WO2021193718A1

WO2021193718A1 - Adhesive sheet and adhesive sheet with release liner

Info

Publication number: WO2021193718A1
Application number: PCT/JP2021/012255
Authority: WO
Inventors: 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: 2020-03-24
Filing date: 2021-03-24
Publication date: 2021-09-30
Also published as: TW202142660A; CN115380093A; KR20220153084A

Abstract

Provided is an adhesive sheet including an adhesive layer. The adhesive sheet has an adhesive surface constituted by 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

Adhesive sheet and adhesive sheet with release liner

The present invention relates to an adhesive sheet and an adhesive sheet with a release liner.
This application is filed on March 24, 2020, Japanese Patent Application No. 2020-052408, Japanese Patent Application No. 2020-166425, filed on September 30, 2020, and March 23, 2021. Priority is claimed under the Japanese patent application 2021-049058 filed, and the entire contents of those applications are incorporated herein by reference.

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.

Japanese Patent Application Publication No. 2014-169382 Japanese Patent Application Publication No. 2017-128732

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, there is no known adhesive sheet that has an adhesive layer that has both a refractive index exceeding 1.570 and good optical characteristics (transparency) suitable for optical applications and exhibits practical adhesive performance. Is the reality.

The present invention has been created in view of the above circumstances, and an object of the present invention is to provide an adhesive sheet having an adhesive layer having both a high refractive index and good optical characteristics. Another object of the present invention is to provide an adhesive sheet with a release liner including the adhesive sheet.

According to this specification, an adhesive sheet containing an adhesive layer and having an adhesive surface composed of the adhesive layer is provided. 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 pressure-sensitive adhesive sheet is useful as a high-refractive-index pressure-sensitive adhesive sheet suitable for optical applications by providing a highly transparent pressure-sensitive adhesive layer. Further, by attaching the adhesive surface of the pressure-sensitive adhesive sheet to the adherend, a pressure-sensitive adhesive layer having a high refractive index can be easily arranged on the adherend.

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.

The adhesive sheet according to some aspects has a peel strength (adhesive strength) of 3 N / 25 mm or more with respect to the glass plate. Having such adhesive strength is preferable from the viewpoint of bonding reliability with the adherend.

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 adhesive surface (such as an adhesive sheet arranged on the viewpoint side of the self-luminous element in a light emitting device), it is possible to suppress the occurrence of luminance unevenness due to the surface state of the adhesive layer. can.

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. As a result, it is possible to suppress the warpage of the pressure-sensitive adhesive sheet or the adherend to which the pressure-sensitive adhesive sheet is attached.

In some embodiments, the pressure-sensitive adhesive sheet is configured as a laminate containing the pressure-sensitive adhesive layer and a light-transmitting base material (for example, a resin film). By attaching the pressure-sensitive adhesive sheet having such a structure to the adherend, it is possible to easily form a structure in which the adherend and the light-transmitting base material are laminated via a pressure-sensitive adhesive layer having a high refractive index. can.

In some embodiments, the pressure-sensitive adhesive sheet is a double-sided adhesive pressure-sensitive adhesive sheet composed of the pressure-sensitive adhesive layer. The double-sided adhesive pressure-sensitive adhesive sheet composed of the pressure-sensitive adhesive layer has excellent flexibility because it does not have a non-peelable base material (supporting base material). According to the double-sided adhesive adhesive sheet having no non-peelable base material (hereinafter, also referred to as a base material-less double-sided pressure-sensitive adhesive sheet), a high-refractive-index adhesive layer can be easily installed on the adherend. It is possible to form a highly flexible bond between the adherend and another member via the adhesive sheet.

Further, according to this specification, an adhesive sheet with a release liner is provided, which includes any of the adhesive sheets disclosed herein and a release liner arranged on the adhesive surface of the adhesive sheet. The adhesive sheet disclosed here is manufactured, stored, distributed, processed, etc. in the form of an adhesive sheet with a release liner in which a release liner is arranged on the adhesive surface in this way, and is adhered before being attached to an adherend. It can be preferably used in a mode of peeling the release liner from the surface.

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.

