部以下でもよい。ここに開示される技術は、粘着剤層におけるベースポリマー100重量部に対する屈折率向上剤の使用量が1重量部未満であるか、または屈折率向上剤を実質的に使用しない態様でも好ましく実施することができる。ここで、実質的に使用しないとは、少なくとも意図的には使用しないことをいう。 The amount of the refractive index improver used with respect to 100 parts by weight of the base polymer (when a plurality of types of refractive index improvers are used, the total amount thereof) is not particularly limited and can be set according to the purpose. From the viewpoint of increasing the refractive index of the pressure-sensitive adhesive, the amount of the refractive index improver used with respect to 100 parts by weight of the base polymer can be, for example, 1 part by weight or more, and it is advantageous to use 3 parts by weight or more. It is preferably 7 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more. Further, in some embodiments, the amount of the refractive index improver used with respect to 100 parts by weight of the base polymer can be, for example, 80 parts by weight or less, so that the refractive index of the pressure-sensitive adhesive is increased and the deterioration of the pressure-sensitive adhesive properties and the optical properties is suppressed. From the viewpoint of achieving a good balance between the above and the like, it is advantageous to use 60 parts by weight or less, and preferably 45 parts by weight or less. In some embodiments where more adhesive properties and optical properties are emphasized, the amount of the refractive index improver used with respect to 100 parts by weight of the base polymer may be, for example, 30 parts by weight or less, 20 parts by weight or less, or 15 parts by weight. It may be 10 parts by weight or less, 5 parts by weight or less, or 3 parts by weight or less. The technique disclosed herein is preferably carried out even in an embodiment in which the amount of the refractive index improver used in 100 parts by weight of the base polymer in the pressure-sensitive adhesive layer is less than 1 part by weight, or the refractive index improver is substantially not used. be able to. Here, "not practically used" means that it is not used at least intentionally.
 (添加剤(HRO))
 いくつかの態様において、屈折率向上剤としては、ベースポリマーよりも高屈折率の有機材料を好ましく採用し得る。以下、このような有機材料を「添加剤(HRO)」と表記することがある。ここで、上記「HRO」は、高屈折率(High Refractive index)の有機材料(Organic material)であることを表す。ベースポリマー(例えばアクリル系ポリマー、好ましくはアクリル系ポリマー(A))と添加剤(HRO)とを組み合わせて用いることにより、屈折率と粘着特性(剥離強度、柔軟性等)および/または光学特性(全光線透過率、ヘイズ値等)とをより好適に両立する粘着剤を実現し得る。添加剤(HRO)として用いられる有機材料は、重合体であってもよく、非重合体であってもよい。また、重合性官能基を有していてもよく、有していなくてもよい。添加剤(HRO)は、1種を単独でまたは2種以上を組み合わせて用いることができる。
(Additive (H RO ))
In some embodiments, the refractive index improver may preferably be an organic material having a higher refractive index than the base polymer. Hereinafter, such an organic material may be referred to as "additive (HRO)". Here, the above-mentioned "H RO " represents an organic material having a high refractive index. By using a base polymer (for example, an acrylic polymer, preferably an acrylic polymer (A)) in combination with an additive (HRO ), the refractive index and adhesive properties (peeling strength, flexibility, etc.) and / or optical properties can be used. It is possible to realize an adhesive that more preferably balances (total light transmittance, haze value, etc.). The organic material used as an additive ( HRO ) may be a polymer or a non-polymer. Further, it may or may not have a polymerizable functional group. The additive (H RO ) may be used alone or in combination of two or more.
 添加剤(HRO)の屈折率は、モノマーの屈折率と同様に、アッベ屈折率計を用いて、測定波長589nm、測定温度25℃の条件で測定される。メーカー等から25℃における屈折率の公称値が提供されている場合は、その公称値を採用することができる。 The refractive index of the additive (H RO ) is measured using an Abbe refractive index meter under the conditions of a measurement wavelength of 589 nm and a measurement temperature of 25 ° C., similarly to the refractive index of the monomer. If the manufacturer or the like provides a nominal value of the refractive index at 25 ° C., the nominal value can be adopted.
 添加剤(HRO)として使用する有機材料の分子量は、特に限定されず、目的に応じて選択し得る。高屈折率化の効果と他の特性(例えば、粘着剤に適した柔軟性、ヘイズ等の光学特性)とをバランスよく両立する観点から、いくつかの態様において、添加剤(HRO)の分子量は、凡そ10000未満であることが適当であり、5000未満であることが好ましく、3000未満(例えば1000未満)であることがより好ましく、800未満でもよく、600未満でもよく、500未満でもよく、400未満でもよい。添加剤(HRO)の分子量が大きすぎないことは、粘着剤層内における相溶性向上の観点から有利となり得る。また、添加剤(HRO)の分子量は、例えば130以上であってよく、150以上でもよい。いくつかの態様において、添加剤(HRO)の分子量は、該添加剤(HRO)の高屈折率化の観点から、170以上であることが好ましく、200以上であることがより好ましく、230以上でもよく、250以上でもよく、270以上でもよく、500以上でもよく、1000以上でもよく、2000以上でもよい。いくつかの態様において、分子量が1000~10000程度(例えば1000以上5000未満)の重合体を、添加剤(HRO)として用いることができる。
 添加剤(HRO)の分子量としては、非重合体または低重合度(例えば2~5量体程度)の重合体については、化学構造に基づいて算出される分子量、もしくはマトリックス支援レーザー脱離イオン化飛行時間型質量分析法(MALDI-TOF-MS)を用いた測定値を用いることができる。添加剤(HRO)がより重合度の高い重合体である場合は、適切な条件で行われるGPCに基づく重量平均分子量(Mw)を用いることができる。メーカー等から分子量の公称値が提供されている場合は、その公称値を採用することができる。
The molecular weight of the organic material used as an additive ( HRO ) is not particularly limited and can be selected according to the intended purpose. In some embodiments, the molecular weight of the additive (HRO ) is balanced from the viewpoint of achieving a good balance between the effect of increasing the refractive index and other properties (for example, flexibility suitable for an adhesive and optical properties such as haze). Is more than about 10,000, preferably less than 5,000, more preferably less than 3,000 (eg, less than 1,000), less than 800, less than 600, less than 500, and more. It may be less than 400. It may be advantageous from the viewpoint of improving the compatibility in the pressure-sensitive adhesive layer that the molecular weight of the additive (H RO) is not too large. The molecular weight of the additive ( HRO ) may be, for example, 130 or more, or 150 or more. In some embodiments, the molecular weight of the additive (H RO), from the viewpoint of increasing the refractive index of the additive (H RO), preferably at least 170, more preferably 200 or more, 230 It may be 250 or more, 270 or more, 500 or more, 1000 or more, 2000 or more. In some embodiments, a polymer having a molecular weight of about 1000-10000 (eg, 1000 or more and less than 5000) can be used as the additive (HRO).
As for the molecular weight of the additive (HRO ), for a non-polymer or a polymer having a low degree of polymerization (for example, about 2 to 5 mer), the molecular weight is calculated based on the chemical structure, or matrix-assisted laser desorption / ionization. Measurements using time-of-flight mass spectrometry (MALDI-TOF-MS) can be used. When the additive (H RO ) is a polymer having a higher degree of polymerization, a weight average molecular weight (Mw) based on GPC performed under appropriate conditions can be used. If a manufacturer or the like provides a nominal value of molecular weight, that nominal value can be adopted.
 添加剤(HRO)の選択肢となり得る有機材料の例には、芳香環を有する有機化合物、複素環(芳香環でもよく、非芳香族性の複素環でもよい。)を有する有機化合物、等が含まれるが、これらに限定されない。 Examples of organic materials that can be an additive ( HRO ) option include organic compounds having an aromatic ring, organic compounds having a heterocycle (which may be an aromatic ring or a non-aromatic heterocycle), and the like. Included, but not limited to.
 添加剤(HRO)として用いられる上記芳香環を有する有機化合物(以下、「芳香環含有化合物」ともいう。)の有する芳香環は、モノマー(m1)として用いられる化合物の有する芳香環と同様のものから選択され得る。 The aromatic ring of the organic compound having an aromatic ring used as an additive ( HRO ) (hereinafter, also referred to as “aromatic ring-containing compound”) is the same as that of the aromatic ring of the compound used as the monomer (m1). Can be selected from.
 上記芳香環は、環構成原子上に1または2以上の置換基を有していてもよく、置換基を有していなくてもよい。置換基を有する場合、該置換基としては、アルキル基、アルコキシ基、アリールオキシ基、水酸基、ハロゲン原子(フッ素原子、塩素原子、臭素原子等)、ヒドロキシアルキル基、ヒドロキシアルキルオキシ基、グリシジルオキシ基等が例示されるが、これらに限定されない。炭素原子を含む置換基において、該置換基に含まれる炭素原子の数は、例えば1~10であり、有利には1~6であり、好ましくは1~4であり、より好ましくは1~3であり、例えば1または2であり得る。いくつかの態様において、上記芳香環は、環構成原子上に置換基を有しないか、アルキル基、アルコキシ基およびハロゲン原子(例えば臭素原子)からなる群から選択される1または2以上の置換基を有する芳香環であり得る。 The aromatic ring may have one or more substituents on the ring-constituting atom, and may not have a substituent. When it has a substituent, the substituent includes an alkyl group, an alkoxy group, an aryloxy group, a hydroxyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydroxyalkyl group, a hydroxyalkyloxy group, and a glycidyloxy group. Etc., but are not limited thereto. Among the substituents containing carbon atoms, the number of carbon atoms contained in the substituent is, for example, 1 to 10, preferably 1 to 6, preferably 1 to 4, and more preferably 1 to 3. And can be, for example, 1 or 2. In some embodiments, the aromatic ring has one or more substituents that do not have a substituent on the ring-constituting atom or are selected from the group consisting of an alkyl group, an alkoxy group and a halogen atom (eg, a bromine atom). It can be an aromatic ring having.
 添加剤(HRO)として用いられ得る芳香環含有化合物の例としては、例えば:モノマー(m1)として用いられ得る化合物;モノマー(m1)として用いられ得る化合物をモノマー単位として含むオリゴマー;モノマー(m1)として用いられ得る化合物から、エチレン性不飽和基を有する基(環構成原子に結合した置換基であり得る。)または該基のうちエチレン性不飽和基を構成する部分を除き、水素原子またはエチレン性不飽和基を有しない基(例えば、水酸基、アミノ基、ハロゲン原子、アルキル基、アルコキシ基、ヒドロキシアルキル基、ヒドロキシアルキルオキシ基、グリシジルオキシ基等)に置き換えた構造の化合物;等が挙げられるが、これらに限定されない。添加剤(HRO)として用いられ得る芳香環含有化合物の非限定的な具体例には、ベンジルアクリレート、m-フェノキシベンジルアクリレート、2-(o-フェニルフェノキシ)エチルアクリレート、フェノキシエチルアクリレート、フェノキシジエチレングリコールアクリレート、フェノキシポリエチレングリコールアクリレート、2-ヒドロキシ-3-フェノキシプロピルアクリレート、上述したフルオレン構造を有するモノマー、ジナフトチオフェン構造を有するモノマー、ジベンゾチオフェン構造を有するモノマー等の芳香環含有モノマー;3-フェノキシベンジルアルコール、ジナフトチオフェンおよびその誘導体(例えば、ジナフトチオフェン環に、ヒドロキシ基、メタノール基、ジエタノール基、グリシジル基等から選択される1種または2種以上の置換基が、1または2以上結合した構造の化合物)等の、エチレン性不飽和基を有しない芳香環含有化合物;等が含まれ得る。また、芳香環含有化合物は、このような芳香環含有モノマーをモノマー単位として含むオリゴマー(好ましくは分子量が凡そ5000以下、より好ましくは凡そ1000以下のオリゴマー。例えば2~5量体程度の低重合物)であり得る。上記オリゴマーは、例えば:芳香環含有モノマーの単独重合体;1種または2種以上の芳香環含有モノマーの共重合体;1種または2種以上の芳香環含有モノマーと他のモノマーとの共重合体;等であり得る。上記他のモノマーとしては、芳香環を有しないモノマーの1種または2種以上が用いられ得る。 Examples of the aromatic ring-containing compound which can be used as additives (H RO), for example: compounds may be used as the monomer (m1); oligomers containing a compound that may be used as the monomer (m1) as a monomer unit; monomer (m1 ), Except for a group having an ethylenically unsaturated group (which may be a substituent bonded to a ring-constituting atom) or a portion of the group constituting an ethylenically unsaturated group, a hydrogen atom or Compounds having a structure replaced with a group having no ethylenically unsaturated group (for example, a hydroxyl group, an amino group, a halogen atom, an alkyl group, an alkoxy group, a hydroxyalkyl group, a hydroxyalkyloxy group, a glycidyloxy group, etc.); However, it is not limited to these. Non-limiting examples of aromatic ring-containing compounds that can be used as additives ( HRO ) include benzyl acrylate, m-phenoxybenzyl acrylate, 2- (o-phenylphenoxy) ethyl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol. Aromatic ring-containing compounds such as acrylates, phenoxypolyethylene glycol acrylates, 2-hydroxy-3-phenoxypropyl acrylates, the above-mentioned monomers having a fluorene structure, monomers having a dinaphthophene structure, and monomers having a dibenzothiophene structure; 3-phenoxybenzyl Alcohol, dinaphthophene and derivatives thereof (for example, one or two or more substituents selected from a hydroxy group, a methanol group, a diethanol group, a glycidyl group and the like are bonded to the dinaphthophene ring. Aromatic ring-containing compounds that do not have ethylenically unsaturated groups, such as structural compounds); etc. may be included. The aromatic ring-containing compound is an oligomer containing such an aromatic ring-containing monomer as a monomer unit (preferably an oligomer having a molecular weight of about 5000 or less, more preferably about 1000 or less. For example, a low polymer of about 2 to pentameric. ) Can be. The oligomer is, for example: a homopolymer of an aromatic ring-containing monomer; a copolymer of one or more aromatic ring-containing monomers; a copolymer of one or two or more aromatic ring-containing monomers and another monomer. Coalescence; etc. As the other monomer, one kind or two or more kinds of monomers having no aromatic ring may be used.
 いくつかの態様において、添加剤(HRO)としては、高い高屈折率化効果が得られやすいことから、1分子中に2以上の芳香環を有する有機化合物(以下、「芳香環複数含有化合物」ともいう。)を好ましく採用し得る。芳香環複数含有化合物は、エチレン性不飽和基等の重合性官能基を有していてもよく、有していなくてもよい。また、芳香環複数含有化合物は、重合体であってもよく、非重合体であってもよい。また、上記重合体は、芳香環複数含有モノマーをモノマー単位として含むオリゴマー(好ましくは分子量が凡そ5000以下、より好ましくは凡そ1000以下のオリゴマー。例えば2~5量体程度の低重合物)であり得る。上記オリゴマーは、例えば:芳香環複数含有モノマーの単独重合体;1種または2種以上の芳香環複数含有モノマーの共重合体;1種または2種以上の芳香環複数含有モノマーと他のモノマーとの共重合体;等であり得る。上記他のモノマーは、芳香環複数含有モノマーに該当しない芳香環含有モノマーでもよく、芳香環を有しないモノマーでもよく、これらの組合せであってもよい。 In some embodiments, the additive ( HRO ) is an organic compound having two or more aromatic rings in one molecule because a high refractive index increasing effect can be easily obtained (hereinafter, “a compound containing a plurality of aromatic rings”). ”) Can be preferably adopted. The compound containing a plurality of aromatic rings may or may not have a polymerizable functional group such as an ethylenically unsaturated group. Further, the compound containing a plurality of aromatic rings may be a polymer or a non-polymer. The polymer is an oligomer containing a monomer containing a plurality of aromatic rings as a monomer unit (preferably an oligomer having a molecular weight of about 5000 or less, more preferably about 1000 or less, for example, a low polymer of about 2 to pentamer). obtain. The above oligomers include, for example: a homopolymer of a plurality of aromatic ring-containing monomers; a copolymer of one or more kinds of multiple aromatic ring-containing monomers; and one or more kinds of multiple aromatic ring-containing monomers and other monomers. Copolymer; etc. The other monomer may be an aromatic ring-containing monomer that does not correspond to a monomer containing a plurality of aromatic rings, a monomer having no aromatic ring, or a combination thereof.
 芳香環複数含有化合物の非限定的な例としては、2以上の非縮合芳香環がリンキング基を介して結合した構造を有する化合物、2以上の非縮合芳香環が直接(すなわち、他の原子を介さずに)化学結合した構造を有する化合物、縮合芳香環構造を有する化合物、フルオレン構造を有する化合物、ジナフトチオフェン構造を有する化合物、ジベンゾチオフェン構造を有する化合物、等が挙げられる。芳香環複数含有化合物は、1種を単独でまたは2種以上を組み合せて用いることができる。 A non-limiting example of a compound containing a plurality of aromatic rings is a compound having a structure in which two or more non-condensed aromatic rings are bonded via a linking group, and two or more non-condensed aromatic rings directly (that is, other atoms). Examples thereof include a compound having a chemically bonded structure (without intervening), a compound having a condensed aromatic ring structure, a compound having a fluorene structure, a compound having a dinaphthophene structure, a compound having a dibenzothiophene structure, and the like. The compound containing a plurality of aromatic rings may be used alone or in combination of two or more.
 上記フルオレン構造を有する化合物の具体例としては、上述したフルオレン構造を有するモノマーや、かかるモノマーの単独重合体または共重合体であるオリゴマーのほか、9,9-ビス(4-ヒドロキシフェニル)フルオレン(屈折率:1.68)、9,9-ビス(4-アミノフェニル)フルオレン(屈折率:1.73)、9,9-ビス(4-ヒドロキシ-3-メチルフェニル)フルオレン(屈折率:1.68)、9,9-ビス[4-(2-ヒドロキシエトキシ)フェニル]フルオレン(屈折率:1.65)等の、9,9-ビスフェニルフルオレンおよびその誘導体が挙げられる。 Specific examples of the compound having a fluorene structure include the above-mentioned monomer having a fluorene structure, an oligomer which is a homopolymer or a copolymer of such a monomer, and 9,9-bis (4-hydroxyphenyl) fluorene ( Refraction rate: 1.68), 9,9-bis (4-aminophenyl) fluorene (refractive rate: 1.73), 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (refractive rate: 1) .68), 9,9-bisphenylfluorene and its derivatives such as 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (refractive index: 1.65) can be mentioned.
 上記ジナフトチオフェン構造を有する化合物の具体例としては、上述したジナフトチオフェン構造を有するモノマーや、かかるモノマーの単独重合体または共重合体であるオリゴマーのほか、ジナフトチオフェン(屈折率:1.808);6-ヒドロキシメチルジナフトチオフェン(屈折率:1.766)等のヒドロキシアルキルジナフトチオフェン;2,12-ジヒドロキシジナフトチオフェン(屈折率:1.750)等のジヒドロキシジナフトチオフェン;2,12-ジヒドロキエチルオキシジナフトチオフェン(屈折率:1.677)等のジヒドロキシアルキルオキシジナフトチオフェン;2,12-ジグリシジルオキシジナフトチオフェン(屈折率1.723)等のジグリシジルオキシジナフトチオフェン;2,12-ジアリルオキシジナフトチオフェン(略号:2,12-DAODNT、屈折率1.729)等の、エチレン性不飽和基を2以上有するジナフトチオフェン;等の、ジナフトチオフェンおよびその誘導体が挙げられる。 Specific examples of the compound having a dinaphthophene structure include the above-mentioned monomer having a dinaphthophene structure, an oligomer which is a homopolymer or a copolymer of such a monomer, and dinaphthophene (refractive index: 1. 808); hydroxyalkyl dinaphthophenes such as 6-hydroxymethyldinaphthophene (refractive index: 1.766); dihydroxydinaphthophenes such as 2,12-dihydroxydinaphthophene (refractive index: 1.750); 2 , 12-Dihydrochiethyloxydinaphthophene (refractive index: 1.677) and other dihydroxyalkyloxydinaphthophenes; Naftthiophene; dinaphthophene having two or more ethylenically unsaturated groups such as 2,12-dialyloxydinaphthophene (abbreviation: 2,12-DAODNT, refractive index 1.729); The derivative is mentioned.
 上記ジベンゾチオフェン構造を有する化合物の具体例としては、上述したジベンゾチオフェン構造を有するモノマーや、かかるモノマーの単独重合体または共重合体であるオリゴマーのほか、ジベンゾチオフェン(屈折率:1.607)、4-ジメチルジベンゾチオフェン(屈折率:1.617)、4,6-ジメチルジベンゾチオフェン(屈折率:1.617)、等が挙げられる。 Specific examples of the compound having the above-mentioned dibenzothiophene structure include the above-mentioned monomer having the dibenzothiophene structure, an oligomer which is a homopolymer or a copolymer of the above-mentioned monomer, and dibenzothiophene (refractive rate: 1.607). Examples thereof include 4-dimethyldibenzothiophene (refractive rate: 1.617), 4,6-dimethyldibenzothiophene (refractive rate: 1.617), and the like.
 添加剤(HRO)の選択肢となり得る、複素環を有する有機化合物(以下、複素環含有有機化合物ともいう。)の例としては、チオエポキシ化合物、トリアジン環を有する化合物、等が挙げられる。チオエポキシ化合物の例としては、日本国特許第3712653号公報に記載のビス(2,3-エピチオプロピル)ジスルフィドおよびその重合物(屈折率1.74)が挙げられる。トリアジン環を有する化合物の例としては、1分子内にトリアジン環を少なくとも1つ(例えば3~40個、好ましくは5~20個))有する化合物が挙げられる。なお、トリアジン環は芳香族性を有するため、トリアジン環を有する化合物は上記芳香環含有化合物の概念にも包含され、また、トリアジン環を複数有する化合物は上記芳香環複数含有化合物の概念にも包含される。 It can be the choice of the additives (H RO), an organic compound having a heterocyclic ring (hereinafter, heterocyclic also called containing organic compound.) Examples of thioepoxy compound, a compound having a triazine ring, and the like. Examples of the thioepoxy compound include bis (2,3-epithiopropyl) disulfide described in Japanese Patent No. 3712653 and a polymer thereof (refractive index 1.74). Examples of the compound having a triazine ring include a compound having at least one triazine ring (for example, 3 to 40, preferably 5 to 20) in one molecule. Since the triazine ring has aromaticity, the compound having a triazine ring is also included in the concept of the above-mentioned aromatic ring-containing compound, and the compound having a plurality of triazine rings is also included in the concept of the above-mentioned compound containing a plurality of aromatic rings. Will be done.
 いくつかの態様において、添加剤(HRO)としては、エチレン性不飽和基を有しない化合物を好ましく採用し得る。これにより、熱や光による粘着剤組成物の変質(ゲル化の進行や粘度上昇によるレベリング性の低下)を抑制し、保存安定性を高めることができる。エチレン性不飽和基を有しない添加剤(HRO)を採用することは、該添加剤(HRO)を含む粘着剤層を有する粘着型光学フィルムや、該粘着型光学フィルムを含む積層体等において、エチレン性不飽和基の反応に起因する寸法変化や変形(反り、波打ち等)、光学歪の発生等を抑制する観点からも好ましい。 In some embodiments, the additive ( HRO ) may preferably be a compound that does not have an ethylenically unsaturated group. As a result, deterioration of the pressure-sensitive adhesive composition due to heat or light (decrease in leveling property due to progress of gelation or increase in viscosity) can be suppressed, and storage stability can be improved. Adopting an additive (H RO ) having no ethylenically unsaturated group means an adhesive optical film having an adhesive layer containing the additive (H RO ), a laminate containing the adhesive optical film, or the like. From the viewpoint of suppressing dimensional changes, deformations (warping, waviness, etc.), occurrence of optical strain, etc. due to the reaction of ethylenically unsaturated groups, it is also preferable.
 添加剤(HRO)としてオリゴマーを使用する態様において、該オリゴマーは、対応するモノマー成分を公知の方法で重合させることにより得ることができる。上記オリゴマーをラジカル重合により製造する場合には、上記モノマー成分に、ラジカル重合に用いられる重合開始剤、連鎖移動剤、乳化剤等を適宜添加して 、重合を行うことができる。上記ラジカル重合に用いられる重合開始剤、連鎖移動剤、乳化剤等は、特に限定されず、適宜選択して使用することができる。なお、オリゴマーの重量平均分子量は、重合開始剤、連鎖移動剤の使用量、反応条件により制御可能であり、これらの種類に応じて適宜その使用量が調整される。
 上記連鎖移動剤としては、例えば、ラウリルメルカプタン、グリシジルメルカプタン、メルカプト酢酸、2-メルカプトエタノール、α-チオグリセロール、チオグリコール酸、チオグルコール酸2-エチルヘキシル、2,3-ジメルカプト-1-プロパノール等が挙げられる。連鎖移動剤は、1種を単独で使用してもよく、2種以上を混合して使用してもよい。連鎖移動剤の使用量は、オリゴマーの合成に用いられるモノマー成分の組成や連鎖移動剤の種類等に応じて、所望の重量平均分子量のオリゴマーが得られるように設定することができる。いくつかの態様において、オリゴマーの合成に用いられるモノマーの全量100重量部に対する連鎖移動剤の使用量は、凡そ15重量部以下とすることが適当であり、10重量部以下でもよく、5重量部程度以下でもよい。オリゴマーの合成に用いられるモノマーの全量100重量部に対する連鎖移動剤の使用量の下限は特に制限されないが、例えば0.01重量部以上であってよく、0.1重量部以上でもよく、0.5重量部以上でもよく、1重量部以上でもよい。
In an embodiment in which an oligomer is used as an additive ( HRO ), the oligomer can be obtained by polymerizing the corresponding monomer component in a known manner. When the above-mentioned oligomer is produced by radical polymerization, polymerization can be carried out by appropriately adding a polymerization initiator, a chain transfer agent, an emulsifier and the like used for radical polymerization to the above-mentioned monomer component. The polymerization initiator, chain transfer agent, emulsifier and the like used in the above radical polymerization are not particularly limited and can be appropriately selected and used. The weight average molecular weight of the oligomer can be controlled by the amount of the polymerization initiator and the chain transfer agent used, and the reaction conditions, and the amount used is appropriately adjusted according to these types.
Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, α-thioglycerol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2,3-dimercapto-1-propanol and the like. Be done. The chain transfer agent may be used alone or in combination of two or more. The amount of the chain transfer agent used can be set so that an oligomer having a desired weight average molecular weight can be obtained according to the composition of the monomer component used for the synthesis of the oligomer, the type of the chain transfer agent, and the like. In some embodiments, the amount of the chain transfer agent used with respect to 100 parts by weight of the total amount of the monomers used in the synthesis of the oligomer is preferably about 15 parts by weight or less, and may be 10 parts by weight or less, and 5 parts by weight. It may be less than or equal to the degree. The lower limit of the amount of the chain transfer agent used with respect to 100 parts by weight of the total amount of the monomers used for the synthesis of the oligomer is not particularly limited, but may be, for example, 0.01 parts by weight or more, 0.1 parts by weight or more, and 0. It may be 5 parts by weight or more, or 1 part by weight or more.
 屈折率向上剤として添加剤(HRO)を使用する態様において、ベースポリマー100重量部に対する添加剤(HRO)の使用量(複数種の化合物を用いる場合は、それらの合計量)は、特に限定されず、目的に応じて設定することができる。粘着剤の高屈折率化の観点から、ベースポリマー100重量部に対する添加剤(HRO)の使用量は、例えば1重量部以上とすることができ、3重量部以上とすることが有利であり、5重量部以上とすることが好ましく、7重量部以上でもよく、10重量部以上でもよく、15重量部以上でもよく、20重量部以上でもよい。いくつかの態様において、ベースポリマー100重量部に対する添加剤(HRO)の使用量は、例えば80重量部以下とすることができ、粘着剤の高屈折率化と粘着特性や光学特性の低下抑制とをバランスよく両立する観点から、60重量部以下とすることが有利であり、45重量部以下とすることが好ましい。より粘着特性や光学特性を重視するいくつかの態様において、ベースポリマー100重量部に対する添加剤(HRO)の使用量は、例えば30重量部以下であってよく、20重量部以下でもよく、15重量部以下でもよく、10重量部以下でもよい。 In embodiments using an additive (H RO) as a refractive index enhancing agent, the amount of additive to 100 parts by weight of the base polymer (H RO) (in the case of using a plurality of compounds, their total amount), particularly It is not limited and can be set according to the purpose. From the viewpoint of increasing the refractive index of the pressure-sensitive adhesive, the amount of the additive ( HRO ) used with respect to 100 parts by weight of the base polymer can be, for example, 1 part by weight or more, and it is advantageous to use 3 parts by weight or more. It is preferably 5 parts by weight or more, 7 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more. In some embodiments, the amount of the additive (HRO ) used with respect to 100 parts by weight of the base polymer can be, for example, 80 parts by weight or less, so that the refractive index of the pressure-sensitive adhesive is increased and the deterioration of the pressure-sensitive adhesive properties and the optical properties is suppressed. From the viewpoint of achieving a good balance between the above and the like, it is advantageous to use 60 parts by weight or less, and preferably 45 parts by weight or less. In some embodiments where more adhesive properties and optical properties are emphasized, the amount of the additive (HRO ) used per 100 parts by weight of the base polymer may be, for example, 30 parts by weight or less, 20 parts by weight or less, and 15 parts by weight. It may be 10 parts by weight or less.
 (可塑化材料)
 ここに開示される粘着型光学フィルムのいくつかの態様において、粘着剤層は、上述のようなベースポリマー(例えば、アクリル系ポリマー(A))に加えて、該ベースポリマーより低分子量の可塑化材料を含み得る。可塑化材料の使用により、粘着剤層の柔軟性を高め、被着体に対する密着性や、粘着型光学フィルム全体としての柔軟性や変形に対する追従性を向上させ得る。可塑化材料としては、粘着剤層内における相溶性や透明性の観点から、有機材料を好ましく採用し得る。可塑化材料は、上述した屈折率向上剤(例えば、上記添加剤(HRO))としても用いられ得る材料であってもよい。
(Therplastic material)
In some aspects of the pressure-sensitive optical film disclosed herein, the pressure-sensitive adhesive layer is a plasticized product having a lower molecular weight than the base polymer, in addition to the base polymer as described above (for example, the acrylic polymer (A)). May include material. By using the thermoplastic material, the flexibility of the pressure-sensitive adhesive layer can be increased, and the adhesion to the adherend, the flexibility of the pressure-sensitive optical film as a whole, and the followability to deformation can be improved. As the plasticizing material, an organic material can be preferably adopted from the viewpoint of compatibility and transparency in the pressure-sensitive adhesive layer. The thermoplastic material may be a material that can also be used as the above-mentioned refractive index improver (for example, the above-mentioned additive ( HRO)).
 可塑化材料の分子量は、ベースポリマーより低ければよく、特に限定されない。いくつかの態様において、可塑化材料の分子量は、可塑化効果を発現しやすくする観点から、30000以下でもよく、25000以下でもよく、10000未満でもよく、5000未満であることが好ましく、3000未満(例えば1000未満)であることがより好ましく、800未満でもよく、600未満でもよく、500未満でもよく、400未満でもよい。可塑化材料の分子量が大きすぎないことは、粘着剤層内における相溶性向上等の観点から有利となり得る。また、いくつかの態様において、可塑化材料の分子量は、十分な可塑化効果を発揮しやすくする観点から、130以上であることが適当であり、150以上であることが好ましく、170以上でもよく、200以上でもよく、250以上でもよく、300以上でもよい。いくつかの態様において、可塑化材料の分子量は、500以上であってもよく、1000以上であってもよく、2000以上であってもよい。可塑化材料の分子量が低すぎないことは、耐熱性能や被着体の汚染抑制の観点からも好ましい。 The molecular weight of the plasticizing material may be lower than that of the base polymer, and is not particularly limited. In some embodiments, the molecular weight of the plasticizing material may be 30,000 or less, 25,000 or less, less than 10,000, preferably less than 5,000, and less than 3,000 (preferably less than 3,000, from the viewpoint of facilitating the development of the plasticizing effect. For example, less than 1000) is more preferable, and it may be less than 800, less than 600, less than 500, or less than 400. The fact that the molecular weight of the plasticized material is not too large can be advantageous from the viewpoint of improving compatibility in the pressure-sensitive adhesive layer. Further, in some embodiments, the molecular weight of the plasticizing material is preferably 130 or more, preferably 150 or more, and may be 170 or more, from the viewpoint of facilitating the exertion of a sufficient plasticizing effect. , 200 or more, 250 or more, 300 or more. In some embodiments, the molecular weight of the thermoplastic material may be 500 or greater, 1000 or greater, or 2000 or greater. It is preferable that the molecular weight of the plasticized material is not too low from the viewpoint of heat resistance and suppression of contamination of the adherend.
 可塑化材料の選択肢となり得る化合物の非限定的な例には、モノマー(m1)として用いられ得る化合物(例えば、ベンジル基、フェノキシ基、ナフチル基等の芳香環を有する(メタ)アクリレート、フルオレン構造を有するモノマー、ジナフトチオフェン構造を有するモノマー、ジベンゾチオフェン構造を有するモノマー等);モノマー(m1)として用いられ得る化合物をモノマー単位として含むオリゴマー;モノマー(m1)として用いられ得る化合物から、エチレン性不飽和基を有する部分を除き、水素原子またはエチレン性不飽和基を有しない基に置き換えた構造の化合物(例えば、3-フェノキシベンジルアルコール);等が含まれる。モノマー(m1)として用いられ得る化合物をモノマー単位として含むオリゴマーには、柔軟性向上の観点から、例えばn-ブチルアクリレートや2-エチルヘキシルアクリレート等の低Tgモノマーが共重合されていてもよい。可塑化材料として、公知の可塑剤(例えば、フタル酸エステル系、テレフタル酸エステル系、アジピン酸エステル系、アジピン酸系ポリエステル、安息香酸グリコールエステル等)の1種または2種以上を利用してもよい。 Non-limiting examples of compounds that can be options for plasticizing materials include compounds that can be used as monomers (m1) (eg, (meth) acrylates having aromatic rings such as benzyl group, phenoxy group, naphthyl group, fluorene structure. Monomer having, dinaphthophene structure, monomer having dibenzothiophene structure, etc.); Monomer containing a compound that can be used as a monomer (m1) as a monomer unit; Ethylene property from a compound that can be used as a monomer (m1) A compound having a structure in which a hydrogen atom or a group having no ethylenically unsaturated group is replaced except for a portion having an unsaturated group (for example, 3-phenoxybenzyl alcohol); and the like are included. From the viewpoint of improving flexibility, a low Tg monomer such as n-butyl acrylate or 2-ethylhexyl acrylate may be copolymerized with the oligomer containing a compound that can be used as the monomer (m1) as a monomer unit. As the plasticizing material, one or more known plasticizers (for example, phthalate ester, terephthalic acid ester, adipate ester, adipate polyester, benzoic acid glycol ester, etc.) may be used. good.
 いくつかの態様において、可塑化材料としては、屈折率が凡そ1.50以上(より好ましくは1.53以上)の有機材料が好ましく用いられ得る。可塑化材料の選択肢となり得る化合物の具体例には、ジエチレングリコールジベンゾエート(屈折率1.55)、ジプロピレングリコールジベンゾエート(屈折率1.54)、3-フェノキシトルエン(屈折率1.57)、3-エチルビフェニル(屈折率1.59)、3-メトキシビフェニル(屈折率1.61)、4-メトキシビフェニル(屈折率1.57)、ポリエチレングリコールジベンゾエート、3-フェノキシベンジルアルコール(屈折率1.59)、トリフェニルホスフェート(屈折率1.56)、安息香酸ベンジル(屈折率1.57)、4-(tert-ブチル)フェニルジフェニルホスフェート(屈折率1.56)、トリメチルフェニルホスフェート(屈折率1.55)、ブチルベンジルフタレート(屈折率1.54)、ロジンメチルエステル(屈折率1.53)、アルキルベンジルフタレート(屈折率1.53)、ブチル(フェニルスルホニル)アミン(屈折率1.53)、トリメチルトリメリテート(屈折率1.52)、ベンジルフタレート(屈折率1.52)、2-エチルヘキシルジフェニルホスフェート(屈折率1.51)、亜りん酸トリス(2,4-ジ-tert-ブチルフェニル)、等が含まれるが、これらに限定されない。屈折率および相溶性の観点から、例えばジエチレングリコールジベンゾエートを好ましく採用し得る。可塑化材料の屈折率の上限は、特に制限されず、例えば3.00以下であり得る。いくつかの態様において、粘着剤組成物の調製容易性や、粘着剤内における相溶性等の観点から、可塑化材料の屈折率は、2.50以下であることが適当であり、2.00以下であることが有利であり、1.90以下でもよく、1.80以下でもよく、1.70以下でもよい。
 なお、可塑化材料の屈折率は、モノマーの屈折率と同様に、アッベ屈折率計を用いて、測定波長589nm、測定温度25℃の条件で測定される。メーカー等から25℃における屈折率の公称値が提供されている場合は、その公称値を採用することができる。
In some embodiments, as the thermoplastic material, an organic material having a refractive index of about 1.50 or more (more preferably 1.53 or more) can be preferably used. Specific examples of compounds that can be options for plasticizing materials include diethylene glycol dibenzoate (refraction: 1.55), dipropylene glycol dibenzoate (refraction: 1.54), 3-phenoxytoluene (refraction: 1.57), 3-Ethylbiphenyl (refraction 1.59), 3-methoxybiphenyl (refraction 1.61), 4-methoxybiphenyl (refraction 1.57), polyethylene glycol dibenzoate, 3-phenoxybenzyl alcohol (refraction 1) .59), triphenyl phosphate (refraction rate 1.56), benzyl benzoate (refraction rate 1.57), 4- (tert-butyl) phenyldiphenyl phosphate (refraction rate 1.56), trimethylphenyl phosphate (refraction rate 1.56) 1.55), butylbenzylphthalate (refraction 1.54), rosinmethyl ester (refraction 1.53), alkylbenzylphthalate (refraction 1.53), butyl (phenylsulfonyl) amine (refraction 1.53) ), Trimethyltrimeritate (refraction: 1.52), benzylphthalate (refraction: 1.52), 2-ethylhexyldiphenyl phosphate (refraction: 1.51), tris phosphite (2,4-di-tert-) Butylphenyl), etc., but not limited to these. From the viewpoint of refractive index and compatibility, for example, diethylene glycol dibenzoate can be preferably adopted. The upper limit of the refractive index of the plasticized material is not particularly limited and may be, for example, 3.00 or less. In some embodiments, the refractive index of the thermoplastic material is preferably 2.50 or less, 2.00, from the viewpoint of ease of preparation of the pressure-sensitive adhesive composition, compatibility in the pressure-sensitive adhesive, and the like. It is advantageous that it is 1.90 or less, 1.80 or less, or 1.70 or less.
The refractive index of the plasticized material is measured using an Abbe refractive index meter under the conditions of a measurement wavelength of 589 nm and a measurement temperature of 25 ° C., similarly to the refractive index of the monomer. If the manufacturer or the like provides a nominal value of the refractive index at 25 ° C., the nominal value can be adopted.
 可塑化材料を使用する態様において、ベースポリマー100重量部に対する可塑化材料の使用量は、特に限定されず、目的に応じて設定することができる。可塑化効果を高める観点から、ベースポリマー100重量部に対する可塑化材料の使用量は、例えば0.1重量部以上であってよく、0.5重量部以上であってもよく、より高い可塑化効果を得る観点から1重量部以上とすることが好ましく、3重量部以上とすることがより好ましく、5重量部以上でもよく、7重量部以上でもよく、10重量部以上でもよく、15重量部以上でもよく、20重量部以上でもよい。また、粘着剤の高屈折率化と透明性および可塑化効果とをバランスよく両立する観点から、ベースポリマー100重量部に対する可塑化材料の使用量は、凡そ100重量部以下とすることが適当であり、80重量部以下とすることが好ましく、60重量部以下とすることがより好ましく、45重量部以下でもよく、35重量部以下でもよく、25重量部以下でもよい。より粘着特性や光学特性を重視するいくつかの態様において、ベースポリマー100重量部に対する可塑化材料の使用量は、15重量部以下でもよく、10重量部以下でもよく、5重量部以下でもよい。 In the embodiment in which the plasticized material is used, the amount of the plasticized material used with respect to 100 parts by weight of the base polymer is not particularly limited and can be set according to the purpose. From the viewpoint of enhancing the plasticizing effect, the amount of the plasticizing material used with respect to 100 parts by weight of the base polymer may be, for example, 0.1 part by weight or more, 0.5 parts by weight or more, and higher plasticization. From the viewpoint of obtaining the effect, it is preferably 1 part by weight or more, more preferably 3 parts by weight or more, 5 parts by weight or more, 7 parts by weight or more, 10 parts by weight or more, and 15 parts by weight. It may be more than 20 parts by weight. Further, from the viewpoint of achieving a good balance between high refractive index of the pressure-sensitive adhesive, transparency and plasticizing effect, it is appropriate that the amount of the plasticizing material used with respect to 100 parts by weight of the base polymer is about 100 parts by weight or less. It is preferably 80 parts by weight or less, more preferably 60 parts by weight or less, 45 parts by weight or less, 35 parts by weight or less, or 25 parts by weight or less. In some embodiments where more adhesive properties and optical properties are emphasized, the amount of the thermoplastic material used with respect to 100 parts by weight of the base polymer may be 15 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.
 (レベリング剤)
 いくつかの態様において、粘着剤層の形成に用いられる粘着剤組成物には、該組成物から形成される粘着剤層の外観向上(例えば、厚みの均一性の向上)や上記粘着剤組成物の塗工性向上等の目的で、必要に応じてレベリング剤を含有させることができる。レベリング剤の非限定的な例としては、アクリル系レベリング剤、フッ素系レベリング剤、シリコーン系レベリング剤などが挙げられる。レベリング剤は、例えば、市販のレベリング剤から適切なものを選択し、常法により用いることができる。
(Leveling agent)
In some embodiments, the pressure-sensitive adhesive composition used to form the pressure-sensitive adhesive layer includes an improvement in the appearance of the pressure-sensitive adhesive layer formed from the composition (for example, improvement in thickness uniformity) and the above-mentioned pressure-sensitive adhesive composition. A leveling agent can be contained as needed for the purpose of improving the coatability of the above. Non-limiting examples of the leveling agent include an acrylic leveling agent, a fluorine-based leveling agent, a silicone-based leveling agent, and the like. As the leveling agent, for example, an appropriate leveling agent can be selected from commercially available leveling agents and used by a conventional method.
 いくつかの態様において、上記レベリング剤として、ポリオルガノシロキサン骨格を有するモノマー(以下、「モノマーS1」ともいう。)とアクリル系モノマーとを含むモノマー原料(以下、「モノマー原料B」ともいう。)の重合物であるポリマー(以下、「ポリマー(B)」ともいう。)を好ましく用いることができる。ポリマー(B)は、モノマーS1とアクリル系モノマーとの共重合体ということができる。ポリマー(B)は、一種を単独でまたは二種以上を組み合わせて使用することができる。 In some embodiments, as the leveling agent, a monomer raw material containing a monomer having a polyorganosiloxane skeleton (hereinafter, also referred to as “monomer S1”) and an acrylic monomer (hereinafter, also referred to as “monomer raw material B”). A polymer (hereinafter, also referred to as “polymer (B)”) which is a polymer of the above can be preferably used. The polymer (B) can be said to be a copolymer of the monomer S1 and the acrylic monomer. The polymer (B) can be used alone or in combination of two or more.
 モノマーS1としては、特に限定されず、ポリオルガノシロキサン骨格を含有する任意のモノマーを用いることができる。モノマーS1としては、片末端に重合性反応基を有する構造のものを好ましく用いることができる。なかでも、片末端に重合性反応基を有し、かつ、他の末端にベースポリマー(該レベリング剤が配合される粘着剤組成物のベースポリマーを指す。例えばアクリル系ポリマー)と架橋反応を生じる官能基を有しない構造のモノマーS1を好ましく採用し得る。市販品としては、例えば、信越化学工業社製の片末端反応性シリコーンオイル(例えば、X-22-174ASX、X-22-2426、X-22-2475、KF-2012等の品番)が挙げられる。モノマーS1は、一種を単独でまたは二種以上を組み合わせて使用することができる。 The monomer S1 is not particularly limited, and any monomer containing a polyorganosiloxane skeleton can be used. As the monomer S1, a monomer having a structure having a polymerizable reactive group at one end can be preferably used. Among them, it has a polymerizable reactive group at one end and causes a cross-linking reaction with a base polymer (refers to a base polymer of a pressure-sensitive adhesive composition containing the leveling agent, for example, an acrylic polymer) at the other end. A monomer S1 having a structure having no functional group can be preferably adopted. Examples of commercially available products include one-ended reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. (for example, product numbers of X-22-174ASX, X-22-2426, X-22-2475, KF-2012, etc.). .. Monomer S1 can be used alone or in combination of two or more.
 モノマーS1の官能基当量は、例えば100g/mol~30000g/mol程度であり得る。いくつかの好ましい態様では、上記官能基当量は、例えば500g/mol以上であり、800g/mol以上でもよく、1500g/mol以上でもよく、2000g/mol以上でもよい。また、上記官能基当量は、例えば20000g/mol以下であってよく、10000g/mol未満でもよく、7000g/mol以下でもよく、5500g/mol以下でもよい。モノマーS1の官能基当量が上記範囲内であると、良好なレベリング効果が発揮されやすい。
 なお、モノマーS1として官能基当量が異なる二種類以上のモノマーを用いる場合、モノマーS1の官能基当量とは、各種類のモノマーの官能基当量と該モノマーの重量分率との積の総和を用いることができる。
The functional group equivalent of the monomer S1 can be, for example, about 100 g / mol to 30,000 g / mol. In some preferred embodiments, the functional group equivalent may be, for example, 500 g / mol or more, 800 g / mol or more, 1500 g / mol or more, or 2000 g / mol or more. The functional group equivalent may be, for example, 20000 g / mol or less, less than 10000 g / mol, 7000 g / mol or less, or 5500 g / mol or less. When the functional group equivalent of the monomer S1 is within the above range, a good leveling effect is likely to be exhibited.
When two or more types of monomers having different functional group equivalents are used as the monomer S1, the functional group equivalent of the monomer S1 is the sum of the products of the functional group equivalents of each type of monomer and the weight fraction of the monomer. be able to.
 ここで、「官能基当量」とは、官能基1個当たりに結合している主骨格(例えばポリジメチルシロキサン)の重量を意味する。標記単位g/molに関しては、官能基1molと換算している。モノマーS1の官能基当量は、例えば、核磁気共鳴(NMR)に基づくH-NMR(プロトンNMR)のスペクトル強度から算出することができる。H-NMRのスペクトル強度に基づくモノマーS1の官能基当量(g/mol)の算出は、H-NMRスペクトル解析に係る一般的な構造解析手法に基づいて、必要であれば日本国特許第5951153号公報の記載を参照して行うことができる。モノマーS1の官能基当量において、上記官能基とは、重合性官能基(例えば、(メタ)アクリロイル基、ビニル基、アリル基等のエチレン性不飽和基)を意味する。 Here, the "functional group equivalent" means the weight of the main skeleton (for example, polydimethylsiloxane) bonded to each functional group. The title unit g / mol is converted to 1 mol of functional group. The functional group equivalent of the monomer S1 can be calculated, for example, from the spectral intensity of 1 H-NMR (proton NMR) based on nuclear magnetic resonance (NMR). 1 The calculation of the functional group equivalent (g / mol) of the monomer S1 based on the spectral intensity of 1 H-NMR is based on the general structural analysis method related to 1 1 H-NMR spectrum analysis, and if necessary, the Japanese Patent No. 1 This can be done with reference to the description in Publication No. 5591153. In terms of the functional group equivalent of the monomer S1, the functional group means a polymerizable functional group (for example, an ethylenically unsaturated group such as a (meth) acryloyl group, a vinyl group or an allyl group).
 モノマー原料BにおけるモノマーS1の含有量は、該モノマーS1を用いて所望の効果が発揮される範囲で適切な値を採用することができ、特定の範囲に限定されない。いくつかの態様において、モノマー原料BにおけるモノマーS1の含有量は、例えば5~60重量%であってよく、10~50重量%でもよく、15~40重量%でもよい。 The content of the monomer S1 in the monomer raw material B can be an appropriate value within a range in which the desired effect is exhibited by using the monomer S1, and is not limited to a specific range. In some embodiments, the content of the monomer S1 in the monomer raw material B may be, for example, 5-60% by weight, 10-50% by weight, or 15-40% by weight.
 モノマー原料Bは、モノマーS1に加えて、モノマーS1と共重合可能なアクリル系モノマーを含む。これにより、粘着剤層内におけるポリマー(B)の相溶性を改善し得る。モノマー原料Bに使用し得るアクリル系モノマーとしては、例えば、アクリル酸アルキルエステルが挙げられる。ここでいう「アルキル」は、鎖状(直鎖状、分岐鎖状を包含する。)のアルキル(基)をいい、後述の脂環式炭化水素基を含まない。いくつかの態様において、モノマー原料Bは、(メタ)アクリル酸C4-12アルキルエステル(好ましくは(メタ)アクリル酸C4-10アルキルエステル、例えば(メタ)アクリル酸C6-10アルキルエステル)の少なくとも一種を含有し得る。他のいくつかの態様において、モノマー原料Bは、メタクリル酸C1-18アルキルエステル(好ましくはメタクリル酸C1-14アルキルエステル、例えばメタクリル酸C1-10アルキルエステル)の少なくとも一種を含有し得る。モノマー原料Bは、アクリル系モノマーとして、例えば、メタクリル酸メチル(MMA)、メタクリル酸n-ブチル(BMA)およびメタクリル酸2-エチルヘキシル(2EHMA)から選択される一種または二種以上を含み得る。 The monomer raw material B contains an acrylic monomer copolymerizable with the monomer S1 in addition to the monomer S1. Thereby, the compatibility of the polymer (B) in the pressure-sensitive adhesive layer can be improved. Examples of the acrylic monomer that can be used for the monomer raw material B include acrylic acid alkyl esters. The term "alkyl" as used herein refers to a chain-like (including linear and branched-chain) alkyl (groups), and does not include the alicyclic hydrocarbon group described later. In some embodiments, the monomer raw material B is a (meth) acrylic acid C 4-12 alkyl ester (preferably a (meth) acrylic acid C 4-10 alkyl ester, eg, a (meth) acrylic acid C 6-10 alkyl ester). Can contain at least one of. In some other embodiments, the monomer raw material B may contain at least one of a methacrylic acid C 1-18 alkyl ester (preferably a methacrylic acid C 1-14 alkyl ester, such as a methacrylic acid C 1-10 alkyl ester). .. The monomer raw material B may contain, for example, one or more selected from methyl methacrylate (MMA), n-butyl methacrylate (BMA) and 2-ethylhexyl methacrylate (2EHMA) as the acrylic monomer.
 上記アクリル系モノマーの他の例として、脂環式炭化水素基を有する(メタ)アクリル酸エステルが挙げられる。例えば、シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、1-アダマンチル(メタ)アクリレート等を用いることができる。脂環式炭化水素基を有する(メタ)アクリル酸エステルを使用しなくてもよい。 Another example of the above acrylic monomer is a (meth) acrylic acid ester having an alicyclic hydrocarbon group. For example, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate and the like can be used. It is not necessary to use a (meth) acrylic acid ester having an alicyclic hydrocarbon group.