It is sectional drawing which shows typically the structure of the pressure-sensitive adhesive sheet which concerns on one Embodiment. It is sectional drawing which shows typically the structure of the pressure-sensitive adhesive sheet which concerns on another embodiment. It is sectional drawing which shows typically the optical member with an adhesive sheet which attached the adhesive sheet which concerns on one Embodiment to an optical member.

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.

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.

<Structure example of adhesive sheet>
This specification provides a pressure-sensitive adhesive sheet having an pressure-sensitive surface composed of a pressure-sensitive adhesive layer. The pressure-sensitive adhesive sheet may be a pressure-sensitive adhesive sheet with a base material having a pressure-sensitive adhesive layer on one side or both sides of a non-peelable base material (supporting base material), and the pressure-sensitive adhesive layer is held by a release liner. It may be a base material-less pressure-sensitive adhesive sheet (that is, a pressure-sensitive adhesive sheet having no non-peelable base material, typically a pressure-sensitive adhesive sheet composed of a pressure-sensitive adhesive layer). The concept of the pressure-sensitive adhesive sheet as used herein may include what is called an pressure-sensitive adhesive tape, a pressure-sensitive adhesive label, a pressure-sensitive adhesive film, or the like. The pressure-sensitive adhesive sheet disclosed herein may be in the form of a roll or in the form of a single leaf. Alternatively, it may be an adhesive sheet in a form further processed into various shapes.

FIG. 1 shows an example of the configuration of the adhesive sheet disclosed here. The pressure-sensitive adhesive sheet 1 has a pressure-sensitive adhesive layer 10 in which the first surface 10A is a surface (adhesive surface) to be attached to an adherend, and a supporting base material laminated on the second surface 10B of the pressure-sensitive adhesive layer 10. 20 and is configured as a single-sided adhesive adhesive sheet (single-sided adhesive sheet). The second surface 10B of the pressure-sensitive adhesive layer 10 is bonded to the first surface (non-peelable surface) 20A of the support base material 20. As the support base material 20, for example, a plastic film such as a polyester film can be used. The support base material 20 may be, for example, an optical film such as a polarizing plate. The pressure-sensitive adhesive sheet 1 before use (before sticking to the adherend) has a peel-off liner 30 in which the pressure-sensitive adhesive surface 10A has at least a peelable surface (peeling surface) on the pressure-sensitive adhesive layer side, as shown in FIG. 1, for example. It may be in the form of an adhesive sheet 50 with a release liner protected by. Alternatively, the second surface 20B of the support base material 20 (the surface opposite to the first surface 20A and also referred to as the back surface) is a peeling surface, and the adhesive surface 10A abuts on the second surface 20B. The adhesive surface 10A may be protected by being wound or laminated as described above. 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 pressure-sensitive adhesive sheet disclosed here may be in the form of a base-less double-sided pressure-sensitive adhesive sheet composed of a pressure-sensitive adhesive layer. As shown in FIG. 2, the base material-less double-sided adhesive sheet 2 has a first surface (first adhesive surface) 10A and a second surface (second adhesive surface) 10B of the adhesive layer 10 before use. , At least the adhesive layer side may be a form protected by a

release liner

31 or 32 having a releaseable surface (release surface). Alternatively, the back surface of the release liner 31 (the surface opposite to the adhesive side) is the release surface, and the adhesive surface is wound or laminated so that the adhesive surface 10B abuts on the back surface of the release liner 31. 10A and 10B may be in a protected form. Such a base material-less double-sided pressure-sensitive adhesive sheet is, for example, a base material (preferably a light-transmitting base material, and an optical member such as an optical film) on at least one of the first pressure-sensitive adhesive surface and the second pressure-sensitive adhesive surface. Can be used by joining. The pressure-sensitive adhesive layer constituting the base-less double-sided pressure-sensitive adhesive sheet may have a single-layer structure similar to the pressure-sensitive adhesive layer 10 in the pressure-sensitive adhesive sheet 1 shown in FIG. It may have a laminated structure in which they are directly contacted and laminated.