 モノマー原料Bにおける上記(メタ)アクリル酸アルキルエステルおよび上記脂環式炭化水素基を有する(メタ)アクリル酸エステルの含有量は、例えば10重量%以上95重量%以下であってよく、20重量%以上95重量%以下であってもよく、30重量%以上90重量%以下であってもよく、40重量%以上90重量%以下であってもよく、50重量%以上85重量%以下であってもよい。 The content of the (meth) acrylic acid alkyl ester and the (meth) acrylic acid ester having an alicyclic hydrocarbon group in the monomer raw material B may be, for example, 10% by weight or more and 95% by weight or less, and 20% by weight. It may be 95% by weight or less, 30% by weight or more and 90% by weight or less, 40% by weight or more and 90% by weight or less, and 50% by weight or more and 85% by weight or less. May be good.
 モノマーS1とともにモノマー原料Bに含まれ得るモノマーの他の例として、アクリル系ポリマーに用いられ得るモノマーとして上記で例示したカルボキシ基含有モノマー、酸無水物基含有モノマー、水酸基含有モノマー、エポキシ基含有モノマー、シアノ基含有モノマー、イソシアネート基含有モノマー、アミド基含有モノマー、窒素原子含有環を有するモノマー、(メタ)アクリル酸アミノアルキル類、ビニルエステル類、ビニルエーテル類、オレフィン類、芳香族炭化水素基を有する(メタ)アクリル酸エステル、ハロゲン原子含有(メタ)アクリレート等が挙げられる。 As another example of the monomer that can be contained in the monomer raw material B together with the monomer S1, the carboxy group-containing monomer, the acid anhydride group-containing monomer, the hydroxyl group-containing monomer, and the epoxy group-containing monomer exemplified above as the monomers that can be used for the acrylic polymer. , Cyano group-containing monomer, isocyanate group-containing monomer, amide group-containing monomer, monomer having nitrogen atom-containing ring, aminoalkyl (meth) acrylate, vinyl esters, vinyl ethers, olefins, aromatic hydrocarbon group Examples thereof include (meth) acrylic acid ester and halogen atom-containing (meth) acrylate.
 ポリマー(B)のMwは、例えば5,000以上であってよく、10,000以上であることが好ましく、15,000以上でもよい。また、ポリマー(B)のMwは、例えば200,000以下であってよく、100,000以下であることが好ましく、50,000以下でもよく、30,000以下でもよい。ポリマー(B)のMwを適当な範囲に設定することにより、好適な相溶性およびレベリング性が発揮され得る。 The Mw of the polymer (B) may be, for example, 5,000 or more, preferably 10,000 or more, and may be 15,000 or more. The Mw of the polymer (B) may be, for example, 200,000 or less, preferably 100,000 or less, 50,000 or less, or 30,000 or less. By setting the Mw of the polymer (B) in an appropriate range, suitable compatibility and leveling properties can be exhibited.
 ポリマー(B)は、例えば、上述したモノマーを、溶液重合法、エマルション重合法、バルク重合法、懸濁重合法、光重合法等の公知の手法により重合させることで作製することができる。
 ポリマー(B)の分子量を調整するために、必要に応じて連鎖移動剤を用いることができる。使用する連鎖移動剤の例としては、t-ドデシルメルカプタン、メルカプトエタノール、α-チオグリセロール等のメルカプト基を有する化合物;チオグリコール酸、チオグリコール酸メチル等のチオグリコール酸エステル類;α-メチルスチレンダイマー;等が挙げられる。連鎖移動剤の使用量は特に制限されず、所望の分子量を有するポリマー(B)が得られるように適宜設定し得る。いくつかの態様において、モノマー100重量部に対する連鎖移動剤の使用量は、例えば0.1~5重量部であってよく、0.2~3重量部でもよく、0.5~2重量部でもよい。
The polymer (B) can be produced, for example, by polymerizing the above-mentioned monomer by a known method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or a photopolymerization method.
Chain transfer agents can be used as needed to adjust the molecular weight of the polymer (B). Examples of chain transfer agents used include compounds having a mercapto group such as t-dodecyl mercaptoethanol, mercaptoethanol, α-thioglycerol; thioglycolic acid esters such as thioglycolic acid and methyl thioglycolate; α-methylstyrene. Dimer; etc. The amount of the chain transfer agent used is not particularly limited, and can be appropriately set so that the polymer (B) having a desired molecular weight can be obtained. In some embodiments, the amount of the chain transfer agent used per 100 parts by weight of the monomer may be, for example, 0.1 to 5 parts by weight, 0.2 to 3 parts by weight, or 0.5 to 2 parts by weight. good.
 ベースポリマー(例えば、アクリル系ポリマー)100重量部に対するポリマー(B)の使用量は、例えば0.001重量部以上とすることができ、より高い使用効果を得る観点から0.01重量部以上としてもよく、0.03重量部以上としてもよい。また、上記ポリマー(B)の使用量は、例えば3重量部以下であってよく、屈折率への影響を軽減する観点から1重量部以下とすることが適当であり、0.5重量部以下でもよく、0.1重量部以下でもよい。 The amount of the polymer (B) used with respect to 100 parts by weight of the base polymer (for example, acrylic polymer) can be, for example, 0.001 part by weight or more, and 0.01 part by weight or more from the viewpoint of obtaining a higher use effect. It may be 0.03 part by weight or more. The amount of the polymer (B) used may be, for example, 3 parts by weight or less, and it is appropriate to use 1 part by weight or less from the viewpoint of reducing the influence on the refractive index, and 0.5 parts by weight or less. However, it may be 0.1 parts by weight or less.
 (無機粒子)
 ここに開示される技術は、屈折率向上剤としての無機粒子を実質的に使用しない態様で好ましく実施することができる。もっとも、ここに開示される粘着型光学フィルムのいくつかの態様において、所望の光学特性(全光線透過率、ヘイズ値)を満足し、かつ粘着剤としての特性を大きく損なわない限度で、屈折率向上剤として無機粒子を使用することは許容され得る。屈折率向上剤として使用し得る無機粒子の例としては、チタニア(酸化チタン、TiO)、ジルコニア(酸化ジルコニウム、ZrO)、酸化アルミニウム、酸化亜鉛、酸化スズ、酸化銅、チタン酸バリウム、酸化ニオブ(Nb等)等の無機酸化物(具体的には金属酸化物)により構成された無機粒子が挙げられる。上記無機粒子の平均粒径(レーザ散乱・回折法に基づく50%体積平均粒子径をいう。)は、例えば10nm~100nm程度の範囲から選択し得る。なお、無機粒子の屈折率は、当該無機粒子を構成する材料の単層膜(屈折率測定が可能な膜厚とする。)につき、市販の分光エリプソメーターを用いて、測定波長589nm、測定温度23℃の条件で測定される。分光エリプソメーターとしては、例えば製品名「EC-400」(JA.Woolam社製)またはその相当品が用いられる。屈折率向上剤として無機粒子を使用する場合における使用量は、ベースポリマー100重量部に対して5重量部未満とすることが好ましく、1重量部未満とすることがより好ましい。また、添加剤(HRO)を使用する態様では、上記無機粒子の使用量は、重量基準で、上記添加剤(HRO)の使用量の2倍以下とすることが好ましく、1倍以下または0.5倍以下とすることがより好ましい。
(Inorganic particles)
The technique disclosed herein can be preferably carried out in a manner in which inorganic particles as a refractive index improver are substantially not used. However, in some aspects of the adhesive optical film disclosed herein, the refractive index is such that the desired optical properties (total light transmittance, haze value) are satisfied and the properties as an adhesive are not significantly impaired. It may be acceptable to use inorganic particles as the improver. Examples of inorganic particles that can be used as a refractive index improver include titania (titanium oxide, TiO 2 ), zirconia ( zinc oxide, ZrO 2 ), aluminum oxide, zinc oxide, tin oxide, copper oxide, barium titanate, and oxidation. Examples thereof include inorganic particles composed of inorganic oxides (specifically, metal oxides) such as niobium (Nb 2 O 5 and the like). The average particle size of the inorganic particles (referring to the 50% volume average particle size based on the laser scattering / diffraction method) can be selected from the range of, for example, about 10 nm to 100 nm. The refractive index of the inorganic particles is determined by using a commercially available spectroscopic ellipsometer for a single-layer film (a film thickness capable of measuring the refractive index) of the material constituting the inorganic particles, with a measurement wavelength of 589 nm and a measurement temperature. It is measured under the condition of 23 ° C. As the spectroscopic ellipsometer, for example, the product name "EC-400" (manufactured by JA.Woolam) or an equivalent product thereof is used. When the inorganic particles are used as the refractive index improver, the amount used is preferably less than 5 parts by weight and more preferably less than 1 part by weight with respect to 100 parts by weight of the base polymer. Further, in the embodiment in which the additive (H RO ) is used, the amount of the inorganic particles used is preferably 2 times or less, preferably 1 times or less, or less than twice the amount of the additive (H RO) used on a weight basis. More preferably, it is 0.5 times or less.
 (架橋剤)
 ここに開示される技術において、粘着剤層の形成に使用する粘着剤組成物には、粘着剤の凝集力の調整等の目的で、必要に応じて架橋剤を含有させることができる。架橋剤としては、イソシアネート系架橋剤、エポキシ系架橋剤、アジリジン系架橋剤、オキサゾリン系架橋剤、メラミン系樹脂、金属キレート系架橋剤等の、粘着剤の分野において公知の架橋剤を使用することができる。なかでもイソシアネート系架橋剤を好ましく採用し得る。架橋剤の他の例として、1分子内に2以上のエチレン性不飽和基を有するモノマー、すなわち多官能性モノマーが挙げられる。架橋剤は、1種を単独でまたは2種以上を組み合わせて用いることができる。
(Crosslinking agent)
In the technique disclosed herein, the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer may contain a cross-linking agent, if necessary, for the purpose of adjusting the cohesive force of the pressure-sensitive adhesive. As the cross-linking agent, a cross-linking agent known in the field of adhesives such as an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, an aziridine-based cross-linking agent, an oxazoline-based cross-linking agent, a melamine-based resin, and a metal chelate-based cross-linking agent shall be used. Can be done. Of these, an isocyanate-based cross-linking agent can be preferably used. Another example of the cross-linking agent is a monomer having two or more ethylenically unsaturated groups in one molecule, that is, a polyfunctional monomer. The cross-linking agent may be used alone or in combination of two or more.
 イソシアネート系架橋剤としては、2官能以上のイソシアネート化合物を用いることができ、例えば、トリメチレンジイソシアネート、ブチレンジイソシアネート、ヘキサメチレンジイソシアネート(HDI)、ダイマー酸ジイソシアネートなどの脂肪族ポリイソシアネート類;シクロペンチレンジイソシアネート、シクロヘキシレンジイソシアネート、イソホロンジイソシアネート(IPDI)、1,3-ビス(イソシアナトメチル)シクロヘキサンなどの脂環族イソシアネート類;2,4-トリレンジイソシアネート、4,4’-ジフェニルメタンジイソシアネート、キシリレンジイソシアネート(XDI)などの芳香族イソシアネート類;上記イソシアネート化合物をアロファネート結合、ビウレット結合、イソシアヌレート結合、ウレトジオン結合、ウレア結合、カルボジイミド結合、ウレトンイミン結合、オキサジアジントリオン結合などにより変性したポリイソシネート変性体;などが挙げられる。市販品の例としては、商品名タケネート300S、タケネート500、タケネート600、タケネートD165N、タケネートD178N(以上、武田薬品工業社製)、スミジュールT80、スミジュールL、デスモジュールN3400(以上、住化バイエルウレタン社製)、ミリオネートMR、ミリオネートMT、コロネートL、コロネートHL、コロネートHX(以上、東ソー社製)などが挙げられる。イソシアネート化合物は、1種を単独でまたは2種以上を組み合わせて用いることができる。2官能のイソシアネート化合物と3官能以上のイソシアネート化合物を併用してもよい。 As the isocyanate-based cross-linking agent, a bifunctional or higher functional isocyanate compound can be used, for example, aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), and dimerate diisocyanate; cyclopentylene diisocyanate. , Cyclohexylene diisocyanate, isophorone diisocyanate (IPDI), alicyclic isocyanates such as 1,3-bis (isocyanatomethyl) cyclohexane; 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate (xylylene diisocyanate) Aromatic isocyanates such as XDI); polyisocyanate modified products obtained by modifying the above isocyanate compounds with allophanate bonds, biuret bonds, isocyanurate bonds, uretdione bonds, urea bonds, carbodiimide bonds, uretonimine bonds, oxadiazine trione bonds, etc. Can be mentioned. Examples of commercially available products include trade names Takenate 300S, Takenate 500, Takenate 600, Takenate D165N, Takeda D178N (above, manufactured by Takeda Pharmaceutical Company Limited), Sumijuru T80, Sumijuru L, Death Module N3400 (above, Sumika Bayer). (Made by Urethane), Millionate MR, Millionate MT, Coronate L, Coronate HL, Coronate HX (all manufactured by Tosoh) and the like. The isocyanate compound may be used alone or in combination of two or more. A bifunctional isocyanate compound and a trifunctional or higher functional isocyanate compound may be used in combination.
 エポキシ系架橋剤としては、例えば、ビスフェノールA、エピクロルヒドリン型のエポキシ系樹脂、エチレングリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、1,6-ヘキサンジオールグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、ジアミングリシジルアミン、N,N,N’,N’-テトラグリシジル-m-キシリレンジアミンおよび1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン等を挙げることができる。これらは1種を単独でまたは2種以上を組み合わせて用いることができる。 Examples of the epoxy-based cross-linking agent include bisphenol A, epichlorohydrin-type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, and trimethylol. Propanetriglycidyl ether, diglycidyl aniline, diglycidylamine, N, N, N', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, etc. Can be mentioned. These can be used alone or in combination of two or more.
 多官能性モノマーとしては、例えば、エチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、1,12-ドデカンジオールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、テトラメチロールメタントリ(メタ)アクリレート、アリル(メタ)アクリレート、ビニル(メタ)アクリレート、ジビニルベンゼン、ビスフェノキシエタノールフルオレンジ(メタ)アクリレート、ビスフェノールAジ(メタ)アクリレート、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート、ブチルジオール(メタ)アクリレート、ヘキシルジオールジ(メタ)アクリレート等が挙げられる。多官能性モノマーは、1種を単独でまたは2種以上を組み合わせて用いることができる。 Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like. Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecane Didioldi (meth) acrylate, trimethylolpropantri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, bisphenoxyethanol full orange (meth) acrylate, bisphenol Examples thereof include A-di (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, butyldiol (meth) acrylate, and hexyldiol di (meth) acrylate. The polyfunctional monomer may be used alone or in combination of two or more.
 架橋剤(多官能性モノマーであり得る。)を用いる場合における使用量は、特に限定されず、例えば、ベースポリマー100重量部に対して0.001重量部~5.0重量部程度の範囲とすることができる。粘着剤の柔軟性向上の観点から、いくつかの態様において、ベースポリマー100重量部に対する架橋剤の使用量は、好ましくは3.0重量部以下、より好ましくは2.0重量部以下であり、1.0重量部以下でもよく、0.5重量部以下でもよく、0.2重量部以下でもよい。また、架橋剤の使用効果を適切に発揮する観点から、いくつかの態様において、ベースポリマー100重量部に対する架橋剤の使用量は、例えば0.005重量部以上であってよく、0.01重量部以上であってもよく、0.05重量部以上でもよく、0.08重量部以上でもよい。 When a cross-linking agent (which may be a polyfunctional monomer) is used, the amount used is not particularly limited, and is, for example, in the range of about 0.001 part by weight to 5.0 parts by weight with respect to 100 parts by weight of the base polymer. can do. From the viewpoint of improving the flexibility of the pressure-sensitive adhesive, in some embodiments, the amount of the cross-linking agent used with respect to 100 parts by weight of the base polymer is preferably 3.0 parts by weight or less, more preferably 2.0 parts by weight or less. It may be 1.0 part by weight or less, 0.5 part by weight or less, or 0.2 part by weight or less. Further, from the viewpoint of appropriately exerting the effect of using the cross-linking agent, in some embodiments, the amount of the cross-linking agent used with respect to 100 parts by weight of the base polymer may be, for example, 0.005 parts by weight or more, and 0.01 weight by weight. It may be parts or more, 0.05 parts by weight or more, or 0.08 parts by weight or more.
 架橋反応をより効果的に進行させるために、架橋触媒を用いてもよい。架橋触媒の例としては、テトラ-n-ブチルチタネート、テトライソプロピルチタネート、ナーセム第二鉄、ブチルスズオキシド、ジオクチルスズジラウレート等の金属系架橋触媒等が挙げられる。なかでも、ジオクチルスズジラウレート等のスズ系架橋触媒が好ましい。架橋触媒の使用量は特に制限されない。ベースポリマー100重量部に対する架橋触媒の使用量は、架橋反応速度の速さと粘着剤組成物のポットライフの長さとのバランスを考慮して、例えば凡そ0.0001重量部以上1重量部以下の範囲とすることができ、0.001重量部以上0.5重量部以下の範囲とすることが好ましい。 A cross-linking catalyst may be used to allow the cross-linking reaction to proceed more effectively. Examples of the cross-linking catalyst include metal-based cross-linking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, ferric nasem, butyl tin oxide, and dioctyl tin dilaurate. Of these, tin-based cross-linking catalysts such as dioctyl tin dilaurate are preferable. The amount of the cross-linking catalyst used is not particularly limited. The amount of the cross-linking catalyst used with respect to 100 parts by weight of the base polymer is, for example, in the range of about 0.0001 parts by weight or more and 1 part by weight or less in consideration of the balance between the speed of the cross-linking reaction rate and the length of the pot life of the pressure-sensitive adhesive composition. The range is preferably 0.001 part by weight or more and 0.5 part by weight or less.
 粘着剤組成物には、架橋遅延剤として、ケト-エノール互変異性を生じる化合物を含有させることができる。これにより、粘着剤組成物のポットライフを延長する効果が実現され得る。例えば、イソシアネート系架橋剤を含む粘着剤組成物において、ケト-エノール互変異性を生じる化合物を好ましく利用し得る。ケト-エノール互変異性を生じる化合物としては、各種のβ-ジカルボニル化合物を用いることができる。例えば、β-ジケトン類(アセチルアセトン、2,4-ヘキサンジオン等)やアセト酢酸エステル類(アセト酢酸メチル、アセト酢酸エチル等)を好ましく採用し得る。ケト-エノール互変異性を生じる化合物は、1種を単独でまたは2種以上を組み合わせて用いることができる。ケト-エノール互変異性を生じる化合物の使用量は、ベースポリマー100重量部に対して、例えば0.1重量部以上20重量部以下とすることができ、0.5重量部以上10重量部以下としてもよく、1重量部以上5重量部以下としてもよい。 The pressure-sensitive adhesive composition can contain a compound that causes keto-enol tautomerism as a cross-linking retarder. Thereby, the effect of extending the pot life of the pressure-sensitive adhesive composition can be realized. For example, in a pressure-sensitive adhesive composition containing an isocyanate-based cross-linking agent, a compound that causes keto-enol tautomerism can be preferably used. Various β-dicarbonyl compounds can be used as the compound that causes keto-enol telecommunication. For example, β-diketones (acetylacetone, 2,4-hexanedione, etc.) and acetoacetic esters (methyl acetoacetate, ethyl acetoacetate, etc.) can be preferably adopted. The compounds that cause keto-enol tautomerism can be used alone or in combination of two or more. The amount of the compound that causes keto-enol telecommunication can be, for example, 0.1 parts by weight or more and 20 parts by weight or less, and 0.5 parts by weight or more and 10 parts by weight or less, based on 100 parts by weight of the base polymer. It may be 1 part by weight or more and 5 parts by weight or less.
 (粘着付与剤)
 ここに開示される技術における粘着剤層には、粘着付与剤を含有させてもよい。粘着付与剤としては、ロジン系粘着付与樹脂、テルペン系粘着付与樹脂、フェノール系粘着付与樹脂、炭化水素系粘着付与樹脂、ケトン系粘着付与樹脂、ポリアミド系粘着付与樹脂、エポキシ系粘着付与樹脂、エラストマー系粘着付与樹脂等の公知の粘着付与樹脂を用いることができる。これらは、1種を単独でまたは2種以上を組み合わせて用いることができる。粘着付与樹脂の使用量は特に限定されず、目的や用途に応じて適切な粘着性能が発揮されるように設定することができる。いくつかの態様において、屈折率や透明性の観点から、粘着付与剤の使用量は、粘着剤層のベースポリマー100重量部に対して30重量部以下とすることが適当であり、10重量部以下とすることが好ましく、5重量部以下とすることがより好ましい。ここに開示される技術は、粘着付与剤を使用しない態様で好ましく実施され得る。
(Adhesive)
The pressure-sensitive adhesive layer in the technique disclosed herein may contain a pressure-sensitive adhesive. Examples of the pressure-sensitive adhesive include rosin-based pressure-sensitive adhesive resin, terpen-based pressure-sensitive adhesive resin, phenol-based pressure-sensitive adhesive resin, hydrocarbon-based pressure-sensitive adhesive resin, ketone-based pressure-sensitive adhesive resin, polyamide-based pressure-sensitive adhesive resin, epoxy-based pressure-sensitive adhesive resin, and elastomer. A known pressure-sensitive adhesive resin such as a system-based pressure-sensitive adhesive resin can be used. These can be used alone or in combination of two or more. The amount of the tackifying resin used is not particularly limited, and can be set so as to exhibit appropriate adhesive performance according to the purpose and application. In some embodiments, from the viewpoint of refractive index and transparency, it is appropriate that the amount of the tackifier used is 30 parts by weight or less with respect to 100 parts by weight of the base polymer of the pressure-sensitive adhesive layer, and 10 parts by weight. It is preferably less than or equal to, and more preferably less than or equal to 5 parts by weight. The techniques disclosed herein can be preferably performed in a manner that does not use a tackifier.
 (その他の添加剤)
 ここに開示される技術において、粘着剤層の形成に使用する粘着剤組成物は、本発明の効果が著しく妨げられない範囲で、可塑剤、軟化剤、着色剤、帯電防止剤、老化防止剤、紫外線吸収剤、酸化防止剤、光安定剤、防腐剤等の、粘着剤組成物に使用され得る公知の添加剤を、必要に応じて含んでいてもよい。このような各種添加剤については、従来公知のものを常法により使用することができ、特に本発明を特徴づけるものではないので、詳細な説明は省略する。
(Other additives)
In the techniques disclosed herein, the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer is a plasticizer, a softener, a colorant, an antistatic agent, and an anti-aging agent as long as the effects of the present invention are not significantly impaired. , UV absorbers, antioxidants, light stabilizers, preservatives, and other known additives that can be used in the pressure-sensitive adhesive composition may be included, if necessary. As for such various additives, conventionally known ones can be used by a conventional method and do not particularly characterize the present invention, and thus detailed description thereof will be omitted.
 (粘着剤層の作製)
 ここに開示される技術において、粘着剤層を構成する粘着剤は、溶剤型、活性エネルギー線硬化型、水分散型、ホットメルト型等の形態の粘着剤組成物を、乾燥、架橋、重合、冷却等により硬化させてなる粘着剤、すなわち上記粘着剤組成物の硬化物であり得る。粘着剤組成物の硬化手段(例えば乾燥、架橋、重合、冷却等)は、1種のみを適用してもよく、2種以上を同時に、または多段階にわたって適用してもよい。溶剤型粘着剤組成物では、典型的には該組成物を乾燥(好ましくは、さらに架橋)させて粘着剤を形成することができる。活性エネルギー線硬化型粘着剤組成物では、典型的には活性エネルギー線を照射して重合反応および/または架橋反応を進行させることにより粘着剤が形成される。活性エネルギー線硬化型粘着剤組成物で乾燥させる必要がある場合は、乾燥後に活性エネルギー線を照射するとよい。
(Preparation of adhesive layer)
In the technique disclosed herein, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is a pressure-sensitive adhesive composition in the form of a solvent type, an active energy ray-curable type, an aqueous dispersion type, a hot melt type, etc. It may be a pressure-sensitive adhesive cured by cooling or the like, that is, a cured product of the above-mentioned pressure-sensitive adhesive composition. As the curing means (for example, drying, cross-linking, polymerization, cooling, etc.) of the pressure-sensitive adhesive composition, only one type may be applied, or two or more types may be applied simultaneously or in multiple stages. In solvent-based pressure-sensitive adhesive compositions, the composition can typically be dried (preferably further crosslinked) to form a pressure-sensitive adhesive. In the active energy ray-curable pressure-sensitive adhesive composition, a pressure-sensitive adhesive is typically formed by irradiating with active energy rays to proceed with a polymerization reaction and / or a cross-linking reaction. When it is necessary to dry with the active energy ray-curable pressure-sensitive adhesive composition, it is advisable to irradiate the active energy ray after drying.
 ここに開示される粘着型光学フィルムの粘着剤層は、粘着剤組成物を適当な表面に付与(例えば塗布)した後、該組成物を硬化させることにより形成され得る。粘着剤組成物の塗布は、例えば、グラビアロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーコーター等の慣用のコーターを用いて実施することができる。 The pressure-sensitive adhesive layer of the pressure-sensitive optical film disclosed herein can be formed by applying (for example, applying) a pressure-sensitive adhesive composition to an appropriate surface and then curing the composition. The application of the pressure-sensitive adhesive composition can be carried out using a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater.