The pressure-sensitive adhesive sheet disclosed herein can be a component of an optical member with a pressure-sensitive adhesive sheet in which an optical member is bonded to at least one surface of the pressure-sensitive adhesive layer. For example, the pressure-sensitive adhesive sheet 1 shown in FIG. 1 may be a component of the optical member 100 with a pressure-sensitive adhesive sheet to which the optical member 70 is bonded to the first surface 10A of the pressure-sensitive 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 pressure-sensitive adhesive sheet 1 shown in FIG. 1, when the supporting base material 20 is an optical member such as an optical film, the pressure-sensitive adhesive sheet 1 is a pressure-sensitive adhesive in which the optical member is bonded to the second surface 10B of the pressure-sensitive adhesive layer 10. It can be grasped as an optical member with a sheet.

Further, although not particularly shown, the pressure-sensitive adhesive sheet disclosed herein includes a support base material having a non-peelable first surface and a second surface, and a first pressure-sensitive adhesive layer is fixedly laminated on the first surface. It may be in the form of a double-sided adhesive pressure-sensitive adhesive sheet with a base material (double-sided pressure-sensitive adhesive sheet with a base material) in which a second pressure-sensitive adhesive layer is fixedly laminated on the second surface. As a configuration example of such a double-sided pressure-sensitive adhesive sheet with a base material, in the single-sided pressure-sensitive adhesive sheet 1 shown in FIG. The two pressure-sensitive adhesive layers are provided, and the second surface of the second pressure-sensitive adhesive layer is bonded to the second surface 20B of the support base material 20, and the first surface (with the second surface) of the second pressure-sensitive adhesive layer is bonded. The surface on the opposite side) is the second adhesive surface of the double-sided adhesive sheet with a base material. 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 pressure-sensitive adhesive sheet with a base material before use may be in a form in which the first pressure-sensitive adhesive surface and the second pressure-sensitive adhesive surface are protected by a release liner, similarly to the above-mentioned base material-less double-sided pressure-sensitive adhesive sheet.

<Characteristics of adhesive layer>
(Refractive index)
The pressure-sensitive adhesive sheet 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 adhesive sheet containing the pressure-sensitive adhesive can be provided.

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.).

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.

The adhesive sheet disclosed herein is a double-sided adhesive sheet having one surface as a first adhesive surface and the other surface as a second adhesive surface (base-less double-sided adhesive sheet and double-sided adhesive with a base material). Both of the sheets are included. Unless otherwise specified, the same shall apply hereinafter.) In the case of the form, at least the first adhesive surface may satisfy any of the above-mentioned refractive indexes, and the refractive index of the second adhesive surface is particularly high. Not 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 of the adhesive sheet and the refractive index n ₂ _{of the second adhesive surface, i.e. n 1-} n _2, is greater than, for example, 0.00. It may be 0.01 or more, 0.03 or more, 0.05 or more, 0.10 or more, 0.15 or more, 0.20 or more, 0.25 or more. good. The magnitude relationship between n ₁ and n _{2 may be reversed.} The double-sided pressure-sensitive adhesive sheets having different refractive indices from the first adhesive surface and the second adhesive surface are, for example, the first and second adhesive layers having different refractive indices from each other on the non-peelable supporting base material in the double-sided pressure-sensitive adhesive sheet with a base material. Or a base-less double-sided adhesive sheet having a laminated structure of two or more sub-adhesive layers, and the refractive index of the adhesive constituting the first adhesive surface and the adhesive constituting the second adhesive surface in the laminated structure. This can be achieved by making the refractive index of the agent different from each other.

(Total light transmittance)
The pressure-sensitive adhesive sheet 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 pressure-sensitive adhesive sheet having a highly transparent pressure-sensitive adhesive layer as described above can be used for applications where high light transmission is required (for example, optical applications) in a configuration having or not having a base material, or an adherend through the pressure-sensitive adhesive sheet. It can be preferably applied to applications that require good visible performance. 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.

When the pressure-sensitive adhesive sheet disclosed herein is in the form of a double-sided pressure-sensitive adhesive sheet with a base material in which a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer are fixedly laminated on a supporting base material, at least the first pressure-sensitive adhesive layer is Any of the above-mentioned total light transmittances may be satisfied, and the total light transmittance 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 pressure-sensitive adhesive sheet, it is preferable that the total light transmittance of the second pressure-sensitive adhesive layer satisfies any of the total light transmittance 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.