 ここに開示される粘着型光学フィルムの粘着剤層は、後硬化性を有する粘着剤層であってもよく、後硬化性を有しない粘着剤層であってもよい。ここで、後硬化性を有する粘着剤層とは、熱または活性エネルギー線(例えば紫外線)の照射によってさらに硬化させることが可能な粘着剤層をいう。後硬化性を有する粘着剤層の例として、ベースポリマーの側鎖に未反応のエチレン性不飽和基を有する粘着剤層や、未反応の多官能性モノマーを含む粘着剤層が挙げられる。いくつかの態様において、粘着剤層は後硬化性を有しないことが好ましい。後硬化性を有しない粘着剤層は、後硬化反応に伴う寸法変化を生じない(すなわち、寸法安定性がよい)ので、粘着型光学フィルムまたは該粘着型光学フィルムを含む積層体の反りを抑制しやすい。後硬化による寸法変化(例えば硬化収縮)が生じないことは、粘着剤層の光学歪を抑制する観点からも有利となり得る。 The pressure-sensitive adhesive layer of the pressure-sensitive optical film disclosed herein may be a pressure-sensitive adhesive layer having post-curability, or may be a pressure-sensitive adhesive layer having no post-curability. Here, the pressure-sensitive adhesive layer having post-curability refers to a pressure-sensitive adhesive layer that can be further cured by irradiation with heat or active energy rays (for example, ultraviolet rays). Examples of the post-curable pressure-sensitive adhesive layer include a pressure-sensitive adhesive layer having an unreacted ethylenically unsaturated group in the side chain of the base polymer, and a pressure-sensitive adhesive layer containing an unreacted polyfunctional monomer. In some embodiments, the pressure-sensitive adhesive layer preferably does not have post-curing properties. Since the pressure-sensitive adhesive layer having no post-curing property does not cause a dimensional change due to the post-curing reaction (that is, has good dimensional stability), the warpage of the adhesive optical film or the laminate containing the adhesive optical film is suppressed. It's easy to do. The fact that dimensional changes (for example, curing shrinkage) due to post-curing do not occur can be advantageous from the viewpoint of suppressing optical distortion of the pressure-sensitive adhesive layer.
 粘着剤層の厚さは特に限定されず、例えば3μm以上とすることができ、5μm以上であることが好ましい。厚さ5μm以上の粘着剤層によると、良好な粘着特性が得られやすい。また、かかる厚さの粘着剤層は、被着体表面に存在し得る凹凸を吸収して該被着体に密着性よく接合させやすい。粘着剤層の厚さが5μm以上であることは、光干渉による色付きや色むらを防止する観点からも好ましい。いくつかの態様において、粘着剤層の厚さは、10μm以上であってもよく、20μm以上でもよく、30μm以上でもよく、50μm以上でもよく、70μm以上または85μm以上でもよい。また、いくつかの態様において、粘着剤層の厚さは、例えば300μm以下であってよく、250μm以下でもよく、200μm以下でもよく、150μm以下でもよく、120μm以下でもよい。粘着剤層の厚さが大きすぎないことは、粘着型光学フィルムの薄型化等の観点から有利となり得る。ここに開示される技術は、例えば、粘着剤層の厚さが3μm~200μm(より好ましくは5μm~100μm)の範囲となる態様で好ましく実施され得る。光透過性部材の第1面および第2面に第1粘着剤層および第2粘着剤層を有する形態の粘着型光学フィルムでは、上述した粘着剤層の厚さは、少なくとも第1粘着剤層の厚さに適用され得る。第2粘着剤層の厚さも同様の範囲から選択され得る。 The thickness of the pressure-sensitive adhesive layer is not particularly limited, and can be, for example, 3 μm or more, preferably 5 μm or more. According to the pressure-sensitive adhesive layer having a thickness of 5 μm or more, good pressure-sensitive adhesive properties can be easily obtained. Further, the pressure-sensitive adhesive layer having such a thickness absorbs irregularities that may exist on the surface of the adherend and is easily bonded to the adherend with good adhesion. It is preferable that the thickness of the pressure-sensitive adhesive layer is 5 μm or more from the viewpoint of preventing coloring and color unevenness due to light interference. In some embodiments, the thickness of the pressure-sensitive adhesive layer may be 10 μm or greater, 20 μm or greater, 30 μm or greater, 50 μm or greater, 70 μm or greater, or 85 μm or greater. Further, in some embodiments, the thickness of the pressure-sensitive adhesive layer may be, for example, 300 μm or less, 250 μm or less, 200 μm or less, 150 μm or less, or 120 μm or less. It is possible that the thickness of the pressure-sensitive adhesive layer is not too large, which is advantageous from the viewpoint of reducing the thickness of the pressure-sensitive optical film. The technique disclosed herein can be preferably carried out, for example, in an embodiment in which the thickness of the pressure-sensitive adhesive layer is in the range of 3 μm to 200 μm (more preferably 5 μm to 100 μm). In the pressure-sensitive optical film having the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer on the first and second surfaces of the light-transmitting member, the thickness of the pressure-sensitive adhesive layer described above is at least the first pressure-sensitive adhesive layer. Can be applied to the thickness of. The thickness of the second pressure-sensitive adhesive layer can be selected from the same range.
 (剥離強度)
 ここに開示される粘着型光学フィルムのいくつかの態様において、該粘着型光学フィルムのガラス板に対する剥離強度は、凡そ1.0N/25mm以上(例えば1.5N/25mm以上)であることが適当であり、好ましくは2N/25mm以上、より好ましくは3N/25mm以上であり、4N/25mm以上でもよく、6N/25mm以上でもよく、8N/25mm以上でもよく、10N/25mm以上でもよく、12N/25mm以上でもよい。剥離強度の上限は特に制限されず、例えば30N/25mm以下、25N/25mm以下または20N/25mm以下であり得る。
(Peeling strength)
In some aspects of the adhesive optical film disclosed herein, it is appropriate that the peel strength of the adhesive optical film with respect to the glass plate is approximately 1.0 N / 25 mm or more (for example, 1.5 N / 25 mm or more). It is preferably 2N / 25mm or more, more preferably 3N / 25mm or more, 4N / 25mm or more, 6N / 25mm or more, 8N / 25mm or more, 10N / 25mm or more, 12N / It may be 25 mm or more. The upper limit of the peel strength is not particularly limited, and may be, for example, 30 N / 25 mm or less, 25 N / 25 mm or less, or 20 N / 25 mm or less.
 ここで、上記剥離強度は、被着体としてのアルカリガラス板に圧着して23℃、50%RHの環境で30分間放置し、次いで加圧脱泡装置(オートクレーブ)に投入して温度50℃、圧力0.5MPaの条件で30分間のオートクレーブ処理を行い、さらに23℃、50%RHの雰囲気下で24時間放置した後に、剥離角度180度、引張速度300mm/分の条件で180°引きはがし粘着力を測定することにより把握される。測定にあたっては、必要に応じて、測定対象の粘着型光学フィルムに適切な裏打ち材(例えば、厚さ25μm程度~50μm程度のポリエチレンテレフタレート(PET)フィルム)を貼り付けて補強することができる。剥離強度は、より具体的には、後述する実施例に記載の方法に準じて測定することができる。
 ここに開示される粘着型光学フィルムが第1粘着面および第2粘着面を有する両面粘着型光学フィルムの形態である場合、いくつかの態様において、上述した剥離強度は、好ましくは少なくとも第1粘着面に適用され、より好ましくは第1粘着面および第2粘着面の両方に適用される。第1粘着面のガラス板に対する剥離強度と、第2粘着面のガラスに対する剥離強度とは、同程度であってもよく、異なっていてもよい。
Here, the peel strength is such that the peel strength is pressure-bonded to an alkaline glass plate as an adherend, left to stand in an environment of 23 ° C. and 50% RH for 30 minutes, and then put into a pressure defoaming device (autoclave) to have a temperature of 50 ° C. After autoclaving for 30 minutes under the condition of pressure of 0.5 MPa and further leaving for 24 hours in the atmosphere of 23 ° C. and 50% RH, peeling off by 180 ° under the condition of peeling angle of 180 degrees and tensile speed of 300 mm / min. It is grasped by measuring the adhesive strength. In the measurement, if necessary, an appropriate backing material (for example, a polyethylene terephthalate (PET) film having a thickness of about 25 μm to about 50 μm) can be attached to the adhesive optical film to be measured to reinforce it. More specifically, the peel strength can be measured according to the method described in Examples described later.
When the adhesive optical film disclosed herein is in the form of a double-sided adhesive optical film having a first adhesive surface and a second adhesive surface, in some embodiments, the above-mentioned peel strength is preferably at least the first adhesive. It is applied to the surface, more preferably to both the first adhesive surface and the second adhesive surface. The peel strength of the first adhesive surface to the glass plate and the peel strength of the second adhesive surface to the glass may be the same or different.
<光透過性部材>
 ここに開示される技術において、光透過性部材の材質は特に限定されず、粘着型光学フィルムの使用目的や使用態様等に応じて適宜選択することができる。粘着型光学フィルムを構成する光透過性部材の例には、後述する光学部材(例えば、偏光板等の機能性フィルム)が包含される。
<Light transmissive member>
In the technique disclosed herein, the material of the light transmissive member is not particularly limited, and can be appropriately selected depending on the purpose of use, the mode of use, and the like of the adhesive optical film. Examples of the light-transmitting member constituting the adhesive optical film include an optical member (for example, a functional film such as a polarizing plate) described later.
 いくつかの態様において、光透過性部材として各種のフィルム基材を好ましく用いることができる。上記フィルム基材としては、独立して形状維持可能な(自立型の、あるいは非依存性の)樹脂フィルムをベースフィルムとして含むものが好ましい。ここで「樹脂フィルム」とは、非多孔質の構造であって、典型的には実質的に気泡を含まない(ボイドレスの)樹脂フィルムを意味する。したがって、上記樹脂フィルムは、発泡体フィルムや不織布とは区別される概念である。上記樹脂フィルムとしては、独立して形状維持可能な(自立型の、あるいは非依存性の)ものが好ましく用いられ得る。上記樹脂フィルムは、単層構造であってもよく、2層以上の多層構造(例えば、3層構造)であってもよい。 In some embodiments, various film substrates can be preferably used as the light transmissive member. The film base material preferably contains a resin film (self-supporting or independent) whose shape can be maintained independently as a base film. Here, the "resin film" means a resin film (of voidless) having a non-porous structure and typically containing substantially no bubbles. Therefore, the resin film is a concept that is distinguished from foam films and non-woven fabrics. As the resin film, one that can independently maintain its shape (self-supporting or independent) can be preferably used. The resin film may have a single-layer structure or a multi-layer structure having two or more layers (for example, a three-layer structure).
 樹脂フィルムを構成する材料としては、例えば、ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート(PBT)、ポリエチレンナフタレート(PEN)等のポリエステルを主成分とするポリエステル系樹脂、ポリエチレン(PE)、ポリプロピレン(PP)、エチレン-プロピレン共重合体、エチレン-ブテン共重合体等のポリオレフィンを主成分とするポリオレフィン系樹脂、トリアセチルセルロース等のセルロース樹脂、アセテート系樹脂、ポリスルホン系樹脂、ポリエーテルスルホン系樹脂、ポリカーボネート系樹脂、ナイロン6、ナイロン66、部分芳香族ポリアミド等のポリアミド(PA)系樹脂、ポリイミド(PI)系樹脂、透明ポリイミド樹脂、ポリアミドイミド(PAI)、ポリエーテルエーテルケトン(PEEK)、ポリエーテルスルホン(PES)、ノルボルネン系樹脂等の環状ポリオレフィン樹脂、(メタ)アクリル系樹脂、ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、ポリスチレン系樹脂、ポリビニルアルコール系樹脂、エチレン-酢酸ビニル共重合体樹脂、エチレン-ビニルアルコール共重合体樹脂、ポリアリレート系樹脂、ポリフェニレンサルファイド(PPS)系樹脂、ポリウレタン(PU)、エチレン-酢酸ビニル共重合体(EVA)、ポリテトラフルオロエチレン(PTFE)やフッ素化ポリイミド等のフッ素樹脂、等が挙げられる。 Examples of the material constituting the resin film include a polyester-based resin containing a polyester as a main component, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyethylene (PE), and polypropylene (PP). ), Polyimide-propylene copolymer, polyolefin-based resin such as ethylene-butene copolymer, cellulose resin such as triacetyl cellulose, acetate resin, polysulfone resin, polyethersulfone resin, polycarbonate Polyaceous resins, nylon 6, nylon 66, polyamide (PA) resins such as partially aromatic polyamide, polyimide (PI) resins, transparent polyimide resins, polyamideimide (PAI), polyether ether ketone (PEEK), polyether sulfone (PES), cyclic polyolefin resin such as norbornene resin, (meth) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer resin, Ethylene-vinyl alcohol copolymer resin, polyallylate resin, polyphenylene sulfide (PPS) resin, polyurethane (PU), ethylene-vinyl acetate copolymer (EVA), polytetrafluoroethylene (PTFE), fluorinated polyimide, etc. Fluororesin, etc.
 上記樹脂フィルムは、このような樹脂の1種を単独で含む樹脂材料を用いて形成されたものであってもよく、2種以上がブレンドされた樹脂材料を用いて形成されたものであってもよい。上記樹脂フィルムは、無延伸であってもよく、延伸(例えば一軸延伸または二軸延伸)されたものであってもよい。いくつかの態様において、例えば、PETフィルム、PBTフィルム、PENフィルム、無延伸ポリプロピレン(CPP)フィルム、二軸延伸ポリプロピレン(OPP)フィルム、低密度ポリエチレン(LDPE)フィルム、直鎖状低密度ポリエチレン(LLDPE)フィルム、PP/PEブレンドフィルム等が好ましく用いられ得る。強度や寸法安定性の観点から好ましい樹脂フィルムの例として、PETフィルム、PENフィルム、PPSフィルムおよびPEEKフィルムが挙げられる。入手容易性等の観点からPETフィルムおよびPPSフィルムが特に好ましく、なかでもPETフィルムが好ましい。 The resin film may be formed by using a resin material containing one kind of such a resin alone, or may be formed by using a resin material in which two or more kinds are blended. May be good. The resin film may be unstretched or stretched (for example, uniaxially stretched or biaxially stretched). In some embodiments, for example, PET film, PBT film, PEN film, unstretched polypropylene (CPP) film, biaxially stretched polypropylene (OPP) film, low density polyethylene (LDPE) film, linear low density polyethylene (LLDPE). ) Film, PP / PE blend film and the like can be preferably used. Examples of preferable resin films from the viewpoint of strength and dimensional stability include PET film, PEN film, PPS film and PEEK film. From the viewpoint of availability, PET film and PPS film are particularly preferable, and PET film is particularly preferable.
 樹脂フィルムには、本発明の効果が著しく妨げられない範囲で、光安定剤、酸化防止剤、帯電防止剤、着色剤(染料、顔料等)、充填材、スリップ剤、アンチブロッキング剤等の公知の添加剤を、必要に応じて配合することができる。添加剤の配合量は特に限定されず、粘着型光学フィルムの用途等に応じて適宜設定することができる。 Known resin films include light stabilizers, antioxidants, antistatic agents, colorants (dyees, pigments, etc.), fillers, slip agents, antiblocking agents, etc., as long as the effects of the present invention are not significantly impaired. Additives can be blended as needed. The blending amount of the additive is not particularly limited, and can be appropriately set according to the application of the adhesive optical film and the like.
 樹脂フィルムの製造方法は特に限定されない。例えば、押出成形、インフレーション成形、Tダイキャスト成形、カレンダーロール成形等の、従来公知の一般的な樹脂フィルム成形方法を適宜採用することができる。 The manufacturing method of the resin film is not particularly limited. For example, conventionally known general resin film molding methods such as extrusion molding, inflation molding, T-die casting molding, and calendar roll molding can be appropriately adopted.
 上記光透過性部材は、このようなベースフィルムから実質的に構成されたものであり得る。あるいは、上記光透過性部材は、上記ベースフィルムの他に、補助的な層を含むものであってもよい。上記補助的な層の例としては、光学特性調整層(例えば着色層、反射防止層)、所望の外観を付与するための印刷層やラミネート層、帯電防止層、下塗り層、剥離層等の表面処理層が挙げられる。 The light transmissive member may be substantially composed of such a base film. Alternatively, the light transmissive member may include an auxiliary layer in addition to the base film. Examples of the auxiliary layer include an optical property adjusting layer (for example, a coloring layer and an antireflection layer), a surface such as a printing layer or a laminating layer for imparting a desired appearance, an antistatic layer, an undercoat layer, and a peeling layer. A processing layer can be mentioned.
 いくつかの態様において、光透過性部材の全光線透過率は、例えば50%超であってよく、70%以上であってもよい。いくつかの好ましい態様では、光透過性部材の全光線透過率は80%以上であり、より好ましくは90%以上であり、95%以上(例えば95~100%)であってもよい。上記全光線透過率は、JIS K 7136:2000に準拠して、市販の透過率計を使用して測定される。透過率計としては、村上色彩技術研究所製の商品名「HAZEMETER HM-150」またはその相当品が用いられる。上記光透過性部材の好適例として、光透過性を有する樹脂フィルムが挙げられる。上記光透過性部材は、光学フィルムであってもよい。 In some embodiments, the total light transmittance of the light transmissive member may be, for example, more than 50%, and may be 70% or more. In some preferred embodiments, the total light transmittance of the light transmissive member is 80% or more, more preferably 90% or more, and may be 95% or more (for example, 95 to 100%). The total light transmittance is measured using a commercially available transmittance meter in accordance with JIS K 7136: 2000. As the transmittance meter, the product name "HAZEMETER HM-150" manufactured by Murakami Color Technology Research Institute or its equivalent is used. A preferable example of the light-transmitting member is a resin film having light-transmitting property. The light transmissive member may be an optical film.
 いくつかの態様において、上記光透過性部材の構成に用いられ得る材料としては、例えば、銅、銀、金、鉄、錫、パラジウム、アルミニウム、ニッケル、チタン、クロム、インジウム、亜鉛等、またはこれらの2種以上を含む合金等の金属材料や、例えばポリイミド系樹脂、アクリル系樹脂、ポリエーテルニトリル系樹脂、ポリエーテルスルホン系樹脂、ポリエステル系樹脂(PET系樹脂、ポリエチレンナフタレート系樹脂等)、ポリ塩化ビニル系樹脂、ポリフェニレンサルファイド系樹脂、ポリエーテルエーテルケトン系樹脂、ポリアミド系樹脂(いわゆるアラミド樹脂等)、ポリアリレート系樹脂、フッ素系樹脂、ポリカーボネート系樹脂、ジアセチルセルロースやトリアセチルセルロース等のセルロース系ポリマー、ビニルブチラール系ポリマー、液晶ポリマー、カーボンナノチューブやグラフェン等のカーボン材料、PEDOT(ポリ(3,4-エチレンジオキシチオフェン))やポリアニリン等に代表される高分子材料、等の各種樹脂材料(典型的にはプラスチック材)、アルミナ、ジルコニア、チタニア、SiO、ITO(酸化インジウムスズ)、ATO(アンチモンドープ酸化スズ)等の金属酸化物及びその混合物、窒化アルミニウム、窒化ケイ素、窒化チタン、窒化ガリウム、窒化インジウム等の窒化物及びその複合物、アルカリガラス、無アルカリガラス、石英ガラス、ホウケイ酸ガラス、サファイアガラス等の無機材料、これらの混合物や複合物、等が挙げられるが、これらに限定されない。 In some embodiments, the materials that can be used in the construction of the light transmissive member include, for example, copper, silver, gold, iron, tin, palladium, aluminum, nickel, titanium, chromium, indium, zinc and the like, or these. Metallic materials such as alloys containing two or more of the above, for example, polyimide resins, acrylic resins, polyether nitrile resins, polyether sulfone resins, polyester resins (PET resins, polyethylene naphthalate resins, etc.), Polyvinyl chloride resin, polyphenylene sulfide resin, polyether ether ketone resin, polyamide resin (so-called aramid resin, etc.), polyarylate resin, fluorine resin, polycarbonate resin, cellulose such as diacetyl cellulose and triacetyl cellulose Various resin materials such as based polymers, vinyl butyral polymers, liquid crystal polymers, carbon materials such as carbon nanotubes and graphene, and polymer materials represented by PEDOT (poly (3,4-ethylenedioxythiophene)) and polyaniline. Metal oxides such as (typically plastic materials), alumina, zirconia, titania, SiO 2 , ITO (indium tin oxide), ATO (antimony-doped tin oxide) and mixtures thereof, aluminum nitride, silicon nitride, titanium nitride, Examples thereof include nitrides such as gallium nitride and indium nitride and their composites, inorganic materials such as alkaline glass, non-alkali glass, quartz glass, borosilicate glass and sapphire glass, and mixtures and composites thereof. Not limited.
 光透過性部材の厚さは、特に限定されず、粘着型光学フィルムの使用目的や使用態様等に応じて選択し得る。光透過性部材の厚さは、例えば500μm以下であってよく、取扱い性や加工性の観点から300μm以下であることが好ましく、150μm以下でもよく、100μm以下でもよく、50μm以下でもよく、25μm以下でもよく、10μm以下でもよい。光透過性部材の厚さが小さくなると、被着体の表面形状への追従性が向上する傾向にある。また、取扱い性や加工性等の観点から、光透過性部材の厚さは、例えば2μm以上であってよく、10μm以上でもよく、25μm以上でもよい。 The thickness of the light-transmitting member is not particularly limited, and can be selected according to the purpose of use, the mode of use, etc. of the adhesive optical film. The thickness of the light transmissive member may be, for example, 500 μm or less, preferably 300 μm or less from the viewpoint of handleability and workability, 150 μm or less, 100 μm or less, 50 μm or less, 25 μm or less. It may be 10 μm or less. As the thickness of the light transmissive member becomes smaller, the ability to follow the surface shape of the adherend tends to improve. Further, from the viewpoint of handleability, workability, and the like, the thickness of the light transmitting member may be, for example, 2 μm or more, 10 μm or more, or 25 μm or more.
 光透過性部材のうち粘着剤層が積層される側の面には、必要に応じて、コロナ放電処理、プラズマ処理、紫外線照射処理、酸処理、アルカリ処理、下塗り剤(プライマー)の塗布による下塗り層の形成等の、従来公知の表面処理が施されていてもよい。このような表面処理は、粘着剤層の光透過性部材への投錨性を向上させるための処理であり得る。下塗り層の形成に用いるプライマーの組成は特に限定されず、公知のものから適宜選択することができる。下塗り層の厚さは特に制限されないが、通常、0.01μm~1μm程度が適当であり、0.1μm~1μm程度が好ましい。必要に応じて光透過性部材に施され得る他の処理として、帯電防止層形成処理、着色層形成処理、印刷処理等が挙げられる。これらの処理は、単独でまたは組み合わせて適用することができる。 If necessary, the surface of the light-transmitting member on the side where the pressure-sensitive adhesive layer is laminated is coated with a corona discharge treatment, a plasma treatment, an ultraviolet irradiation treatment, an acid treatment, an alkali treatment, or an undercoating agent (primer). Conventionally known surface treatments such as layer formation may be applied. Such a surface treatment may be a treatment for improving the anchoring property of the pressure-sensitive adhesive layer on the light-transmitting member. The composition of the primer used for forming the undercoat layer is not particularly limited, and can be appropriately selected from known ones. The thickness of the undercoat layer is not particularly limited, but is usually about 0.01 μm to 1 μm, preferably about 0.1 μm to 1 μm. Other treatments that can be applied to the light transmissive member as needed include an antistatic layer forming treatment, a colored layer forming treatment, a printing treatment, and the like. These treatments can be applied alone or in combination.
 ここに開示される粘着型光学フィルムの厚さは、例えば1000μm以下であってよく、350μm以下でもよく、200μm以下でもよく、120μm以下でもよく、75μm以下でもよく、50μm以下でもよい。また、粘着型光学フィルムの厚さは、取扱い性等の観点から、例えば10μm以上であってよく、25μm以上でもよく、80μm以上でもよく、130μm以上でもよい。
 なお、粘着型光学フィルムの厚さとは、被着体に貼り付けられる部分の厚さをいう。例えば図1に示す構成の粘着型光学フィルム1では、粘着剤層の第1の表面(粘着面)10Aから光透過性部材の第2面20Bまでの厚さを指し、剥離ライナー30の厚さは含まない。
The thickness of the adhesive optical film disclosed herein may be, for example, 1000 μm or less, 350 μm or less, 200 μm or less, 120 μm or less, 75 μm or less, or 50 μm or less. The thickness of the adhesive optical film may be, for example, 10 μm or more, 25 μm or more, 80 μm or more, or 130 μm or more from the viewpoint of handleability and the like.
The thickness of the adhesive optical film means the thickness of the portion to be attached to the adherend. For example, in the adhesive optical film 1 having the configuration shown in FIG. 1, it refers to the thickness from the first surface (adhesive surface) 10A of the pressure-sensitive adhesive layer to the second surface 20B of the light-transmitting member, and is the thickness of the release liner 30. Does not include.
<剥離ライナー付き粘着型光学フィルム>
 ここに開示される粘着型光学フィルムは、粘着剤層の表面(粘着面)を剥離ライナーの剥離面に当接させた粘着製品の形態をとり得る。したがって、この明細書により、ここに開示されるいずれかの粘着型光学フィルムと、該粘着型光学フィルムの粘着面に当接する剥離面を有する剥離ライナーと、を含む剥離ライナー付き粘着型光学フィルム(粘着製品)が提供される。
<Adhesive optical film with release liner>
The adhesive optical film disclosed herein may take the form of an adhesive product in which the surface (adhesive surface) of the adhesive layer is brought into contact with the release surface of the release liner. Accordingly, according to this specification, an adhesive optical film with a release liner comprising any of the adhesive optical films disclosed herein and a release liner having a release surface that abuts the adhesive surface of the adhesive optical film. Adhesive products) are provided.