(Haze value)
The pressure-sensitive adhesive sheet 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, and even more preferably 0.9% or less. The pressure-sensitive adhesive sheet having a highly transparent pressure-sensitive adhesive layer as described above can be used for applications where high light transmission is required (for example, optical applications) in a configuration having or not having a base material, or an adherend through the pressure-sensitive adhesive sheet. It can be preferably applied to applications that require good visible performance. In some embodiments, the haze value of the pressure-sensitive adhesive layer 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. These haze values for the pressure-sensitive adhesive layer are the haze values of the pressure-sensitive adhesive sheet when the technique disclosed herein is carried out in the form of a base material-less pressure-sensitive adhesive sheet (typically, a pressure-sensitive adhesive sheet composed of a pressure-sensitive adhesive layer). Can also be preferably applied.

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.

When the pressure-sensitive adhesive sheet disclosed herein is in the form of a double-sided pressure-sensitive adhesive sheet with a base material in which a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer are fixedly laminated on a supporting base material, at least the first pressure-sensitive adhesive layer is Any of the above-mentioned haze values may be satisfied, 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 pressure-sensitive adhesive sheet, 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.

(Surface smoothness of adhesive surface)
In some aspects of the pressure-sensitive adhesive sheet disclosed herein, the pressure-sensitive surface of the pressure-sensitive adhesive sheet preferably has high surface smoothness.

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 adhesive surface (such as an adhesive sheet arranged on the viewpoint side of the self-luminous element in a light emitting device), the surface state of the adhesive layer can be adjusted. It is possible to exert the effect of suppressing the occurrence of brightness unevenness caused by it. 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. When the pressure-sensitive adhesive sheet disclosed herein is in the form of a double-sided pressure-sensitive adhesive sheet having a first pressure-sensitive adhesive surface and a second pressure-sensitive adhesive surface, at least the arithmetic mean roughness Ra of the first pressure-sensitive adhesive surface is limited to a predetermined value or less. It is preferable, and it is more preferable that the arithmetic mean roughness Ra of both adhesive surfaces is limited to a predetermined value or less. Since each adhesive surface of the double-sided adhesive sheet has high surface smoothness, it is possible to preferably realize adhesion having excellent optical homogeneity.

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 of the adhesive sheet may be, for example, about 10 nm or more, about 20 nm or more, and about 30 nm or more (for example, about 40 nm or more). But it may be. In the embodiment in which the adhesive sheet has the first adhesive surface and the 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 the same or different. May be.

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. When the pressure-sensitive adhesive sheet disclosed here is in the form of a double-sided pressure-sensitive adhesive sheet having a first pressure-sensitive adhesive surface and a second pressure-sensitive adhesive surface, at least the maximum height Rz of the first pressure-sensitive adhesive surface is limited to a predetermined value or less. It is preferable that the maximum height Rz of both adhesive surfaces is limited to a predetermined value or less. Since each adhesive surface of the double-sided adhesive sheet has high surface smoothness, it is possible to preferably realize adhesion having excellent optical homogeneity.

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 of the adhesive sheet 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. good. In the embodiment in which the adhesive sheet has 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 good.

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.

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.

(Water absorption rate)
In some aspects of the pressure-sensitive adhesive sheet disclosed herein, it is preferable that the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet 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 pressure-sensitive adhesive sheet or the cover to which the pressure-sensitive adhesive sheet is attached due to the discrepancy in the dimensional change between the pressure-sensitive adhesive layer and the layer adjacent to the pressure-sensitive adhesive layer (which may be a supporting base material, a release liner, an adherend, etc.). It is possible to suppress the warp of the body. 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 a pressure-sensitive adhesive sheet used for a member or product containing an element that dislikes water, such as an organic EL element.