 剥離ライナーとしては、特に限定されず、例えば、樹脂フィルムや紙(ポリエチレン等の樹脂がラミネートされた紙であり得る。)等の剥離ライナー基材上に剥離処理層を有する剥離ライナーや、フッ素系ポリマー(ポリテトラフルオロエチレン等)やポリオレフィン系樹脂(ポリエチレン、ポリプロピレン等)のような低接着性材料により形成された樹脂フィルムからなる剥離ライナー等を用いることができる。上記剥離処理層は、剥離ライナー基材を剥離処理剤により表面処理して形成されたものであり得る。剥離処理剤は、シリコーン系剥離処理剤、長鎖アルキル系剥離処理剤、フッ素系剥離処理剤、硫化モリブデン(IV)等の公知の剥離処理剤であり得る。いくつかの態様において、シリコーン系剥離処理剤による剥離処理層を有する剥離ライナーを好ましく採用し得る。剥離処理層の厚さや形成方法は特に限定されず、剥離ライナーの粘着面側表面において適切な剥離性が発揮されるように設定することができる。 The release liner is not particularly limited, and for example, a release liner having a release treatment layer on a release liner base material such as a resin film or paper (paper in which a resin such as polyethylene is laminated) or a fluorine-based release liner. A release liner made of a resin film formed of a low adhesive material such as a polymer (polytetrafluoroethylene or the like) or a polyolefin resin (polyethylene, polypropylene, etc.) can be used. The peeling treatment layer may be formed by surface-treating the peeling liner base material with a peeling treatment agent. The stripping agent may be a known stripping agent such as a silicone-based stripping agent, a long-chain alkyl-based stripping agent, a fluorine-based stripping agent, or molybdenum sulfide (IV). In some embodiments, a release liner having a release treatment layer with a silicone-based release treatment agent can be preferably adopted. The thickness and forming method of the peeling treatment layer are not particularly limited, and can be set so that appropriate peeling property is exhibited on the adhesive surface side surface of the peeling liner.
 いくつかの態様において、粘着面の平滑性等の観点から、剥離ライナー基材としての樹脂フィルム(以下、剥離フィルム基材ともいう。)上に剥離処理層を有する構成の剥離ライナー(以下、剥離フィルムともいう。)を好ましく採用し得る。剥離フィルム基材としては、各種のプラスチックフィルムを用いることができる。この明細書においてプラスチックフィルムとは、典型的には非多孔質のシートであって、例えば不織布とは区別される(すなわち、不織布を含まない)概念である。 In some embodiments, from the viewpoint of smoothness of the adhesive surface and the like, a release liner having a release treatment layer on a resin film (hereinafter, also referred to as a release film base material) as a release liner base material (hereinafter, peeling). (Also referred to as a film) can be preferably adopted. Various plastic films can be used as the release film base material. As used herein, a plastic film is typically a non-porous sheet, a concept that distinguishes it from, for example, non-woven fabrics (ie, does not include non-woven fabrics).
 上記プラスチックフィルムの材料としては、例えば、ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート(PBT)、ポリエチレンナフタレート(PEN)等のポリエステル系樹脂、ポリエチレン(PE)、ポリプロピレン(PP)、エチレン-プロピレン共重合体、エチレン-ブテン共重合体等のポリオレフィン系樹脂、トリアセチルセルロース等のセルロース樹脂、アセテート系樹脂、ポリスルホン系樹脂、ポリエーテルスルホン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ノルボルネン系樹脂等の環状ポリオレフィン樹脂、(メタ)アクリル系樹脂、ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、ポリスチレン系樹脂、ポリビニルアルコール系樹脂、エチレン-酢酸ビニル共重合体樹脂、エチレン-ビニルアルコール共重合体樹脂、ポリアリレート系樹脂、ポリフェニレンサルファイド系樹脂等が挙げられる。これらの樹脂のいずれか1種または2種以上の混合物から形成された剥離フィルム基材を用いることができる。なかでも好ましい剥離フィルム基材として、ポリエステル系樹脂から形成されたポリエステル系樹脂フィルム(例えばPETフィルム)が挙げられる。 Examples of the material of the plastic film include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP), and ethylene-propylene co-weight. Combined, polyolefin resin such as ethylene-butene copolymer, cellulose resin such as triacetyl cellulose, acetate resin, polysulfone resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, norbornene resin Cyclic polyolefin resin such as resin, (meth) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol co-weight Examples thereof include a coalesced resin, a polyarylate resin, and a polyphenylene sulfide resin. A release film base material formed from any one or a mixture of two or more of these resins can be used. Among them, a preferable release film base material includes a polyester-based resin film (for example, PET film) formed from a polyester-based resin.
 上述した剥離フィルム基材として用いられるプラスチックフィルムは、無延伸フィルム、一軸延伸フィルム、二軸延伸フィルムのいずれであってもよい。また、上記プラスチックフィルムは、単層構造であってもよく、2層以上のサブ層を含む多層構造であってもよい。上記プラスチックフィルムには、酸化防止剤、老化防止剤、耐熱安定剤、光安定剤、紫外線吸収剤、顔料や染料等の着色剤、滑剤、充填剤、帯電防止剤、核剤等の、粘着シートの剥離フィルム基材に用いられ得る公知の添加剤が配合されていてもよい。多層構造のプラスチックフィルムにおいて、各添加剤は、すべてのサブ層に配合されていてもよく、一部のサブ層にのみ配合されていてもよい。 The plastic film used as the above-mentioned release film base material may be any of a non-stretched film, a uniaxially stretched film, and a biaxially stretched film. Further, the plastic film may have a single-layer structure or a multi-layer structure including two or more sub-layers. The plastic film is an adhesive sheet containing antioxidants, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, colorants such as pigments and dyes, lubricants, fillers, antioxidants, nucleating agents, etc. A known additive that can be used for the release film base material of the above may be blended. In the multi-layered plastic film, each additive may be blended in all sublayers or only in some sublayers.
 いくつかの好ましい態様では、上記剥離フィルム基材(典型的にはプラスチックフィルム)として、その剥離面側の層において無機粒子等の粒子(例えば顔料や滑剤、充填剤等であり得る。)の含有量が制限されているか、あるいはそのような粒子を実質的に含まないものが好ましく用いられ得る。ここで実質的に含まないとは、当該層中の粒子(例えば無機粒子)の量が1重量%未満であることをいい、好ましくは0.1重量%未満(例えば0~0.01重量%)であることをいう。そのような剥離フィルム基材を備える剥離フィルムは、剥離面の算術平均粗さRaや最大高さRzが低いものとなりやすい。上記剥離フィルム基材(典型的にはプラスチックフィルム)が多層構造を有する場合には、剥離面側の層中の粒子含有量は、当該剥離面側層以外の層中の粒子含有量の1/10以下(例えば1/50以下)であり得る。 In some preferred embodiments, the release film substrate (typically a plastic film) contains particles such as inorganic particles (eg, pigments, lubricants, fillers, etc.) in the layer on the release surface side thereof. Those with a limited amount or substantially free of such particles may be preferably used. Here, substantially not contained means that the amount of particles (for example, inorganic particles) in the layer is less than 1% by weight, preferably less than 0.1% by weight (for example, 0 to 0.01% by weight). ). A release film provided with such a release film base material tends to have a low arithmetic mean roughness Ra and maximum height Rz of the release surface. When the release film base material (typically a plastic film) has a multilayer structure, the particle content in the layer on the release surface side is 1 / of the particle content in the layers other than the release surface side layer. It can be 10 or less (for example, 1/50 or less).
 第1粘着面および第2粘着面上にそれぞれ剥離ライナーを有する形態の剥離ライナー付き粘着型光学フィルムにおいて、一方の粘着面上に配置される剥離ライナー(以下、一方の剥離ライナーともいう。)と、他方の粘着面上に配置される剥離ライナー(以下、他方の剥離ライナーともいう。)とは、同種の材料および構成を有するものであってもよく、異なる材料、構成を有するものであってもよい。 In an adhesive optical film with a release liner having a release liner on each of the first adhesive surface and the second adhesive surface, a release liner (hereinafter, also referred to as one release liner) arranged on one of the adhesive surfaces. The release liner (hereinafter, also referred to as the other release liner) arranged on the other adhesive surface may have the same material and composition, or may have a different material and composition. May be good.
 剥離ライナー(好ましくは剥離フィルム)の厚さは特に限定されず、例えば10μm~500μm程度であり得る。剥離ライナーの強度や寸法安定性の観点から、剥離ライナーの厚さは、20μm以上であることが適当であり、30μm以上であることが好ましく、35μm以上でもよく、40μm以上でもよく、45μm以上でもよい。また、剥離ライナーの取扱い性(例えば、巻回しやすさ)等の観点から、剥離ライナーの厚さは、300μm以下であることが適当であり、250μm以下であることが好ましく、200μm以下でもよく、150μm以下でもよく、130μm以下でもよい。いくつかの好ましい態様では、剥離ライナーの厚さは凡そ125μm以下であり、凡そ115μm以下であってもよく、凡そ105μm以下でもよく、凡そ90μm以下でもよく、凡そ70μm以下でもよい。剥離ライナーの厚さを所定値以下とすることで、ロール状にした際の巻き跡がつきづらくなり、粘着剤層からの除去がスムーズとなり、剥離ライナー除去後の粘着面において高い表面平滑性が得られやすい。 The thickness of the release liner (preferably the release film) is not particularly limited, and may be, for example, about 10 μm to 500 μm. From the viewpoint of the strength and dimensional stability of the release liner, the thickness of the release liner is preferably 20 μm or more, preferably 30 μm or more, 35 μm or more, 40 μm or more, or 45 μm or more. good. Further, from the viewpoint of handleability of the release liner (for example, ease of winding), the thickness of the release liner is preferably 300 μm or less, preferably 250 μm or less, and may be 200 μm or less. It may be 150 μm or less, or 130 μm or less. In some preferred embodiments, the thickness of the release liner is approximately 125 μm or less, may be approximately 115 μm or less, may be approximately 105 μm or less, may be approximately 90 μm or less, and may be approximately 70 μm or less. By setting the thickness of the release liner to a predetermined value or less, it becomes difficult to make winding marks when the product is rolled, the removal from the adhesive layer becomes smooth, and the adhesive surface after removing the release liner has high surface smoothness. Easy to obtain.
 一方の剥離ライナーおよび他方の剥離ライナーを備える態様において、それらの剥離ライナーの厚さは、同じであってもよく、異なっていてもよい。いくつかの態様では、剥離作業性等の観点から、一方の剥離ライナーと他方の剥離ライナーとが異なる厚さを有することが好ましく、例えば、より厚い方の剥離ライナーの厚さが、より薄い方の剥離ライナーの厚さの凡そ1.1倍以上(例えば凡そ1.25倍以上。上限は特に制限されないが、例えば5倍以下)であることが好ましい。 In the embodiment including one release liner and the other release liner, the thicknesses of the release liners may be the same or different. In some aspects, from the viewpoint of peeling workability and the like, it is preferable that one peeling liner and the other peeling liner have different thicknesses, for example, the thicker peeling liner has a thinner thickness. The thickness of the release liner is preferably about 1.1 times or more (for example, about 1.25 times or more. The upper limit is not particularly limited, but for example, 5 times or less).
 (粘着面側表面の算術平均粗さRa)
 いくつかの態様において、剥離ライナー(好ましくは剥離フィルム)は、粘着面側表面の算術平均粗さRaが所定値以下(例えば凡そ100nm以下、さらには50nm未満)に制限されていることが、高い表面平滑性を有する粘着面を実現する観点から好ましい。いくつかの態様では、剥離ライナーの粘着面側表面の算術平均粗さRaは、例えば凡そ30nm以下であることが好ましく、凡そ25nm以下であることがより好ましく、凡そ20nm以下でもよく、凡そ18nm以下でもよい。また、剥離ライナーの製造容易性や取扱い性等の観点から、いくつかの態様において、上記算術平均粗さRaは、例えば凡そ5nm以上であってよく、凡そ10nm以上でもよく、凡そ15nm以上でもよい。第1粘着面および第2粘着面上にそれぞれ剥離ライナーが配置された形態の剥離ライナー付き粘着型光学フィルムでは、両剥離ライナーの粘着面側表面がいずれも上述したいずれかの算術平均粗さRaを満たすことが好ましい。両剥離ライナーの粘着面側表面の算術平均粗さRaは、同程度であってもよく、異なっていてもよい。
(Arithmetic Mean Roughness Ra on the surface on the adhesive surface side)
In some embodiments, the release liner (preferably the release film) is often limited in that the arithmetic mean roughness Ra of the surface on the adhesive surface side is limited to a predetermined value or less (for example, about 100 nm or less, further less than 50 nm). It is preferable from the viewpoint of realizing an adhesive surface having surface smoothness. In some embodiments, the arithmetic mean roughness Ra of the adhesive surface side surface of the release liner is, for example, preferably about 30 nm or less, more preferably about 25 nm or less, about 20 nm or less, and about 18 nm or less. It may be. Further, from the viewpoint of ease of manufacture and handleability of the release liner, in some embodiments, the arithmetic mean roughness Ra may be, for example, about 5 nm or more, about 10 nm or more, or about 15 nm or more. .. In the adhesive optical film with a release liner in which the release liner is arranged on the first adhesive surface and the second adhesive surface, the surface on the adhesive surface side of both release liners is any of the above-mentioned arithmetic mean roughness Ra. It is preferable to satisfy. The arithmetic mean roughness Ra of the adhesive surface side surfaces of both release liners may be about the same or different.
 (粘着面側表面の最大高さRz)
 いくつかの態様において、剥離ライナー(好ましくは剥離フィルム)は、粘着面側表面の最大高さRzが700nm以下であることが、高い表面平滑性を有する粘着面を実現する観点から好ましい。いくつかの態様では、剥離ライナーの粘着面側表面の最大高さRzは、好ましくは凡そ600nm以下であり、凡そ500nm以下でもよく、凡そ400nm以下でもよく、凡そ300nm以下でもよい。また、剥離ライナーの製造容易性や取扱い性等の観点から、いくつかの態様において、上記最大高さRzは、例えば凡そ50nm以上であってよく、凡そ80nm以上でもよく、凡そ100nm以上でもよく、凡そ150nm以上でもよく、凡そ200nm以上でもよい。第1粘着面および第2粘着面上にそれぞれ剥離ライナーが配置された形態の剥離ライナー付き粘着型光学フィルムでは、両剥離ライナーの粘着面側表面がいずれも上述したいずれかの最大高さRzを満たすことが好ましい。両剥離ライナーの粘着面側表面の最大高さRzは、同程度であってもよく、異なっていてもよい。
(Maximum height Rz of the surface on the adhesive surface side)
In some embodiments, the release liner (preferably a release film) preferably has a maximum height Rz of the surface on the adhesive surface side of 700 nm or less from the viewpoint of realizing an adhesive surface having high surface smoothness. In some embodiments, the maximum height Rz of the adhesive surface side surface of the release liner is preferably about 600 nm or less, may be about 500 nm or less, may be about 400 nm or less, and may be about 300 nm or less. Further, from the viewpoint of ease of manufacture and handleability of the release liner, in some embodiments, the maximum height Rz may be, for example, about 50 nm or more, about 80 nm or more, or about 100 nm or more. It may be about 150 nm or more, and may be about 200 nm or more. In the adhesive type optical film with a release liner in which the release liner is arranged on the first adhesive surface and the second adhesive surface, the adhesive surface side surfaces of both release liners both have the maximum height Rz of any of the above. It is preferable to satisfy. The maximum height Rz of the adhesive surface side surfaces of both release liners may be about the same or different.
 (背面の表面性状)
 剥離ライナー(好ましくは剥離フィルム)の背面(粘着剤層側の反対面)の算術平均粗さRaや最大高さRzは特に限定されない。剥離ライナーの背面の算術平均粗さRaは、生産性等の観点から、例えば30nm超(例えば35nm超、さらには凡そ50nm以上)であってもよい。剥離ライナーの背面の最大高さRzは、生産性等の観点から、例えば400nm超(例えば凡そ500nm以上)であってもよく、800nm超(例えば1000nm以上)でもよい。
(Surface texture on the back)
The arithmetic mean roughness Ra and the maximum height Rz of the back surface (opposite surface of the adhesive layer side) of the release liner (preferably the release film) are not particularly limited. The arithmetic mean roughness Ra on the back surface of the peeling liner may be, for example, more than 30 nm (for example, more than 35 nm, more preferably about 50 nm or more) from the viewpoint of productivity and the like. The maximum height Rz of the back surface of the release liner may be, for example, more than 400 nm (for example, about 500 nm or more) or more than 800 nm (for example, 1000 nm or more) from the viewpoint of productivity and the like.
 剥離フィルム表面の算術平均粗さRaおよび最大高さRzは、フィルム材料の選択や成形方法、剥離処理等の表面処理等によって調節され得る。例えば、剥離性表面を構成する層(アンチブロッキング層、ハードコート層、オリゴマー防止層等)の平滑性の調節、当該表面層や剥離フィルム基材中のフィラー粒子の減量や不使用(無粒子化)、その他、延伸条件の調整等が挙げられる。 The arithmetic mean roughness Ra and the maximum height Rz of the peeled film surface can be adjusted by the selection of the film material, the molding method, the surface treatment such as the peeling treatment, and the like. For example, adjusting the smoothness of the layers constituting the peelable surface (anti-blocking layer, hard coat layer, oligomer prevention layer, etc.), reducing the amount of filler particles in the surface layer or the release film base material, or eliminating the use (particle-free). ), In addition, adjustment of stretching conditions and the like can be mentioned.
 剥離ライナー(好ましくは剥離フィルム)表面の算術平均粗さRaおよび最大高さRzは、非接触式の表面粗さ測定装置を用いて測定される。非接触式の表面粗さ測定装置としては、光干渉方式の表面粗さ測定装置が用いられ、例えば3次元光学プロファイラー(商品名「NewView7300」、ZYGO社製)またはその相当品を使用することができる。例えば、剥離ライナーの測定面とは反対側の面に、ガラス板(MATSUNAMI社製のソーダライムガラス板、厚さ1.3mm)を粘着剤で貼り合わせて固定し、23℃、50%RHの環境下において、3次元光学プロファイラー(商品名「NewView7300」、ZYGO社製)を用いて表面形状を測定することができる。 The arithmetic mean roughness Ra and the maximum height Rz of the surface of the release liner (preferably the release film) are measured using a non-contact type surface roughness measuring device. As the non-contact type surface roughness measuring device, a light interference type surface roughness measuring device is used, and for example, a three-dimensional optical profiler (trade name "NewView7300", manufactured by ZYGO) or an equivalent product thereof can be used. can. For example, a glass plate (soda lime glass plate manufactured by MATSUNAMI, thickness 1.3 mm) is attached and fixed with an adhesive on the surface opposite to the measurement surface of the release liner, and fixed at 23 ° C. and 50% RH. In an environment, the surface shape can be measured using a three-dimensional optical profiler (trade name "NewView7300", manufactured by ZYGO).
<用途>
 ここに開示される粘着型光学フィルムは、各種の被着体に貼り合わせて用いられ得る。上記被着体の構成材料(被着体材料)としては、特に限定されるものではないが、例えば、銅、銀、金、鉄、錫、パラジウム、アルミニウム、ニッケル、チタン、クロム、インジウム、亜鉛等、またはこれらの2種以上を含む合金等の金属材料や、例えばポリイミド系樹脂、アクリル系樹脂、ポリエーテルニトリル系樹脂、ポリエーテルスルホン系樹脂、ポリエステル系樹脂(PET系樹脂、ポリエチレンナフタレート系樹脂等)、ポリ塩化ビニル系樹脂、ポリフェニレンサルファイド系樹脂、ポリエーテルエーテルケトン系樹脂、ポリアミド系樹脂(いわゆるアラミド樹脂等)、ポリアリレート系樹脂、フッ素系樹脂、ポリカーボネート系樹脂、ジアセチルセルロースやトリアセチルセルロース等のセルロース系ポリマー、ビニルブチラール系ポリマー、液晶ポリマー、グラフェン等のカーボン材料等の各種樹脂材料(典型的にはプラスチック材)、アルミナ、ジルコニア、チタニア、SiO、ITO、ATO等の金属酸化物及びその混合物、窒化アルミニウム、窒化ケイ素、窒化チタン、窒化ガリウム、窒化インジウム等の窒化物及びその複合物、アルカリガラス、無アルカリガラス、石英ガラス、ホウケイ酸ガラス、サファイアガラス等の無機材料等が挙げられる。ここに開示される粘着型光学フィルムは、少なくとも表面が上記材料から構成された部材(例えば光学部材)に貼り付けられて用いられ得る。
<Use>
The adhesive optical film disclosed herein can be used by being bonded to various adherends. The constituent material (adhesion material) of the adherend is not particularly limited, but for example, copper, silver, gold, iron, tin, palladium, aluminum, nickel, titanium, chromium, indium, and zinc. Etc., or metal materials such as alloys containing two or more of these, for example, polyimide-based resin, acrylic-based resin, polyether nitrile-based resin, polyether sulfone-based resin, polyester-based resin (PET-based resin, polyethylene naphthalate-based). Resins, etc.), Polyvinyl chloride resins, polyphenylene sulfide resins, polyether ether ketone resins, polyamide resins (so-called aramid resins, etc.), polyarylate resins, fluorine resins, polycarbonate resins, diacetyl celluloses and triacetyls. Various resin materials (typically plastic materials) such as cellulose-based polymers such as cellulose, vinyl butyral-based polymers, liquid crystal polymers, and carbon materials such as graphene , and metal oxidation of alumina, zirconia, titania, SiO 2 , ITO, ATO, etc. Materials and their mixtures, nitrides such as aluminum nitride, silicon nitride, titanium nitride, gallium nitride, indium nitride and their composites, inorganic materials such as alkaline glass, non-alkali glass, quartz glass, borosilicate glass and sapphire glass. Can be mentioned. The adhesive optical film disclosed herein can be used by being attached to a member (for example, an optical member) whose surface is made of the above material at least.
 ここに開示される粘着型光学フィルムは、被着体に貼り合わせた後、室温程度の温度域(例えば20℃~35℃)よりも高い温度に加熱する処理を必要としない貼付け態様で用いられ得る。また、粘着型光学フィルムの構成材料(例えば、光透過性部材の材質)や被着体の種類に応じて許容される場合には、被着体への貼り合わせ後、貼り合わせの時点、および貼り合わせ前の、少なくともいずれかのタイミングで加熱処理を行ってもよい。加熱処理は、粘着剤の被着体への密着性向上や接着促進等の目的で行うことができる。加熱処理温度は、粘着型光学フィルムの構成材料や被着体の種類に応じて許容される範囲で、被着体の表面状態等を考慮して、所望の効果が得られるように適宜設定することができ、例えば100℃程度またはそれ以下であってよく、80℃以下でもよく、60℃以下でもよく、50℃以下でもよい。 The adhesive optical film disclosed herein is used in a sticking mode that does not require a treatment of sticking to an adherend and then heating to a temperature higher than a temperature range of about room temperature (for example, 20 ° C. to 35 ° C.). obtain. Further, if it is permissible depending on the constituent material of the adhesive optical film (for example, the material of the light transmitting member) and the type of the adherend, after the bonding to the adherend, at the time of bonding, and at the time of bonding, and The heat treatment may be performed at least at any timing before bonding. The heat treatment can be performed for the purpose of improving the adhesion of the pressure-sensitive adhesive to the adherend and promoting adhesion. The heat treatment temperature is appropriately set so as to obtain a desired effect in consideration of the surface condition of the adherend and the like within an allowable range depending on the constituent material of the adhesive optical film and the type of the adherend. For example, it may be about 100 ° C. or lower, 80 ° C. or lower, 60 ° C. or lower, or 50 ° C. or lower.
 粘着型光学フィルムの貼り付け対象である部材や材料(両面粘着型光学フィルムにおいては、少なくとも一方の被着体)は、光透過性を有するものであり得る。このような被着体では、ここに開示される技術を適用して光学特性(透明性等)の低下を抑制しつつ屈折率を高めることの利点が得られやすい。上記被着体の全光線透過率は、例えば50%超であってよく、70%以上でもよい。いくつかの好ましい態様では、上記被着体の全光線透過率は80%以上であり、より好ましくは90%以上であり、さらに好ましくは95%以上(例えば95~100%)である。ここに開示される粘着型光学フィルムは、全光線透過率が所定値以上の被着体(例えば光学部材)に貼り付ける態様で好ましく用いられ得る。上記全光線透過率は、JIS K 7136:2000に準拠して、市販の透過率計を使用して測定される。透過率計としては、村上色彩技術研究所製の商品名「HAZEMETER HM-150」またはその相当品が用いられる。 The member or material to which the adhesive optical film is attached (in the case of the double-sided adhesive optical film, at least one adherend) may have light transmittance. In such an adherend, it is easy to obtain the advantage of increasing the refractive index while suppressing the deterioration of optical characteristics (transparency, etc.) by applying the technique disclosed herein. The total light transmittance of the adherend may be, for example, more than 50%, and may be 70% or more. In some preferred embodiments, the total light transmittance of the adherend is 80% or more, more preferably 90% or more, still more preferably 95% or more (for example, 95 to 100%). The adhesive optical film disclosed herein can be preferably used in a mode of being attached to an adherend (for example, an optical member) having a total light transmittance of a predetermined value or more. The total light transmittance is measured using a commercially available transmittance meter in accordance with JIS K 7136: 2000. As the transmittance meter, the product name "HAZEMETER HM-150" manufactured by Murakami Color Technology Research Institute or its equivalent is used.
 粘着剤層の屈折率と、被着体の屈折率とは、同程度であってもよく、異なっていてもよい。例えば、被着体の屈折率に対して粘着剤層の屈折率を相対的に高くすることにより、被着体側から粘着剤層に臨界角以下の角度で入射する光を正面側に屈折させ、正面輝度を高めることができる。この場合、被着体の屈折率は、例えば1.55以下、1.50以下、1.48以下、1.45以下であってよく、1.45未満であってもよく、また、例えば1.10以上、1.20以上、1.30以上または1.35以上であり得る。また、粘着剤層に対して相対的に高屈折率の被着体によると、粘着剤層側から被着体に入射する光を正面側に屈折させ、正面輝度を高めることができる。この場合、被着体の屈折率は、例えば1.60以上、1.65以上または1.70以上であってよく、また、例えば3.00以下であり、2.50以下または2.00以下であり得る。一方、粘着剤層と被着体との屈折率差を小さくすることにより、界面での光反射を抑制することができる。この場合、被着体の屈折率は、1.55~1.80程度であってよく、1.55~1.75程度でもよく、1.60~1.70程度でもよい。被着体の屈折率は、粘着剤の屈折率と同様の方法で測定され得る。 The refractive index of the pressure-sensitive adhesive layer and the refractive index of the adherend may be the same or different. For example, by making the refractive index of the pressure-sensitive adhesive layer relatively high with respect to the refractive index of the adherend, light incident on the pressure-sensitive adhesive layer from the adherend side at an angle equal to or less than the critical angle is refracted toward the front side. The front brightness can be increased. In this case, the refractive index of the adherend may be, for example, 1.55 or less, 1.50 or less, 1.48 or less, 1.45 or less, less than 1.45, or, for example, 1. It can be .10 or higher, 1.20 or higher, 1.30 or higher, or 1.35 or higher. Further, according to the adherend having a relatively high refractive index with respect to the pressure-sensitive adhesive layer, the light incident on the adherend from the pressure-sensitive adhesive layer side can be refracted to the front side to increase the front luminance. In this case, the refractive index of the adherend may be, for example, 1.60 or more, 1.65 or more or 1.70 or more, and for example, 3.00 or less, 2.50 or less or 2.00 or less. Can be. On the other hand, by reducing the difference in refractive index between the pressure-sensitive adhesive layer and the adherend, light reflection at the interface can be suppressed. In this case, the refractive index of the adherend may be about 1.55 to 1.80, about 1.55 to 1.75, or about 1.60 to 1.70. The refractive index of the adherend can be measured in the same manner as the refractive index of the pressure-sensitive adhesive.
 いくつかの好ましい態様では、上記被着体は、上述したいずれかの屈折率を有し、かつ上述したいずれかの全光線透過率を有するものであり得る。このような被着体に貼り付ける態様において、ここに開示される技術による効果は特に好ましく発揮される。 In some preferred embodiments, the adherend may have any of the refractive indexes described above and any of the total light transmittances described above. In such a mode of sticking to an adherend, the effect of the technique disclosed herein is particularly preferably exhibited.
 好ましい用途の一例として、光学用途が挙げられる。より具体的には、例えば、光学部材を貼り合わせる用途(光学部材貼り合わせ用)や上記光学部材が用いられた製品(光学製品)の製造用途等に用いられる光学用粘着シートとして、ここに開示される粘着型光学フィルムを好ましく用いることができる。 An example of a preferable application is an optical application. More specifically, it is disclosed herein as, for example, an optical adhesive sheet used for bonding optical members (for bonding optical members), manufacturing products using the above optical members (optical products), and the like. The adhesive type optical film to be used can be preferably used.
 上記光学部材とは、光学的特性(例えば、偏光性、光屈折性、光散乱性、光反射性、光透過性、光吸収性、光回折性、旋光性、視認性等)を有する部材をいう。上記光学部材としては、光学的特性を有する部材であれば特に限定されないが、例えば、表示装置(画像表示装置)、入力装置等の機器(光学機器)を構成する部材またはこれらの機器に用いられる部材が挙げられ、例えば、偏光板、波長板、位相差板、光学補償フィルム、輝度向上フィルム、導光板、反射フィルム、反射防止フィルム、ハードコート(HC)フィルム、衝撃吸収フィルム、防汚フィルム、フォトクロミックフィルム、調光フィルム、透明導電フィルム(ITOフィルム)、意匠フィルム、装飾フィルム、表面保護板、プリズム、レンズ、カラーフィルター、透明基板や、さらにはこれらが積層されている部材(これらを総称して「機能性フィルム」と称する場合がある。)等が挙げられる。なお、上記の「板」および「フィルム」は、それぞれ板状、フィルム状、シート状等の形態を含むものとし、例えば、「偏光フィルム」は、「偏光板」や「偏光シート」等を含み、「導光板」は、「導光フィルム」や「導光シート」等を含むものとする。また、上記「偏光板」は、円偏光板を含むものとする。 The optical member is a member having optical characteristics (for example, polarization, light refraction, light scattering, light reflection, light transmission, light absorption, light diffractivity, light turning property, visibility, etc.). say. The optical member is not particularly limited as long as it has optical characteristics, but is used, for example, as a member constituting a device (optical device) such as a display device (image display device) or an input device, or a member thereof. Examples include polarizing plates, wavelength plates, retardation plates, optical compensation films, brightness improving films, light guide plates, reflective films, antireflection films, hard coat (HC) films, shock absorbing films, antifouling films, and the like. Photochromic film, dimming film, transparent conductive film (ITO film), design film, decorative film, surface protection plate, prism, lens, color filter, transparent substrate, and members in which these are laminated (collectively referred to as these). (Sometimes referred to as a "functional film") and the like. The above-mentioned "plate" and "film" are assumed to include a plate-like, a film-like, a sheet-like form, respectively, and for example, a "polarizing film" includes a "polarizing plate", a "polarizing sheet", and the like. The "light guide plate" shall include a "light guide film", a "light guide sheet" and the like. Further, the above-mentioned "polarizing plate" includes a circular polarizing plate.
 上記表示装置としては、例えば、液晶表示装置、有機EL(エレクトロルミネッセンス)表示装置、マイクロLED(μLED)、ミニLED(miniLED)、PDP(プラズマディスプレイパネル)、電子ペーパーなどが挙げられる。また、上記入力装置としては、タッチパネルなどが挙げられる。 Examples of the display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a micro LED (μLED), a mini LED (miniLED), a PDP (plasma display panel), and electronic paper. Further, examples of the input device include a touch panel and the like.
 上記光学部材としては、特に限定されないが、例えば、ガラス、アクリル樹脂、ポリカーボネート、ポリエチレンテレフタレート、金属薄膜等からなる部材(例えば、シート状やフィルム状、板状の部材)等が挙げられる。なお、この明細書における「光学部材」には、表示装置や入力装置の視認性を保ちながら加飾や保護の役割を担う部材(意匠フィルム、装飾フィルムや表面保護フィルム等)も含むものとする。 The optical member is not particularly limited, and examples thereof include members made of glass, acrylic resin, polycarbonate, polyethylene terephthalate, a metal thin film, and the like (for example, sheet-shaped, film-shaped, and plate-shaped members). The "optical member" in this specification also includes a member (design film, decorative film, surface protective film, etc.) that plays a role of decoration and protection while maintaining the visibility of the display device and the input device.
 ここに開示される技術は、例えば、光の透過、反射、拡散、導波、集光、回折等の1または2以上の機能を有するフィルムや蛍光フィルム等の光学フィルムを、他の光学部材(他の光学フィルムであり得る。)に接合するために好ましく用いられ得る。例えば、光透過性部材として上記光学フィルムを備える粘着型光学フィルムを、被着体としての上記他の光学部材に貼り付けることにより、上記光透過性部材が高屈折率の粘着剤層(接合層)を介して上記他の光学部材に接合された構造を形成することができる。また、光透過性部材として上記他の光学部材を備える粘着型光学フィルムを、被着体としての上記光学フィルムに貼り付けることにより、上記他の光学部材が高屈折率の粘着剤層を介して上記光透過性部材に接合された構造を形成することができる。なかでも、光の導波、集光、回折の少なくとも1つの機能を有する光学フィルムの接合においては、接合層のバルク全体が高屈折率であることが望ましく、ここに開示される技術の好ましい適用対象となり得る。 The techniques disclosed herein include, for example, an optical film such as a film or a fluorescent film having one or more functions such as light transmission, reflection, diffusion, waveguide, condensing, and diffraction, and other optical members ( It can be preferably used for bonding to other optical films.). For example, by attaching an adhesive optical film provided with the optical film as a light transmissive member to the other optical member as an adherend, the light transmissive member has a high refractive index pressure-sensitive adhesive layer (bonding layer). ), A structure bonded to the other optical member can be formed. Further, by attaching an adhesive optical film provided with the other optical member as a light transmissive member to the optical film as an adherend, the other optical member can be attached to the other optical member via a pressure-sensitive adhesive layer having a high refractive index. A structure joined to the light transmissive member can be formed. In particular, in the bonding of an optical film having at least one function of light waveguide, light collection, and diffraction, it is desirable that the entire bulk of the bonding layer has a high refractive index, and the techniques disclosed herein are preferably applied. Can be a target.
 ここに開示される技術は、例えば、導光フィルム、拡散フィルム、蛍光フィルム、調色フィルム、プリズムシート、レンチキュラーフィルム、マイクロレンズアレイフィルム等の光学フィルムの接合に好ましく用いられ得る。これらの用途では、光学部材の小型化の傾向や高性能化の観点から、薄型化や光取出し効率の向上が求められている。かかる要請に応え得る粘着剤を備えた粘着型光学フィルムとして、ここに開示される技術は好ましく利用され得る。より詳しくは、例えば導光フィルムや拡散フィルムの接合では、接合層としての粘着剤層の屈折率を調整(例えば高屈折率化)することによって薄型化に寄与し得る。蛍光フィルムの接合では、蛍光発光体と粘着剤との屈折率差を適切に調整することにより、光取出し効率(発光効率としても把握され得る。)を向上させることができる。調色フィルムの接合では、調色用顔料との屈折率差が小さくなるように粘着剤の屈折率を適切に調整することで散乱成分を低減し、光透過性の向上に貢献し得る。プリズムシート、レンチキュラーフィルム、マイクロレンズアレイフィルム等の接合においては、粘着剤の屈折率を適切に調整することにより、光の回折を制御し、輝度および/または視野角の向上に貢献し得る。 The technique disclosed herein can be preferably used for bonding optical films such as a light guide film, a diffusion film, a fluorescent film, a toning film, a prism sheet, a lenticular film, and a microlens array film. In these applications, thinning and improvement of light extraction efficiency are required from the viewpoint of miniaturization and high performance of optical members. The technique disclosed herein can be preferably used as an adhesive optical film provided with an adhesive capable of meeting such demands. More specifically, for example, in joining a light guide film or a diffusion film, it is possible to contribute to thinning by adjusting the refractive index of the pressure-sensitive adhesive layer as the bonding layer (for example, increasing the refractive index). In the bonding of the fluorescent film, the light extraction efficiency (which can also be grasped as the luminous efficiency) can be improved by appropriately adjusting the difference in the refractive index between the fluorescent light emitter and the pressure-sensitive adhesive. In the bonding of the toning film, the scattering component can be reduced and the light transmittance can be improved by appropriately adjusting the refractive index of the pressure-sensitive adhesive so that the difference in the refractive index from the toning pigment is small. In joining prism sheets, lenticular films, microlens array films, etc., the diffraction of light can be controlled by appropriately adjusting the refractive index of the pressure-sensitive adhesive, which can contribute to the improvement of brightness and / or viewing angle.
 ここに開示される粘着型光学フィルムは、高屈折率の被着体(高屈折率の層や部材等であり得る。)に貼り付けられる態様で好ましく用いられて、上記被着体との界面反射を抑制することができる。かかる態様で用いられる粘着型光学フィルムは、上述のように被着体との屈折率差が小さく、かつ被着体との界面における密着性が高いことが好ましい。また、外観の均質性を高める観点から、粘着剤層の厚みの均一性が高いことが好ましく、例えば粘着面の表面平滑性が高いことが好ましい。高屈折率の被着体の厚みが比較的小さい場合(例えば5μm以下、4μm以下、または2μm以下である場合)には、反射光の干渉による色付きや色むらを抑制する観点から、界面での反射を抑えることが特に有意義である。このような使用態様の一例として、偏光子と第1位相差層と第2位相差層とをこの順に備える位相差層付き偏光板において上記偏光子と上記第1位相差層との接合および/または上記第1位相差層と上記第2位相差層との接合に用いられる態様が挙げられる。 The adhesive optical film disclosed herein is preferably used in a manner of being attached to an adherend having a high refractive index (which may be a layer or a member having a high refractive index), and is an interface with the adherend. Reflection can be suppressed. As described above, the adhesive optical film used in such an embodiment preferably has a small difference in refractive index from the adherend and has high adhesion at the interface with the adherend. Further, from the viewpoint of enhancing the homogeneity of the appearance, it is preferable that the thickness of the pressure-sensitive adhesive layer is high, and for example, the surface smoothness of the pressure-sensitive adhesive surface is high. When the thickness of the adherend with a high refractive index is relatively small (for example, when it is 5 μm or less, 4 μm or less, or 2 μm or less), from the viewpoint of suppressing coloring and color unevenness due to the interference of reflected light, at the interface. Suppressing reflexes is especially meaningful. As an example of such a usage mode, in a polarizing plate with a retardation layer including a polarizing element, a first retardation layer, and a second retardation layer in this order, a junction between the polarizer and the first retardation layer and / Alternatively, an embodiment used for joining the first retardation layer and the second retardation layer can be mentioned.
 また、ここに開示される粘着型光学フィルムは、粘着剤層の高屈折率化に適することから、光半導体等の発光層(例えば、主に無機材料により構成された高屈折の発光層)に貼り付けられる態様で好ましく用いられ得る。発光層と粘着剤層との屈折率差を小さくすることにより、それらの界面における反射を抑制し、光取出し効率を向上させ得る。かかる態様で用いられる粘着型光学フィルムは、高屈折率の粘着剤層を備えることが好ましい。また、水分による自発光素子の劣化を未然に防ぐ観点から、粘着剤層の吸水率は低いことが好ましい。輝度向上の観点から、粘着型光学フィルムは低着色であることが好ましい。このことは、粘着型光学フィルムに起因する非意図的な着色を抑制する観点からも有利となり得る。 Further, since the pressure-sensitive optical film disclosed herein is suitable for increasing the refractive index of the pressure-sensitive adhesive layer, it can be used as a light-emitting layer such as an optical semiconductor (for example, a high-refraction light-emitting layer mainly composed of an inorganic material). It can be preferably used in a manner in which it is attached. By reducing the difference in refractive index between the light emitting layer and the pressure-sensitive adhesive layer, reflection at their interfaces can be suppressed and the light extraction efficiency can be improved. The pressure-sensitive optical film used in such an embodiment preferably includes a pressure-sensitive adhesive layer having a high refractive index. Further, from the viewpoint of preventing deterioration of the self-luminous element due to moisture, it is preferable that the water absorption rate of the pressure-sensitive adhesive layer is low. From the viewpoint of improving the brightness, the adhesive optical film is preferably low in color. This can also be advantageous from the viewpoint of suppressing unintentional coloring caused by the adhesive optical film.
 この明細書により開示される粘着剤は、カメラや発光装置等の構成部材として用いられるマイクロレンズその他のレンズ部材(例えば、マイクロレンズアレイフィルムを構成するマイクロレンズや、カメラ用マイクロレンズ等のレンズ部材)において、レンズ面を覆うコーティング層、上記レンズ面に対向する部材(例えば、レンズ面に対応する表面形状を有する部材)との接合層、上記レンズ面と上記部材との間に充填される充填層、等として好ましく用いられ得る。ここに開示される粘着剤は、高屈折率化に適することから、高屈折率のレンズ(例えば、高屈折率樹脂により構成されたレンズや、高屈折率樹脂製の表面層を有するレンズ)であっても該レンズとの屈折率差を低減することができる。このことは、上記レンズおよび該レンズを備えた製品の薄型化の観点から有利であり、収差の抑制やアッベ数の向上にも貢献し得る。ここに開示される粘着剤は、例えば適切な透明部材の凹部または空隙に充填された形態で、それ自体をレンズ樹脂として利用することも可能である。 The adhesive disclosed in this specification is a microlens or other lens member used as a constituent member of a camera, a light emitting device, or the like (for example, a microlens constituting a microlens array film or a lens member such as a camera microlens). ), A coating layer covering the lens surface, a bonding layer with a member facing the lens surface (for example, a member having a surface shape corresponding to the lens surface), and a filling filled between the lens surface and the member. It can be preferably used as a layer, etc. Since the pressure-sensitive adhesive disclosed herein is suitable for increasing the refractive index, a lens having a high refractive index (for example, a lens made of a high refractive index resin or a lens having a surface layer made of a high refractive index resin) is used. Even if there is, the difference in refractive index from the lens can be reduced. This is advantageous from the viewpoint of reducing the thickness of the lens and the product provided with the lens, and can also contribute to the suppression of aberration and the improvement of the Abbe number. The pressure-sensitive adhesive disclosed herein can also be used as a lens resin by itself, for example, in the form of being filled in the recesses or voids of a suitable transparent member.
 ここに開示される粘着型光学フィルムは、粘着型光学部材としても把握され得る。また、ここに開示される粘着型光学フィルムにおける光透過性部材として上記機能性フィルムを用いた場合には、ここに開示される粘着型光学フィルムは、機能性フィルムの少なくとも片面側にここに開示される粘着剤層を有する「粘着型機能性フィルム」としても把握され得る。 The adhesive optical film disclosed here can also be grasped as an adhesive optical member. Further, when the functional film is used as the light transmissive member in the adhesive optical film disclosed herein, the adhesive optical film disclosed herein is disclosed here on at least one side of the functional film. It can also be grasped as a "adhesive type functional film" having an adhesive layer to be formed.
 上記より、ここに開示される技術によると、ここに開示される粘着型光学フィルムを備える積層体が提供される。粘着型光学フィルムが貼り付けられる部材は、上述した被着体材料の屈折率を有するものであり得る。また、粘着型光学フィルムの屈折率と部材の屈折率との差(屈折率差)は、上述した被着体と粘着型光学フィルムとの屈折率差であり得る。積層体を構成する部材については、上述の部材、材料、被着体として説明したとおりであるので、重複する説明は繰り返さない。 From the above, according to the technique disclosed herein, a laminate comprising the adhesive optical film disclosed herein is provided. The member to which the adhesive optical film is attached may have the refractive index of the adherend material described above. Further, the difference between the refractive index of the adhesive optical film and the refractive index of the member (refractive index difference) may be the difference in refractive index between the adherend and the adhesive optical film described above. Since the members constituting the laminated body have been described as the above-mentioned members, materials, and adherends, the overlapping description will not be repeated.
 以上の説明および以下の実施例から理解されるように、この明細書により開示される事項には以下のものが含まれる。
 〔1〕 粘着剤層を含む粘着シートであって、
 上記粘着剤層により構成された粘着面を有し、
 上記粘着剤層は、屈折率が1.570超であり、全光線透過率が86%以上であり、かつヘイズ値が3.0%以下である、粘着シート。
 〔2〕 上記粘着剤層は、厚さが5μm以上である、上記〔1〕に記載の粘着シート。
 〔3〕 粘着力が3N/25mm以上である、上記〔1〕また〔2〕に記載の粘着シート。
 〔4〕 上記粘着面は、算術平均粗さRaが100nm以下である、上記〔1〕~〔3〕のいずれかに記載の粘着シート。
 〔5〕 上記粘着剤層は、吸水率が1.0%以下である、上記〔1〕~〔4〕のいずれかに記載の粘着シート。
 〔6〕 上記粘着剤層と光透過性部材とを含む積層体として構成されている、上記〔1〕~〔5〕のいずれかに記載の粘着シート。
 〔7〕 上記光透過性部材は樹脂フィルムである、上記〔6〕に記載の粘着シート。
 〔8〕 上記粘着剤層からなる両面接着性粘着シートである、上記〔1〕~〔5〕のいずれかに記載の粘着シート。
 〔9〕 上記〔1〕~〔8〕のいずれかに記載の粘着シートと、
 上記粘着シートの粘着面上に配置された剥離ライナーと、
を含む、剥離ライナー付き粘着シート。
 〔91〕 光透過性部材と、該光透過性部材上に積層された粘着剤層と、を含む粘着型光学フィルムであって、
 上記粘着剤層により構成された粘着面を有し、
 上記粘着剤層は、屈折率が1.570超であり、全光線透過率が86%以上であり、かつヘイズ値が3.0%以下である、粘着型光学フィルム。
 〔92〕 上記粘着剤層は、厚さが5μm以上である、上記〔91〕に記載の粘着型光学フィルム。
 〔93〕 ガラス板に対する剥離強度が3N/25mm以上である、上記〔91〕または〔92〕に記載の粘着型光学フィルム。
 〔94〕 上記粘着面は、算術平均粗さRaが100nm以下である、上記〔91〕~〔93〕のいずれかに記載の粘着型光学フィルム。
 〔95〕 上記粘着剤層は、吸水率が1.0%以下である、上記〔91〕~〔94〕のいずれかに記載の粘着型光学フィルム。
 〔96〕 上記光透過性部材は樹脂フィルムである、上記〔91〕~〔95〕のいずれかに記載の粘着型光学フィルム。
 〔97〕 上記光透過性部材は、偏光板、保護フィルムおよびカバーウィンドウ部材からなる群から選択される、上記〔91〕~〔96〕のいずれかに記載の粘着型光学フィルム。
 〔98〕 上記〔91〕~〔97〕のいずれかに記載の粘着型光学フィルムと、
 上記粘着型光学フィルムの粘着面上に配置された剥離ライナーと、
を含む、剥離ライナー付き粘着型光学フィルム。
 〔10〕 上記〔1〕~〔8〕のいずれかに記載の粘着シートの粘着剤層または上記〔91〕~〔97〕のいずれかに記載の粘着型光学フィルムの粘着剤層を形成するために用いられる、粘着剤組成物。
As will be understood from the above description and the following examples, the matters disclosed by this specification include the following.
[1] An adhesive sheet containing an adhesive layer.
It has an adhesive surface composed of the above adhesive layer and has an adhesive surface.
The pressure-sensitive adhesive layer is a pressure-sensitive adhesive sheet having a refractive index of more than 1.570, a total light transmittance of 86% or more, and a haze value of 3.0% or less.
[2] The pressure-sensitive adhesive sheet according to [1] above, wherein the pressure-sensitive adhesive layer has a thickness of 5 μm or more.
[3] The adhesive sheet according to the above [1] and [2], which has an adhesive strength of 3 N / 25 mm or more.
[4] The adhesive sheet according to any one of [1] to [3] above, wherein the adhesive surface has an arithmetic mean roughness Ra of 100 nm or less.
[5] The pressure-sensitive adhesive sheet according to any one of [1] to [4] above, wherein the pressure-sensitive adhesive layer has a water absorption rate of 1.0% or less.
[6] The pressure-sensitive adhesive sheet according to any one of [1] to [5] above, which is configured as a laminated body including the pressure-sensitive adhesive layer and a light-transmitting member.
[7] The adhesive sheet according to the above [6], wherein the light transmissive member is a resin film.
[8] The pressure-sensitive adhesive sheet according to any one of [1] to [5] above, which is a double-sided adhesive pressure-sensitive adhesive sheet composed of the pressure-sensitive adhesive layer.
[9] The adhesive sheet according to any one of the above [1] to [8] and
With the release liner placed on the adhesive surface of the adhesive sheet,
Adhesive sheet with release liner, including.
[91] An adhesive optical film comprising a light-transmitting member and an adhesive layer laminated on the light-transmitting member.
It has an adhesive surface composed of the above adhesive layer and has an adhesive surface.
The pressure-sensitive adhesive layer is an adhesive optical film having a refractive index of more than 1.570, a total light transmittance of 86% or more, and a haze value of 3.0% or less.
[92] The pressure-sensitive optical film according to [91], wherein the pressure-sensitive adhesive layer has a thickness of 5 μm or more.
[93] The adhesive optical film according to the above [91] or [92], which has a peel strength against a glass plate of 3 N / 25 mm or more.
[94] The adhesive optical film according to any one of [91] to [93] above, wherein the adhesive surface has an arithmetic mean roughness Ra of 100 nm or less.
[95] The pressure-sensitive optical film according to any one of [91] to [94] above, wherein the pressure-sensitive adhesive layer has a water absorption rate of 1.0% or less.
[96] The adhesive optical film according to any one of [91] to [95] above, wherein the light transmissive member is a resin film.
[97] The adhesive optical film according to any one of [91] to [96], wherein the light transmissive member is selected from the group consisting of a polarizing plate, a protective film, and a cover window member.
[98] The adhesive optical film according to any one of [91] to [97] above,
With the release liner placed on the adhesive surface of the adhesive optical film,
Adhesive optical film with release liner, including.
[10] To form the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet according to any one of [1] to [8] above or the pressure-sensitive adhesive layer of the pressure-sensitive optical film according to any one of [91] to [97] above. Adhesive composition used in.