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. When the pressure-sensitive adhesive sheet disclosed herein is in the form of a double-sided pressure-sensitive adhesive sheet with a base material having a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer, the water absorption rate of at least the first pressure-sensitive adhesive layer is limited to a predetermined value or less. Is preferable. 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. 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

(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 of the pressure-sensitive adhesive sheet (typically, the base material-less pressure-sensitive adhesive sheet) is also preferably in the range exemplified above. 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.

[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

When the pressure-sensitive adhesive sheet disclosed herein is in the form of a double-sided pressure-sensitive adhesive sheet having a first pressure-sensitive adhesive surface and a second pressure-sensitive adhesive surface, the above-mentioned gel fraction can be applied to at least the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive surface. , 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 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.

(Storage modulus G')
In the pressure-sensitive adhesive sheet 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. is the purpose of use and the mode of use. It is set appropriately according to the above, 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.

In the pressure-sensitive adhesive sheet 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 not particularly limited. For example, it can be less than 100 kPa. 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.

In some aspects of the pressure-sensitive adhesive sheets 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).

In some aspects of the pressure-sensitive adhesive sheet 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.

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

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). ..

The pressure-sensitive adhesive sheet disclosed herein includes a double-sided pressure-sensitive adhesive sheet having a first pressure-sensitive adhesive surface and a second pressure-sensitive adhesive surface (for example, a double-sided pressure-sensitive adhesive sheet with a base material having a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer, and a first pressure-sensitive adhesive surface. A substrate-less double-sided adhesive sheet in which the constituent sub-adhesive layer and the sub-adhesive layer constituting the second adhesive surface are laminated without interposing a non-adhesive substrate. The same applies to other similar descriptions.) In the form of, the above-mentioned storage elasticity G'(25), G'(50) and storage elasticity ratio are applied to at least the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive surface, and preferably the first pressure-sensitive adhesive surface. It is applied to both the pressure-sensitive adhesive layer constituting the above 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.

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.

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. ..
When the pressure-sensitive adhesive sheet disclosed herein is in the form of a double-sided pressure-sensitive adhesive sheet having a first pressure-sensitive adhesive surface and a second pressure-sensitive adhesive surface, the above-mentioned Tpeak of the pressure-sensitive adhesive is applied to at least the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive surface. It is preferable, 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.

<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.

Hereinafter, a pressure-sensitive adhesive layer composed of an acrylic pressure-sensitive adhesive, that is, a pressure-sensitive adhesive sheet having an acrylic-based pressure-sensitive adhesive layer will be mainly described, but the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet disclosed herein is composed of an acrylic pressure-sensitive adhesive. It is not intended to be limited to the ones.

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).

(Acrylic polymer (A))
The pressure-sensitive adhesive sheet 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. Can be preferably 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 adhesive sheet with less distortion and warpage.

(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.

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).

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.

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.

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.

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.

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.). 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.

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.

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.

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. 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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.).

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.

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.

_{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.

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.

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.

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). 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.

(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.

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).

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.

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.

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.

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. ..

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.

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.

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.

(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.

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.

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).

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.

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.

(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.

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.

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.

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.

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).

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).

(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.

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.

(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.). ℃).

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.

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.

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.

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.

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

(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.

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.

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.

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.

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.

(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.

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. 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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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} ) that does not have an ethylenically unsaturated group means that the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer containing the additive (H _RO ), the laminate containing the pressure-sensitive adhesive sheet, and the like are ethylenic. It is also preferable from the viewpoint of suppressing dimensional changes and deformations (warping, waviness, etc.) and occurrence of optical strain caused by the reaction of unsaturated groups.

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.

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.

(Therplastic material)
In some aspects of the pressure-sensitive adhesive sheets disclosed herein, the pressure-sensitive adhesive layer comprises, in addition to the base polymer as described above (eg, the acrylic polymer (A)), a plasticized material having a lower molecular weight than the base polymer. Can include. 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 adhesive sheet 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)).

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 the heat resistance performance of the pressure-sensitive adhesive sheet and the 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. 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.

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.

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.

(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.

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.

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.

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.

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).

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. 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.

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.

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.

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.

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.

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.

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.