 〔11〕 芳香環含有モノマー(m1)をモノマー単位として含むアクリル系ポリマー(A)と、
 上記アクリル系ポリマー(A)よりも高屈折率の有機材料である添加剤(HRO)と、
を含む、粘着剤組成物。
 〔12〕 上記添加剤(HRO)の屈折率は1.60以上である、上記〔11〕に記載の粘着剤組成物。
 〔13〕 上記アクリル系ポリマー(A)100重量部に対する上記添加剤(HRO)の含有量は、0重量部を超えて60重量部以下である、上記〔11〕または〔12〕に記載の粘着剤組成物。
 〔14〕 上記添加剤(HRO)は、芳香環含有化合物および複素環含有化合物からなる群から選択される少なくとも1種の化合物を含む、上記〔11〕~〔13〕のいずれかに記載の粘着剤組成物。
 〔15〕 上記添加剤(HRO)は、1分子内に2以上の芳香環を有する化合物を含む、上記〔11〕~〔14〕のいずれかに記載の粘着剤組成物。
 〔16〕 上記添加剤(HRO)は、上記1分子内に2以上の芳香環を有する化合物として、
 (i)2つの非縮合芳香環が直接化学結合した構造を含む、および
 (ii)2つの芳香環が縮合した構造を含む、
の少なくとも一方を満たす化合物を含む、上記〔15〕に記載の粘着剤組成物。
 〔17〕 上記アクリル系ポリマー(A)を構成するモノマー成分において、上記芳香環含有モノマー(m1)の含有量は50重量%以上である、上記〔11〕~〔16〕のいずれかに記載の粘着剤組成物。
 〔18〕 上記アクリル系ポリマー(A)を構成するモノマー成分において、上記芳香環含有モノマー(m1)の含有量は70重量%を超えて100重量%未満であり、
 上記芳香環含有モノマー(m1)のうち50重量%以上は、ホモポリマーのガラス転移温度が10℃以下のモノマーである、上記〔11〕~〔17〕のいずれかに記載の粘着剤組成物。
 〔19〕 上記アクリル系ポリマー(A)を構成するモノマー成分は、水酸基およびカルボキシ基の少なくとも一方を有するモノマー(m2)をさらに含有する、上記〔11〕~〔18〕のいずれかに記載の粘着剤組成物。
 〔20〕 上記〔1〕~〔8〕のいずれかに記載の粘着シートの粘着剤層または上記〔91〕~〔97〕のいずれかに記載の粘着型光学フィルムの粘着剤層を形成するために用いられる、上記〔11〕~〔18〕のいずれかに記載の粘着剤組成物。
 〔21〕 上記〔11〕~〔20〕のいずれかに記載の粘着剤組成物から形成された粘着剤であって、屈折率が1.570より高い、粘着剤。
 〔22〕 上記〔11〕~〔20〕のいずれかに記載の粘着剤組成物から形成された粘着剤により構成された粘着剤層を含む、粘着シート。
 〔23〕 上記粘着剤層のヘイズ値が1.0%以下である、上記〔22〕に記載の粘着シート。
[11] An acrylic polymer (A) containing an aromatic ring-containing monomer (m1) as a monomer unit, and
An additive (HRO ), which is an organic material having a higher refractive index than the above-mentioned acrylic polymer (A),
A pressure-sensitive adhesive composition.
[12] The pressure-sensitive adhesive composition according to the above [11], wherein the additive (H RO) has a refractive index of 1.60 or more.
[13] The above-mentioned [11] or [12], wherein the content of the additive (HRO ) with respect to 100 parts by weight of the acrylic polymer (A) is more than 0 parts by weight and 60 parts by weight or less. Adhesive composition.
[14] The additive (H RO ) according to any one of the above [11] to [13], which comprises at least one compound selected from the group consisting of an aromatic ring-containing compound and a heterocyclic ring-containing compound. Adhesive composition.
[15] The pressure-sensitive adhesive composition according to any one of [11] to [14] above, wherein the additive (H RO) contains a compound having two or more aromatic rings in one molecule.
[16] The additive ( HRO ) is a compound having two or more aromatic rings in one molecule.
(I) Containing a structure in which two non-condensed aromatic rings are directly chemically bonded, and (ii) Containing a structure in which two non-condensed aromatic rings are condensed.
The pressure-sensitive adhesive composition according to the above [15], which comprises a compound satisfying at least one of the above.
[17] The above-mentioned [11] to [16], wherein the content of the aromatic ring-containing monomer (m1) in the monomer component constituting the acrylic polymer (A) is 50% by weight or more. Adhesive composition.
[18] In the monomer component constituting the acrylic polymer (A), the content of the aromatic ring-containing monomer (m1) is more than 70% by weight and less than 100% by weight.
The pressure-sensitive adhesive composition according to any one of [11] to [17] above, wherein 50% by weight or more of the aromatic ring-containing monomer (m1) is a monomer having a homopolymer glass transition temperature of 10 ° C. or less.
[19] The adhesive according to any one of [11] to [18] above, wherein the monomer component constituting the acrylic polymer (A) further contains a monomer (m2) having at least one of a hydroxyl group and a carboxy group. Agent composition.
[20] To form the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet according to any one of [1] to [8] above or the pressure-sensitive adhesive layer of the pressure-sensitive optical film according to any one of [91] to [97] above. The pressure-sensitive adhesive composition according to any one of the above [11] to [18], which is used in the above.
[21] A pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition according to any one of [11] to [20] above, which has a refractive index higher than 1.570.
[22] A pressure-sensitive adhesive sheet containing a pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition according to any one of [11] to [20] above.
[23] The pressure-sensitive adhesive sheet according to [22] above, wherein the haze value of the pressure-sensitive adhesive layer is 1.0% or less.
 〔24〕 光学用途において積層体の層間に配置して用いられる層間シートであって、
 屈折率nが1.570以上である粘弾性層Vを含み、かつ
 全光線透過率が86%以上である;
 ヘイズ値が1.0%以下である;および、
 25℃における貯蔵弾性率G’が30kPa~700kPaである;
を満たす、層間シート。
 〔25〕 厚さが5μm以上である、上記〔24〕に記載の層間シート。
 〔26〕 上記粘弾性層Vは、主ポリマーと、上記主ポリマーより分子量の低い可塑化材料とを含む、上記〔24〕または〔25〕に記載の層間シート。
 〔27〕 上記可塑化材料の重量平均分子量は30000以下である、上記〔26〕に記載の層間シート。
 〔28〕 上記粘弾性層Vに積層された粘弾性層Vをさらに含み、
 上記粘弾性層Vの25℃における貯蔵弾性率G’V2は、上記粘弾性層Vの25℃における貯蔵弾性率G’V1より低い、上記〔24〕~〔27〕のいずれかに記載の層間シート。
 〔29〕 上記粘弾性層Vの屈折率nは、上記粘弾性層Vの屈折率nより低い、上記〔28〕に記載の層間シート。
 〔30〕 上記粘弾性層Vは、上記〔11〕~〔18〕のいずれかに記載の粘着剤組成物から形成された層である、上記〔24〕~〔29〕のいずれかに記載の層間シート。
 〔31〕 上記粘弾性層Vは、上記〔1〕~〔5〕のいずれかに記載の粘着シートにおける粘着剤層である、上記〔24〕~〔29〕のいずれかに記載の層間シート。
 〔32〕 上記〔24〕~〔31〕のいずれか一項に記載の層間シートと、
 上記層間シートに積層された樹脂フィルムと、
を含む、光学積層体。
 〔33〕 上記〔24〕~〔31〕のいずれか一項に記載の層間シートと、
 上記層間シートの少なくとも一方の表面を覆う剥離ライナーと、
を含む、剥離ライナー付き層間シート。
[24] An interlayer sheet used by arranging between layers of a laminated body in optical applications.
Refractive index n 1 comprises a viscoelastic layer V 1 is 1.570 or more, and the total light transmittance is 86% or more;
Haze value is 1.0% or less; and
The storage modulus G'at 25 ° C. is 30 kPa to 700 kPa;
An interlayer sheet that meets the requirements.
[25] The interlayer sheet according to the above [24], which has a thickness of 5 μm or more.
[26] The interlayer sheet according to the above [24] or [25], wherein the viscoelastic layer V 1 contains a main polymer and a thermoplastic material having a molecular weight lower than that of the main polymer.
[27] The interlayer sheet according to the above [26], wherein the weight average molecular weight of the plasticized material is 30,000 or less.
[28] The viscoelastic layer V 2 laminated on the viscoelastic layer V 1 is further included.
'Is V2, the storage modulus G 25 ° C. of the viscoelastic layer V 1' storage modulus G 25 ° C. of the viscoelastic layer V 2 lower than V1, according to any one of [24] - [27] Layered sheet.
[29] the refractive index n 2 of the viscoelastic layer V 2 is lower than the refractive index n 1 of the viscoelastic layer V 1, interlayer sheet according to [28].
[30] the viscoelastic layer V 1 was a layer formed from the pressure-sensitive adhesive composition according to any one of [11] - [18], according to any one of [24] - [29] Layered sheet.
[31] The interlayer sheet according to any one of [24] to [29], wherein the viscoelastic layer V 1 is an adhesive layer in the adhesive sheet according to any one of the above [1] to [5]. ..
[32] The interlayer sheet according to any one of the above [24] to [31] and the interlayer sheet.
The resin film laminated on the interlayer sheet and
Including an optical laminate.
[33] The interlayer sheet according to any one of the above [24] to [31] and the interlayer sheet.
A release liner that covers at least one surface of the interlayer sheet,
Interlayer sheet with release liner, including.
 以下、本発明に関する関連するいくつかの実験例を説明する。なお、以下の説明において、使用量や含有量を表す「部」および「%」は、特に断りがない限り重量基準である。 Hereinafter, some related experimental examples related to the present invention will be described. In the following description, "parts" and "%" representing the amount used and the content are based on weight unless otherwise specified.
<例1>
 (アクリル系ポリマー溶液の調製)
 攪拌羽根、温度計、窒素ガス導入管および冷却器を備えた四つ口フラスコに、モノマー成分としてm-フェノキシベンジルアクリレート(共栄社化学株式会社製、商品名「ライトアクリレートPOB-A」、屈折率:1.566、ホモポリマーのTg:-35℃。以下、「POB-A」と略記する。)99部および4-ヒドロキシブチルアクリレート(4HBA)1部、重合開始剤として2、2’-アゾビスイソブチロニトリル(AIBN)0.2部、および重合溶媒としてトルエン100部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を60℃ 付近に保って6時間重合反応を行い、アクリル系ポリマーA1の溶液(50%)を調製した。上記アクリル系ポリマーA1は、上記モノマー成分の組成に基づくTg(すなわちTg)が-35℃であり、芳香環含有モノマーの組成に基づくTg(すなわちTgm1)が-35℃である。
<Example 1>
(Preparation of acrylic polymer solution)
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube and a cooler, m-phenoxybenzyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name "light acrylate POB-A", refractive index: 1.566, homopolymer Tg: -35 ° C., hereinafter abbreviated as "POB-A") 99 parts and 1 part of 4-hydroxybutyl acrylate (4HBA), 2,2'-azobis as a polymerization initiator. Add 0.2 parts of isobutyronitrile (AIBN) and 100 parts of toluene as a polymerization solvent, introduce nitrogen gas with gentle stirring, keep the liquid temperature in the flask at around 60 ° C, and carry out the polymerization reaction for 6 hours. A solution (50%) of the acrylic polymer A1 was prepared. The acrylic polymer A1 has a Tg (that is, Tg T ) based on the composition of the monomer component at −35 ° C. and a Tg (that is, Tg m1 ) based on the composition of the aromatic ring-containing monomer at −35 ° C.
 (粘着剤組成物の調製)
 上記アクリル系ポリマーA1の溶液(50%)を酢酸エチルで30%に希釈し、この溶液334部(不揮発分100部)に、架橋剤としてヘキサメチレンジイソシアネートのイソシアヌレート体(東ソー社製、商品名「コロネートHX」、3官能イソシアネート化合物)の1%酢酸エチル溶液を10部(不揮発分0.1部)、架橋遅延剤としてアセチルアセトンを2部、架橋触媒としてナーセム第二鉄の1% 酢酸エチル溶液を1部(不揮発分0.01部)加えて攪拌混合し、アクリル系粘着剤組成物C1を調製した。
(Preparation of adhesive composition)
The solution (50%) of the acrylic polymer A1 is diluted to 30% with ethyl acetate, and an isocyanurate compound of hexamethylene diisocyanate (manufactured by Toso Co., Ltd., trade name) is added to 334 parts (nonvolatile content 100 parts) of this solution as a cross-linking agent. 10 parts of 1% ethyl acetate solution of "Coronate HX" (trifunctional isocyanate compound) (0.1 part of non-volatile content), 2 parts of acetylacetone as a cross-linking retardant, 1% ethyl acetate solution of Nasem ferric iron as a cross-linking catalyst 1 part (nonvolatile content 0.01 part) was added and mixed by stirring to prepare an acrylic pressure-sensitive adhesive composition C1.
 (粘着シートの作製)
 上記で調製したアクリル系粘着剤組成物C1を、片面にシリコーン処理が施されたポリエチレンテレフタレート(PET)フィルムR1(厚さ50μm、シリコーン処理面の算術平均粗さRa 21nm、最大高さRz 233nm)のシリコーン処理面に塗布し、130℃で2分間加熱して、厚さ20μmの粘着剤層を形成した。次いで、上記粘着剤層の表面(第1粘着面)に、片面にシリコーン処理が施されたPETフィルムR2(厚さ25μm、シリコーン処理面の算術平均粗さRa 15nm、最大高さRz 180nm)のシリコーン処理面を貼り合わせた。このようにして、上記粘着剤層からなる基材レス両面粘着シートS1を得た。粘着シートS1の両面は、PETフィルム(剥離ライナー)R1,R2によって保護されている。第1粘着面に貼り合わされた剥離ライナーR2は、第2粘着面を保護する剥離ライナーR1(粘着剤組成物が塗布される剥離ライナー)に比べて、相対的に軽剥離である。
(Making an adhesive sheet)
Polyethylene terephthalate (PET) film R1 (thickness 50 μm, arithmetic average roughness Ra 21 nm, maximum height Rz 233 nm) of the silicone-based pressure-sensitive adhesive composition C1 prepared above, which has been treated with silicone on one side. Was applied to the silicone-treated surface of the above and heated at 130 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 20 μm. Next, a PET film R2 (thickness 25 μm, arithmetic mean roughness Ra of the silicone-treated surface Ra 15 nm, maximum height Rz 180 nm) in which one side of the surface (first adhesive surface) of the pressure-sensitive adhesive layer was treated with silicone was applied. The silicone-treated surfaces were bonded together. In this way, a base material-less double-sided pressure-sensitive adhesive sheet S1 composed of the pressure-sensitive adhesive layer was obtained. Both sides of the adhesive sheet S1 are protected by PET films (release liners) R1 and R2. The release liner R2 bonded to the first adhesive surface is relatively lightly peeled as compared with the release liner R1 (release liner to which the pressure-sensitive adhesive composition is applied) that protects the second adhesive surface.
<例2~3,7~8,10~14>
 モノマー成分の組成を表1に示すように変更した他は例1におけるアクリル系ポリマー溶液の調製と同様にして、各例に係るアクリル系ポリマーA2~3,7~8,10~14の溶液を調製した。
 アクリル系ポリマーA1の溶液に代えて上記各例に係るアクリル系ポリマーの溶液をそれぞれ使用した他は例1における粘着剤組成物の調製と同様にして、各例に係るアクリル系粘着剤組成物C2~3,7~8,10~14を調製した。
 アクリル系粘着剤組成物C1に代えて上記各例に係るアクリル系粘着剤組成物をそれぞれ使用し、粘着剤層の厚さを表1に示すとおりとした他は、例1における粘着シートの作製と同様にして、各例に係る粘着シート(粘着剤層からなる基材レス両面粘着シート)S2~3,7~8,10~14を作製した。
 なお、表1に示すモノマー成分の組成において、「NMT-A」は1-ナフチルメチルアクリレート(共栄社化学株式会社製、商品名「ライトアクリレートNMT-A」、屈折率:1.595、ホモポリマーのTg:31℃)を表し、HEAは2-ヒドロキシエチルアクリレート、BAはn-ブチルアクリレート、2EHAは2-エチルヘキシルアクリレートをそれぞれ表す。
<Examples 2 to 3, 7 to 8, 10 to 14>
The solutions of the acrylic polymers A2 to 3,7 to 8,10 to 14 according to each example were prepared in the same manner as in the preparation of the acrylic polymer solution in Example 1 except that the composition of the monomer components was changed as shown in Table 1. Prepared.
The acrylic pressure-sensitive adhesive composition C2 according to each example was prepared in the same manner as in the preparation of the pressure-sensitive adhesive composition in Example 1 except that the solution of the acrylic polymer according to each of the above examples was used instead of the solution of the acrylic polymer A1. ~ 3,7 ~ 8,10 ~ 14 were prepared.
Preparation of the pressure-sensitive adhesive sheet according to Example 1 except that the acrylic pressure-sensitive adhesive composition according to each of the above examples was used instead of the acrylic pressure-sensitive adhesive composition C1 and the thickness of the pressure-sensitive adhesive layer was set as shown in Table 1. In the same manner as in the above, the pressure-sensitive adhesive sheets (base-less double-sided pressure-sensitive adhesive sheets made of a pressure-sensitive adhesive layer) S2 to 3,7 to 8,10 to 14 according to each example were produced.
In the composition of the monomer components shown in Table 1, "NMT-A" is 1-naphthylmethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name "light acrylate NMT-A", refractive index: 1.595, homopolymer. Tg: 31 ° C.), HEA represents 2-hydroxyethyl acrylate, BA represents n-butyl acrylate, and 2EHA represents 2-ethylhexyl acrylate.
<例4>
 例3で調製したアクリル系ポリマーA3の溶液(50%)を酢酸エチルで30%に希釈し、この溶液334部(不揮発分100部)に、添加剤(HRO)として6-アクリロイルオキシメチルジナフトチオフェン(スガイ化学工業株式会社製のジナフトチオフェン-6-メチルアクリレート体、商品名「6MDNTA」、屈折率1.75)を5部、架橋剤としてヘキサメチレンジイソシアネートのイソシアヌレート体(東ソー社製、商品名「コロネートHX」、3官能イソシアネート化合物)の1%酢酸エチル溶液を10部(不揮発分0.1部)、架橋遅延剤としてアセチルアセトンを2部、架橋触媒としてナーセム第二鉄の1% 酢酸エチル溶液を1部(不揮発分0.01部)加えて攪拌混合し、アクリル系粘着剤組成物C4を調製した。
 アクリル系粘着剤組成物C1に代えてアクリル系粘着剤組成物C4を使用し、粘着剤層の厚さを25μmとした他は、例1における粘着シートの作製と同様にして、本例に係る粘着シート(粘着剤層からなる基材レス両面粘着シート)S4を作製した。
<Example 4>
The solution (50%) of the acrylic polymer A3 prepared in Example 3 was diluted to 30% with ethyl acetate, and 6-acryloyloxymethyldi as an additive (HRO) was added to 334 parts (100 parts of non-volatile content) of this solution. 5 parts of naphthophene (dinaphthophen-6-methylacrylate manufactured by Sugai Chemical Industry Co., Ltd., trade name "6MDNTA", refractive index 1.75), isocyanurate of hexamethylenediisocyanate as a cross-linking agent (manufactured by Toso Co., Ltd.) , Trade name "Coronate HX", trifunctional isocyanate compound) 1% ethyl acetate solution (0.1 part non-volatile content), 2 parts acetylacetone as a cross-linking retardant, 1% of Nasem ferric iron as a cross-linking catalyst. One part (0.01 part of non-volatile content) of the ethyl acetate solution was added and mixed by stirring to prepare an acrylic pressure-sensitive adhesive composition C4.
Similar to the production of the pressure-sensitive adhesive sheet in Example 1, except that the acrylic pressure-sensitive adhesive composition C4 was used instead of the acrylic pressure-sensitive adhesive composition C1 and the thickness of the pressure-sensitive adhesive layer was 25 μm. An adhesive sheet (base-less double-sided adhesive sheet composed of an adhesive layer) S4 was produced.
<例5~6>
 添加剤(HRO)の種類とアクリル系ポリマー100部に対する使用量(phr;per hundred resin)を表1に示すように変更した他は、例4におけるアクリル系粘着剤組成物C4の調製と同様にして、例5、6に係るアクリル系粘着剤組成物C5、C6を調製した。ここで、表1中の「BPFL」は、9,9-ビス(4-ヒドロキシフェニル)フルオレン(大阪ガスケミカル株式会社製、屈折率1.68)を表し、「BAFL」は9,9-ビス(4-アミノフェニル)フルオレン(大阪ガスケミカル株式会社製、屈折率1.73)を表す。
 アクリル系粘着剤組成物C4に代えてアクリル系粘着剤組成物C5、C6をそれぞれ使用した他は例4における粘着シートの作製と同様にして、例5、6に係る粘着シート(粘着剤層からなる基材レス両面粘着シート)を作製した。
<Examples 5 to 6>
Similar to the preparation of the acrylic pressure-sensitive adhesive composition C4 in Example 4, except that the type of additive (H RO ) and the amount used per 100 parts of the acrylic polymer (phr; per hundred resin) were changed as shown in Table 1. Then, the acrylic pressure-sensitive adhesive compositions C5 and C6 according to Examples 5 and 6 were prepared. Here, "BPFL" in Table 1 represents 9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.68), and "BAFL" is 9,9-bis. It represents (4-aminophenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd., refractive index 1.73).
The pressure-sensitive adhesive sheets (from the pressure-sensitive adhesive layer) according to Examples 5 and 6 are the same as in the production of the pressure-sensitive adhesive sheet in Example 4, except that the acrylic pressure-sensitive adhesive compositions C5 and C6 are used instead of the acrylic pressure-sensitive adhesive composition C4, respectively. A base material-less double-sided adhesive sheet) was produced.
<例9>
 例8で調製したアクリル系ポリマーA8の溶液(50%)を酢酸エチルで30%に希釈し、この溶液334部(不揮発分100部)に、添加剤(HRO)としてBPFLを10部、架橋剤としてヘキサメチレンジイソシアネートのイソシアヌレート体(東ソー社製、商品名「コロネートHX」、3官能イソシアネート化合物)の1%酢酸エチル溶液を10部(不揮発分0.1部)、架橋遅延剤としてアセチルアセトンを2部、架橋触媒としてナーセム第二鉄の1% 酢酸エチル溶液を1部(不揮発分0.01部)加えて攪拌混合し、アクリル系粘着剤組成物C9を調製した。
 アクリル系粘着剤組成物C8に代えてアクリル系粘着剤組成物C9を使用した他は例8における粘着シートの作製と同様にして、本例に係る粘着シート(粘着剤層からなる基材レス両面粘着シート)S9を作製した。
<Example 9>
The solution of the acrylic polymer A8 prepared in Example 8 (50%) was diluted to 30% with ethyl acetate, to the solution 334 parts (nonvolatile content 100 parts), 10 parts of BPFL as an additive (H RO), crosslinked 10 parts (0.1 part non-volatile content) of a 1% ethyl acetate solution of an isocyanurate compound of hexamethylene diisocyanate (manufactured by Toso Co., Ltd., trade name "Coronate HX", trifunctional isocyanate compound) was used as an agent, and acetylacetone was used as a cross-linking retarder. 2 parts, 1 part (0.01 part of non-volatile content) of 1% ethyl acetate solution of Nasem ferric iron as a cross-linking catalyst was added and mixed by stirring to prepare an acrylic pressure-sensitive adhesive composition C9.
Similar to the production of the pressure-sensitive adhesive sheet in Example 8 except that the acrylic pressure-sensitive adhesive composition C9 was used instead of the acrylic pressure-sensitive adhesive composition C8, the pressure-sensitive adhesive sheet (base-less double-sided surface composed of the pressure-sensitive adhesive layer) was obtained in the same manner as in Example 8. Adhesive sheet) S9 was produced.
<例15>
 モノマー成分の組成を、2-エチルヘキシルアクリレート(2EHA)を90部、4HBAを10部に変更した他は、例1におけるアクリル系ポリマー溶液の調製と同様にして、アクリル系ポリマーA14の溶液(40%)を調製した。
 上記アクリル系ポリマーA14の溶液(40%)を酢酸エチルで20%に希釈し、この溶液500部(不揮発分100部)に、ジルコニア粒子分散液を固形分基準で10部、架橋剤としてヘキサメチレンジイソシアネートのイソシアヌレート体(東ソー社製、商品名「コロネートHX」、3官能イソシアネート化合物)の1%酢酸エチル溶液を10部(不揮発分0.1部)、架橋遅延剤としてアセチルアセトンを2部、架橋触媒としてナーセム第二鉄の1% 酢酸エチル溶液を1部(不揮発分0.01部)加えて攪拌混合し、アクリル系粘着剤組成物C15を調製した。上記ジルコニア粒子分散液としては、表面処理を施したジルコニア粒子(平均粒径20nm、固形分屈折率:1.64、表面処理:カルボン酸系/リン酸系疎水化処理、共栄社化学株式会社製)をプロピレングリコールモノメチルエーテル(PGME)中に分散させた表面処理ジルコニア粒子分散液を用いた。
 アクリル系粘着剤組成物C14に代えてアクリル系粘着剤組成物C15を使用した他は例14における粘着シートの作製と同様にして、例15に係る粘着シート(粘着剤層からなる基材レス両面粘着シート)S15を作製した。
<Example 15>
The composition of the monomer component was changed to 90 parts of 2-ethylhexyl acrylate (2EHA) and 10 parts of 4HBA, but the solution of the acrylic polymer A14 (40%) was the same as the preparation of the acrylic polymer solution in Example 1. ) Was prepared.
The solution (40%) of the acrylic polymer A14 is diluted to 20% with ethyl acetate, and in 500 parts (100 parts of non-volatile content) of this solution, 10 parts of zirconia particle dispersion is added based on the solid content, and hexamethylene as a cross-linking agent. 10 parts (0.1 part of non-volatile content) of 1% ethyl acetate solution of isocyanurate of diisocyanate (manufactured by Toso Co., Ltd., trade name "Coronate HX", trifunctional isocyanate compound), 2 parts of acetylacetone as a cross-linking retardant, cross-linking As a catalyst, 1 part (0.01 part of non-volatile content) of 1% ethyl acetate solution of Narsem ferric iron was added and mixed by stirring to prepare an acrylic pressure-sensitive adhesive composition C15. The zirconia particle dispersion is a surface-treated zirconia particle (average particle size 20 nm, solid content refractive index: 1.64, surface treatment: carboxylic acid / phosphoric acid hydrophobization, manufactured by Kyoeisha Chemical Co., Ltd.). Was dispersed in propylene glycol monomethyl ether (PGME), and a surface-treated zirconia particle dispersion was used.