(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 pressure-sensitive adhesive sheet disclosed herein, a refractive index improver as long as it satisfies the desired optical properties (total light transmittance, haze value) and does not significantly impair the properties as a pressure-sensitive adhesive. It may be acceptable to use inorganic particles as. 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. In embodiments using additives (H _RO), the amount of the inorganic particles, by weight, is preferably not more than 2 times the amount of the additive (H _RO), 1 times or less or 0. More preferably, it is 5 times or less.

(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.

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.

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.

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.

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.

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.

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.

(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.

(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.

(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.

The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 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 adhesive sheet disclosed here 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), it suppresses the warp of the pressure-sensitive adhesive sheet or the adherend to which the pressure-sensitive adhesive sheet is attached. 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 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 may be advantageous from the viewpoint of thinning the pressure-sensitive adhesive sheet that the thickness of the pressure-sensitive adhesive layer is not too large. 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 case of a pressure-sensitive adhesive sheet having a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer on the first and second surfaces of the base material, the thickness of the pressure-sensitive adhesive layer described above is at least the thickness of the first pressure-sensitive adhesive layer. Can be applied to. The thickness of the second pressure-sensitive adhesive layer can be selected from the same range. Further, in the base material-less double-sided pressure-sensitive adhesive sheet composed of the pressure-sensitive adhesive layer, the thickness of the pressure-sensitive adhesive layer is the thickness of the pressure-sensitive adhesive sheet.

(Peeling strength)
In some aspects of the pressure-sensitive adhesive sheet disclosed herein, it is appropriate and preferable that the peel strength of the pressure-sensitive adhesive sheet with respect to the glass plate is approximately 1.0 N / 25 mm or more (for example, 1.5 N / 25 mm or more). Is 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 / 25mm 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.

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 sheet 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 pressure-sensitive adhesive sheet disclosed herein is in the form of a double-sided pressure-sensitive adhesive sheet having a first pressure-sensitive adhesive surface and a second pressure-sensitive adhesive surface, in some embodiments, the above-mentioned peel strength is preferably applied to at least the first pressure-sensitive adhesive surface. , More preferably applied 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.

<Supporting base material>
The pressure-sensitive adhesive sheet according to some aspects may be in the form of a base-attached pressure-sensitive adhesive sheet having an pressure-sensitive adhesive layer on one or both sides of a supporting base material. The material of the supporting base material 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 sheet. Non-limiting examples of base materials that can be used include polyester films containing polyester as a main component such as polypropylene (PP) and ethylene-propylene copolymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene na. Polyester film containing polyester as the main component such as phthalate (PEN), plastic film such as polyvinyl chloride film containing polyvinyl chloride as the main component; foams such as polyurethane foam, polyethylene (PE) foam, and polychloroprene foam. Foam sheet; woven fabrics and non-woven fabrics made of various fibrous substances (natural fibers such as hemp and cotton, synthetic fibers such as polyester and vinylon, semi-synthetic fibers such as acetate, etc.) alone or in a blended manner; Papers such as Japanese paper, high-quality paper, kraft paper, and crepe paper; metal foils such as aluminum foil and copper foil; and the like can be mentioned. A base material having a composite structure of these may be used. Examples of such a composite base material include a base material having a structure in which a metal foil and the plastic film are laminated, a plastic base material reinforced with an inorganic fiber such as glass cloth, and the like.

In some embodiments, various film substrates can be preferably used. The film base material may be a porous base material such as a foam film or a non-woven fabric sheet, or may be a non-porous base material, and may be a porous layer and a non-porous layer. May be a base material having a laminated structure. In some embodiments, as the film base material, those containing an independently shape-maintainable (self-supporting or independent) resin film as a base film can be preferably used. 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).

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.

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). 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. A blended film or 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.

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 use of the pressure-sensitive adhesive sheet and the like.

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.

The base material may be substantially composed of such a base film. Alternatively, the base material 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 printing layer or a laminating layer for imparting a desired appearance to a base material, an antistatic layer, an undercoat layer, and a peeling layer. Such as a surface treatment layer.