Similar to the production of the pressure-sensitive adhesive sheet in Example 14, except that the acrylic pressure-sensitive adhesive composition C15 was used instead of the acrylic pressure-sensitive adhesive composition C14, the pressure-sensitive adhesive sheet according to Example 15 (base-less double-sided surface composed of a pressure-sensitive adhesive layer). Adhesive sheet) S15 was produced.
 得られた粘着シートは、23℃、50%RHの環境に十分馴染ませた後に、以下の測定および評価に使用した。 The obtained adhesive sheet was sufficiently acclimatized to an environment of 23 ° C. and 50% RH, and then used for the following measurements and evaluations.
<測定および評価(1)>
 (屈折率)
 各例に係る粘着剤層(基材レス両面粘着シート)について、測定波長589nm、測定温度25℃の条件で、アッベ屈折率計(ATAGO社製、型式「DR-M4」)を使用して屈折率を測定した。結果を表1に示す。
<Measurement and evaluation (1)>
(Refractive index)
The pressure-sensitive adhesive layer (base-less double-sided pressure-sensitive adhesive sheet) according to each example is refracted using an Abbe refractive index meter (manufactured by ATAGO, model "DR-M4") under the conditions of a measurement wavelength of 589 nm and a measurement temperature of 25 ° C. The rate was measured. The results are shown in Table 1.
 (全光線透過率およびヘイズ値)
 各例に係る粘着剤層を無アルカリガラス(厚さ0.8~1.0mm、全光線透過率92%、ヘイズ0.4%)に貼り合わせた試験片を用い、23℃の測定環境下において、ヘイズメータ(村上色彩技術研究所製、商品名「HAZEMETER HM-150」)を用いて、上記試験片の全光線透過率およびヘイズを測定した。測定値から上記無アルカリガラスの全光線透過率およびヘイズを差し引いた値を、粘着剤層の全光線透過率およびヘイズ値とした。結果を表1に示す。
(Total light transmittance and haze value)
Using a test piece in which the pressure-sensitive adhesive layer according to each example was bonded to non-alkali glass (thickness 0.8 to 1.0 mm, total light transmittance 92%, haze 0.4%), under a measurement environment of 23 ° C. In, the total light transmittance and haze of the test piece were measured using a haze meter (manufactured by Murakami Color Technology Laboratory, trade name "HAZEMETER HM-150"). The value obtained by subtracting the total light transmittance and haze of the non-alkali glass from the measured value was taken as the total light transmittance and haze value of the pressure-sensitive adhesive layer. The results are shown in Table 1.
 (吸水率)
 上述した方法により、各例に係る粘着剤の吸水率を測定した。結果を表1に示す。
(Water absorption rate)
The water absorption rate of the pressure-sensitive adhesive according to each example was measured by the method described above. The results are shown in Table 1.
 なお、上述の方法で各例に係る粘着剤層の貯蔵弾性率G’(25)を測定したところ、例1~14ではいずれも350kPa以下であることが確認された。一方、高屈折率の無機粒子を配合することで屈折率を向上させた例15の粘着剤層は、貯蔵弾性率G’(25)が750kPaと高く、柔軟性および粘着性に欠けるものであった。 When the storage elastic modulus G'(25) of the pressure-sensitive adhesive layer according to each example was measured by the above-mentioned method, it was confirmed that all of Examples 1 to 14 were 350 kPa or less. On the other hand, the pressure-sensitive adhesive layer of Example 15 in which the refractive index was improved by blending inorganic particles having a high refractive index had a high storage elastic modulus G'(25) of 750 kPa and lacked flexibility and adhesiveness. rice field.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
<例16>
 厚さ5μmの粘着剤層が形成されるようにアクリル系粘着剤組成物C3の塗布量を調節した他は、例3に係る基材レス両面粘着シートS3の作製と同様にして、本例に係る基材レス両面粘着シートS16を得た。
<Example 16>
In this example, the coating amount of the acrylic pressure-sensitive adhesive composition C3 was adjusted so as to form a pressure-sensitive adhesive layer having a thickness of 5 μm, as in the production of the base material-less double-sided pressure-sensitive adhesive sheet S3 according to Example 3. A substrate-less double-sided pressure-sensitive adhesive sheet S16 was obtained.
<測定および評価(2)>
 上記で作成した粘着シートのいくつかについて、さらに以下の測定および評価を行った。結果を表2に示す。
<Measurement and evaluation (2)>
The following measurements and evaluations were further performed on some of the adhesive sheets prepared above. The results are shown in Table 2.
 (粘着面の算術平均粗さ(Ra)および最大高さ(Rz))
 各例に係る基材レス両面粘着シートを、第1、第2粘着面を保護する剥離ライナーR1,R2ごと、長さ150mm、幅50mmのサイズにカットして測定用サンプルを作製した。この測定用サンプルの剥離ライナーR1側を試験板に固定し、引張試験機(装置名「オートグラフAG-IS」、島津製作所製)を用いて、23℃、50%RHの雰囲気下、引張速度300mm/分、剥離角度180°の条件で、上記測定用サンプルの第1粘着面から剥離ライナーR2を引き剥がして第1粘着面を露出させた。30分静置した後、上記第1粘着面につき、23℃、50%RHの環境下において、3次元光学プロファイラー(商品名「NewView7300」、ZYGO社製)を用いて表面形状を測定した。測定したデータから算術表面粗さRaを、JIS B 0601-2001に準じて算出した。
 また、最大高さ(Rz)は、上記測定により得られたデータ(粗さ曲線)について、該粗さ曲線の平均線から上側に最も高い山の高さRpと、上記平均線から下側に最も深い谷の深さRvとの和として求めた。測定条件は以下のとおりである。
 RaおよびRzの測定は5回行い(すなわちN=5)、それらの平均値を採用した。
  [測定条件]
  測定面積:5.62mm×4.22mm
  (対物レンズ:2.5倍、内部レンズ:0.5倍)
  解析モード:
   Remove: Cylinder
   Data Fill: ON(Max:25)
   Remove Spikes: ON (xRMS:1)
   Filter: OFF
(Arithmetic Mean Roughness (Ra) and Maximum Height (Rz) of Adhesive Surface)
The base material-less double-sided adhesive sheet according to each example was cut into a size of 150 mm in length and 50 mm in width for each of the release liners R1 and R2 for protecting the first and second adhesive surfaces to prepare a measurement sample. The release liner R1 side of this measurement sample is fixed to a test plate, and a tensile tester (device name "Autograph AG-IS", manufactured by Shimadzu Corporation) is used to pull the tensile speed at 23 ° C. and 50% RH. Under the conditions of 300 mm / min and a peeling angle of 180 °, the peeling liner R2 was peeled off from the first adhesive surface of the measurement sample to expose the first adhesive surface. After allowing to stand for 30 minutes, the surface shape of the first adhesive surface was measured using a three-dimensional optical profiler (trade name "NewView7300", manufactured by ZYGO) in an environment of 23 ° C. and 50% RH. Arithmetic surface roughness Ra was calculated from the measured data according to JIS B 0601-2001.
The maximum height (Rz) is the height Rp of the highest mountain on the upper side of the average line of the roughness curve and the lower side of the average line of the data (roughness curve) obtained by the above measurement. It was calculated as the sum with the depth Rv of the deepest valley. The measurement conditions are as follows.
Ra and Rz were measured 5 times (ie N = 5) and their average values were taken.
[Measurement condition]
Measurement area: 5.62 mm x 4.22 mm
(Objective lens: 2.5x, internal lens: 0.5x)
Analysis mode:
Remove: Cylinder
Data Fill: ON (Max: 25)
Remove Spirits: ON (xRMS: 1)
Filter: OFF
 (光学歪)
 素板ガラスに銀引製法で作られた市販の鏡(厚さ2mm)を用意し、目視、および鏡単体で後述の記載と同様の手法でスクリーンに反射像を投影させて歪のないことを確認したものを使用する。クリーンルーム内において、上記鏡の表面をクリーンな布で拭いて異物等を除去した後、各例に係る基材レス両面粘着シートから剥離フィルムR2を剥がして第1粘着面を露出させ、上記鏡の表面に異物や気泡、変形のスジが入り込まないように適切な張力をかけて貼り付け、微小な気泡の影響を除去するために加圧脱泡装置(オートクレーブ)による脱泡処理を行った(処理条件:50℃、0.5MPa、30分)。室温で30分以上放冷した後、剥離フィルムR1を剥がして第2粘着面を露出させることにより、光学歪評価サンプル(粘着シートおよび鏡からなる積層体)を作製した。上記評価サンプルを、その粘着シート側を点光源側に向けて、上記点光源からの光線に対する角度が約45度となるように配置した。光線の先に白色スクリーンを設置し、反射させた像を映り込ませた。点光源としては、浜松ホトニクス社製の商品名「キセノンランプC2577」または相当品を使用することができ、今回の実験では上記商品名「キセノンランプC2577」を使用した。点光源、評価サンプルおよびスクリーンは、評価サンプルと点光源までの距離、評価サンプルとスクリーンまでの距離がそれぞれ約50cmの位置となるように配置した。
 上記点光源を点灯し、上記サンプルで反射されて上記スクリーンに投影された像を目視で観察することにより、以下の3水準で光学歪の有無および程度を評価した。
  E:光学歪は認められない。
  A:若干の光学歪が認められるが、実用上許容し得る程度である。
  P:明らかな光学歪が認められる。
(Optical distortion)
Prepare a commercially available mirror (thickness 2 mm) made by the silver pulling method on the base glass, and confirm that there is no distortion by projecting a reflected image on the screen visually and by using the mirror alone in the same manner as described later. Use what you have done. In the clean room, after wiping the surface of the mirror with a clean cloth to remove foreign matters and the like, the release film R2 is peeled off from the base material-less double-sided adhesive sheet according to each example to expose the first adhesive surface of the mirror. It was attached with appropriate tension so that foreign matter, air bubbles, and deformation streaks did not enter the surface, and defoaming treatment was performed with a pressure defoaming device (autoclave) to remove the influence of minute air bubbles (treatment). Conditions: 50 ° C., 0.5 MPa, 30 minutes). After allowing to cool at room temperature for 30 minutes or more, the release film R1 was peeled off to expose the second adhesive surface to prepare an optical strain evaluation sample (a laminate composed of an adhesive sheet and a mirror). The evaluation sample was arranged so that the pressure-sensitive adhesive sheet side was directed toward the point light source side and the angle with respect to the light beam from the point light source was about 45 degrees. A white screen was installed at the tip of the light beam to reflect the reflected image. As the point light source, the trade name "xenon lamp C2577" manufactured by Hamamatsu Photonics Co., Ltd. or an equivalent product can be used, and the above trade name "xenon lamp C2577" was used in this experiment. The point light source, the evaluation sample, and the screen were arranged so that the distance between the evaluation sample and the point light source and the distance between the evaluation sample and the screen were about 50 cm, respectively.
The presence or absence and degree of optical distortion were evaluated at the following three levels by turning on the point light source and visually observing the image reflected by the sample and projected on the screen.
E: No optical distortion is observed.
A: Some optical distortion is observed, but it is practically acceptable.
P: Clear optical distortion is observed.
 (対ガラス板剥離強度)
 23℃、50%RHの測定環境下において、粘着シートの一方の面から剥離ライナーを剥離し、厚み50μmのPETフィルムを貼り合わせて裏打ちした後、幅25mm、長さ100mmのサイズにカットしたものを試験片とした。試験片から他方の面の剥離ライナーを剥離し、被着体としてのアルカリガラス板(松浪硝子工業社製、厚さ1.35mm、青板縁磨品)の表面に、2kgのローラを1往復させて圧着した。これを同環境下に30分間放置し、次いで加圧脱泡装置(オートクレーブ)に投入して温度50℃、圧力0.5MPaの条件で30分間のオートクレーブ処理を行い、さらに23℃、50%RHの雰囲気下で24時間放置した後に、万能引張圧縮試験機を使用して、JIS Z 0237:2000に準じて、引張速度300mm/分、剥離角度180度の条件で、剥離強度(粘着力)[N/25mm]を測定した。万能引張圧縮試験機としては、ミネベア社製の「引張圧縮試験機、TG-1kN」を使用した。
(Peeling strength against glass plate)
A release liner was peeled off from one surface of an adhesive sheet under a measurement environment of 23 ° C. and 50% RH, a PET film having a thickness of 50 μm was attached and lined, and then cut into a size of 25 mm in width and 100 mm in length. Was used as a test piece. The peeling liner on the other side is peeled off from the test piece, and a 2 kg roller is reciprocated once on the surface of the alkaline glass plate (Matsunami Glass Ind., 1.35 mm thick, blue plate edge polished product) as an adherend. And crimped. This was left in the same environment for 30 minutes, then put into a pressure defoaming device (autoclave), autoclaved at a temperature of 50 ° C. and a pressure of 0.5 MPa for 30 minutes, and further at 23 ° C. and 50% RH. After leaving it for 24 hours in the atmosphere of, using a universal tensile compression tester, the peel strength (adhesive strength) [adhesive strength) under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 degrees according to JIS Z 0237: 2000. N / 25 mm] was measured. As the universal tensile compression tester, a "tensile compression tester, TG-1kN" manufactured by Minebea Co., Ltd. was used.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 表1,2に示す例1~13,16の粘着シートは、1.570を超える高い屈折率を示し、かつ高い透明性を示した。また、表2に示されるように、粘着剤として実用的な剥離強度を示し、表面平滑性にも優れていた。同じ粘着剤組成物を用いた例3と例16との対比において、例16では光学歪みの評価においてより良好な結果が得られた。なお、表2には示していないが、例16の吸水率は0.2%であった。これらの粘着シート(基材レス粘着シート)を任意の光透過性部材に貼り合わせることにより、屈折率が1.570超であり、全光線透過率が86%以上であり、かつヘイズ値が3.0%以下である粘着剤層を光透過性部材上に有する粘着型光学フィルムを容易に作製することができる。 The adhesive sheets of Examples 1 to 13 and 16 shown in Tables 1 and 2 showed a high refractive index exceeding 1.570 and high transparency. Further, as shown in Table 2, it showed practical peel strength as an adhesive and was also excellent in surface smoothness. In comparison between Example 3 and Example 16 using the same pressure-sensitive adhesive composition, Example 16 gave better results in the evaluation of optical strain. Although not shown in Table 2, the water absorption rate of Example 16 was 0.2%. By attaching these adhesive sheets (base material-less adhesive sheets) to an arbitrary light-transmitting member, the refractive index is more than 1.570, the total light transmittance is 86% or more, and the haze value is 3. A pressure-sensitive optical film having a pressure-sensitive adhesive layer of 0.0% or less on a light-transmitting member can be easily produced.
 一方、高屈折率の無機粒子を配合することで屈折率を向上させた例15は、例1~13に比べて明らかに透明性に劣り(特に、ヘイズが著しく高く)、表2に示すように表面平滑性も低く、明らかな光学歪みも認められ、かつ粘着剤としての実用に適した粘着性能(剥離強度)を示さないものであった。 On the other hand, Example 15 in which the refractive index was improved by blending inorganic particles having a high refractive index was clearly inferior in transparency (particularly, the haze was remarkably high) as compared with Examples 1 to 13, as shown in Table 2. The surface smoothness was also low, obvious optical distortion was observed, and the adhesive performance (peeling strength) suitable for practical use as an adhesive was not exhibited.
<例17、18、23>
 モノマー成分の組成を表3に示すとおりとした他は例1と同様にして、例17、18、23の各例に係るアクリル系ポリマーの溶液を調製し、アクリル系粘着剤組成物を調製した。アクリル系粘着剤組成物C1に代えて各例に係るアクリル系粘着剤組成物をそれぞれ使用し、粘着剤層の厚さを25μmとした他は、例1における粘着シートの作製と同様にして、各例に係る粘着シートを作製した。
<Examples 17, 18, 23>
A solution of the acrylic polymer according to each of Examples 17, 18 and 23 was prepared in the same manner as in Example 1 except that the composition of the monomer component was as shown in Table 3, and an acrylic pressure-sensitive adhesive composition was prepared. .. The same as in the production of the pressure-sensitive adhesive sheet in Example 1, except that the acrylic pressure-sensitive adhesive composition according to each example was used instead of the acrylic pressure-sensitive adhesive composition C1 and the thickness of the pressure-sensitive adhesive layer was 25 μm. Adhesive sheets according to each example were produced.
 なお、表3に示すモノマー成分の組成において、「BZA」はベンジルアクリレート(大阪有機化学工業株式会社製、商品名「ビスコート#160」、屈折率(nD20):1.519、ホモポリマーのTg:6℃)を表し、「PEA」はフェノキシエチルアクリレート(大阪有機化学工業株式会社製、商品名「ビスコート#192」、屈折率(nD20):1.517、ホモポリマーのTg:2℃)、「P2H-A」はフェノキシジエチレングリコールアクリレート(共栄社化学株式会社製、商品名「ライトアクリレートP2H-A」、屈折率:1.510、ホモポリマーのTg:-35℃)を表し、HEMAは2-ヒドロキシエチルメタクリレート、CBAはエチルカルビトールアクリレートをそれぞれ表す。 In the composition of the monomer components shown in Table 3, "BZA" is benzyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscort # 160", refractive index (nD20): 1.519, homopolymer Tg: 6 ° C.), and "PEA" is phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat # 192", refractive index (nD20): 1.517, homopolymer Tg: 2 ° C.), " "P2HA" represents phenoxydiethylene glycol acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name "light acrylate P2HA", refractive index: 1.510, homopolymer Tg: -35 ° C.), and HEMA is 2-hydroxyethyl. Methacrylate and CBA represent ethyl carbitol acrylate, respectively.
<例19>
 モノマー成分の組成を表3に示すとおりとした他は例1と同様にして、本例に係るアクリル系ポリマーA19の溶液を調製した。アクリル系ポリマーA3の溶液に代えてアクリル系ポリマーA19の溶液を使用し、添加剤(HRO)として2,12-ジアリルオキシジナフトチオフェン(スガイ化学工業株式会社製、略号:2,12-DAODNT、屈折率:1.729)10phrを使用した他は例4と同様にして、本例に係るアクリル系粘着剤組成物を調製し、粘着シートを作製した。
<Example 19>
A solution of the acrylic polymer A19 according to this example was prepared in the same manner as in Example 1 except that the composition of the monomer components was as shown in Table 3. Using the solution of the acrylic polymer A19 in place of the solution of the acrylic polymer A3, additives (H RO) as 2,12- diallyloxymethyl Gina shift thiophene (Sugaikagakukogyo Co., abbreviation: 2,12-DAODNT , Refractive rate: 1.729) The acrylic pressure-sensitive adhesive composition according to this example was prepared in the same manner as in Example 4 except that 10 phr was used, and a pressure-sensitive adhesive sheet was prepared.
<例20~22>
 モノマー成分の組成を表3に示すとおりとした他は例1と同様にして、例20~22の各例に係るアクリル系ポリマーの溶液を調製した。アクリル系ポリマーA3の溶液に代えて各例に係るアクリル系ポリマーの溶液を使用し、添加剤(HRO)として6-エチルアクリレート-ジナフト[2,1-b:1’,2’-d]チオフェン(スガイ化学工業株式会社製の6-アクリロイルオキシエチルジナフトチオフェン、略号:6EDNTA、屈折率:1.722)20phrを使用した他は例4と同様にして、各例に係るアクリル系粘着剤組成物を調製し、粘着シートを作製した。
<Examples 20-22>
A solution of the acrylic polymer according to each of Examples 20 to 22 was prepared in the same manner as in Example 1 except that the composition of the monomer component was as shown in Table 3. Using a solution of acrylic polymer according to the example in place of the solution of the acrylic polymer A3, 6- acrylate as an additive (H RO) - dinaphtho [2,1-b: 1 ', 2'-d] The acrylic pressure-sensitive adhesive according to each example in the same manner as in Example 4 except that thiophene (6-acryloyloxyethyl dinaphthophene manufactured by Sugai Chemical Industry Co., Ltd., abbreviation: 6EDNTA, refractive index: 1.722) was used. The composition was prepared and an adhesive sheet was prepared.
 例17~23により得られた粘着シートを23℃、50%RHの環境に十分馴染ませた後、上述した「測定および評価(1)」と同様にして各項目の測定および評価を行った。結果を表3に示す。 After the adhesive sheets obtained in Examples 17 to 23 were sufficiently acclimatized to the environment of 23 ° C. and 50% RH, each item was measured and evaluated in the same manner as in the above-mentioned "Measurement and evaluation (1)". The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 表3に示す例17~23の粘着シートは、いずれも1.570を超える高い屈折率を示し、かつ高い透明性を示した。これらのうち、例23の粘着シートは、例17~22の粘着シートに比べて硬い感触であり、吸水率も高めであった。
 以上より、例1~14、例16、例17~23の粘着シート(粘着剤層からなる基材レス両面粘着シート)は、光学特性の低下を抑制しつつ高屈折率化されていることから、上記粘着剤層が光透過性部材上に積層された粘着型光学フィルムの形態で、光学部材(例えば、光の導波、集光、回折の少なくとも1つの機能を有する光学フィルム)の接合等の用途に適している。
The adhesive sheets of Examples 17 to 23 shown in Table 3 all showed a high refractive index exceeding 1.570 and high transparency. Of these, the pressure-sensitive adhesive sheet of Example 23 had a harder feel and a higher water absorption rate than the pressure-sensitive adhesive sheets of Examples 17 to 22.
From the above, the pressure-sensitive adhesive sheets of Examples 1 to 14, Examples 16, and Examples 17 to 23 (base-less double-sided pressure-sensitive adhesive sheets composed of an adhesive layer) have a high refractive index while suppressing deterioration of optical characteristics. In the form of an adhesive optical film in which the pressure-sensitive adhesive layer is laminated on a light-transmitting member, bonding of optical members (for example, an optical film having at least one function of waveguideing, condensing, and refracting light), etc. Suitable for applications.
 以上、本発明の具体例を詳細に説明したが、これらは例示にすぎず、請求の範囲を限定するものではない。請求の範囲に記載の技術には、以上に例示した具体例を様々に変形、変更したものが含まれる。 Although specific examples of the present invention have been described in detail above, these are merely examples and do not limit the scope of claims. The techniques described in the claims include various modifications and modifications of the specific examples illustrated above.
  1  粘着型光学フィルム
 10  粘着剤層
 10A 第1の表面(粘着面)
 10B 第2の表面
 20  光透過性部材
 20A 第1面
 20B 第2面(背面)
 30,31,32  剥離ライナー
 50  剥離ライナー付き粘着型光学フィルム
 70  光学部材(被着体)
100  光学積層体
1 Adhesive type optical film 10 Adhesive layer 10A First surface (adhesive surface)
10B Second surface 20 Light transmissive member 20A First surface 20B Second surface (back surface)
30, 31, 32 Release liner 50 Adhesive optical film with release liner 70 Optical member (adhesive body)
100 optical laminate

Claims (8)

  1.  光透過性部材と、該光透過性部材上に積層された粘着剤層と、を含む粘着型光学フィルムであって、
     前記粘着剤層により構成された粘着面を有し、
     前記粘着剤層は、屈折率が1.570超であり、全光線透過率が86%以上であり、かつヘイズ値が3.0%以下である、粘着型光学フィルム。
    An adhesive optical film comprising a light-transmitting member and an adhesive layer laminated on the light-transmitting member.
    It has an adhesive surface composed of the adhesive layer and has an adhesive surface.
    The pressure-sensitive adhesive layer is an adhesive-type optical film having a refractive index of more than 1.570, a total light transmittance of 86% or more, and a haze value of 3.0% or less.
  2.  前記粘着剤層は、厚さが5μm以上である、請求項1に記載の粘着型光学フィルム。 The pressure-sensitive optical film according to claim 1, wherein the pressure-sensitive adhesive layer has a thickness of 5 μm or more.
  3.  ガラス板に対する剥離強度が3N/25mm以上である、請求項1または2に記載の粘着型光学フィルム。 The adhesive optical film according to claim 1 or 2, wherein the peel strength with respect to the glass plate is 3 N / 25 mm or more.
  4.  前記粘着面は、算術平均粗さRaが100nm以下である、請求項1~3のいずれか一項に記載の粘着型光学フィルム。 The adhesive optical film according to any one of claims 1 to 3, wherein the adhesive surface has an arithmetic mean roughness Ra of 100 nm or less.
  5.  前記粘着剤層は、吸水率が1.0%以下である、請求項1~4のいずれか一項に記載の粘着型光学フィルム。 The pressure-sensitive optical film according to any one of claims 1 to 4, wherein the pressure-sensitive adhesive layer has a water absorption rate of 1.0% or less.
  6.  前記光透過性部材は樹脂フィルムである、請求項1~5のいずれか一項に記載の粘着型光学フィルム。 The adhesive optical film according to any one of claims 1 to 5, wherein the light transmissive member is a resin film.
  7.  前記光透過性部材は、偏光板、保護フィルムおよびカバーウィンドウ部材からなる群から選択される、請求項1~6のいずれか一項に記載の粘着型光学フィルム。 The adhesive optical film according to any one of claims 1 to 6, wherein the light transmissive member is selected from the group consisting of a polarizing plate, a protective film, and a cover window member.
  8.  請求項1~7のいずれか一項に記載の粘着型光学フィルムと、
     前記粘着型光学フィルムの粘着面上に配置された剥離ライナーと、
    を含む、剥離ライナー付き粘着型光学フィルム。

     
    The adhesive optical film according to any one of claims 1 to 7.
    A release liner arranged on the adhesive surface of the adhesive optical film,
    Adhesive optical film with release liner, including.

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