In some embodiments, a light-transmitting base material (hereinafter, also referred to as a light-transmitting base material) can be preferably adopted as the supporting base material. This makes it possible to construct an adhesive sheet with a base material having light transmission. The total light transmittance of the light-transmitting substrate may be, for example, more than 50%, and may be 70% or more. In some preferred embodiments, the total light transmittance of the supporting substrate 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 base material is a resin film having light-transmitting property. The light-transmitting substrate may be an optical film.

The thickness of the base material is not particularly limited and can be selected according to the purpose and mode of use of the adhesive sheet. The thickness of the base material may be, for example, 500 μm or less, preferably 300 μm or less from the viewpoint of handleability and processability of the pressure-sensitive adhesive sheet, 150 μm or less, 100 μm or less, 50 μm or less, and 25 μm. It may be less than or equal to 10 μm or less. As the thickness of the base material becomes smaller, the ability to follow the surface shape of the adherend tends to improve. Further, from the viewpoint of handleability, processability and the like, the thickness of the base material may be, for example, 2 μm or more, 10 μm or more, or 25 μm or more.

If necessary, the surface of the base material on the side where the adhesive layer is laminated is subjected to corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and application of an undercoat agent (primer). Conventionally known surface treatments such as 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 base material. 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 substrate as needed include antistatic layer forming treatments, colored layer forming treatments, printing treatments and the like. These treatments can be applied alone or in combination.

When the pressure-sensitive adhesive sheet disclosed herein is in the form of a pressure-sensitive adhesive sheet with a base material, the thickness of the pressure-sensitive adhesive sheet may be, for example, 1000 μm or less, 350 μm or less, 200 μm or less, or 120 μm or less. It may be 75 μm or less, or 50 μm or less. The thickness of the pressure-sensitive adhesive sheet 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 sheet means the thickness of the portion to be attached to the adherend. For example, in the pressure-sensitive adhesive sheet 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 supporting base material, and does not include the thickness of the release liner 30. ..

<Adhesive sheet with release liner>
The pressure-sensitive adhesive sheet disclosed herein may take the form of a pressure-sensitive adhesive product in which the surface (adhesive surface) of the pressure-sensitive adhesive layer is brought into contact with the peel-off surface of the release liner. Therefore, the present specification provides an adhesive sheet (adhesive product) with a release liner including any of the adhesive sheets disclosed herein and a release liner having a release surface that abuts on the adhesive surface of the adhesive sheet. NS.

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.

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).

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.

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.

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).

In an adhesive sheet 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 adhesive surface and the other. The release liner (hereinafter, also referred to as the other release liner) arranged on the adhesive surface of the above may have the same material and composition, or may have a different material and composition. ..

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 sheet becomes smooth, and high surface smoothness is obtained on the adhesive surface after the release liner is removed. Easy to get rid of.

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).

(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 sheet with a release liner in which the release liner is arranged on the first adhesive surface and the second adhesive surface, both the adhesive surface side surfaces of both release liners satisfy any of the above-mentioned arithmetic mean roughness Ra. Is preferable. The arithmetic mean roughness Ra of the adhesive surface side surfaces of both release liners may be about the same or different.

(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 sheet 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 satisfy any of the above-mentioned maximum heights Rz. Is preferable. The maximum height Rz of the adhesive surface side surfaces of both release liners may be about the same or different.

(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.

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. 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).

<Use>
The pressure-sensitive adhesive sheet disclosed herein can be used by being attached 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 polymers, liquid crystal polymers, and carbon materials such as graphene, alumina, zirconia, titania, SiO ₂ , ITO (indium tin oxide), Metal oxides such as ATO (antimonated tin oxide) and their mixtures, nitrides such as aluminum nitride, silicon nitride, titanium nitride, gallium nitride, indium nitride and their composites, alkaline glass, non-alkali glass, quartz glass, hokei Examples thereof include inorganic materials such as acid glass and sapphire glass. The pressure-sensitive adhesive sheet disclosed herein can be used by being attached to a member (for example, an optical member) whose surface is at least made of the above material.

The pressure-sensitive adhesive sheet disclosed here can be used in a bonding mode that does not require a treatment of heating to a temperature higher than a temperature range of about room temperature (for example, 20 ° C. to 35 ° C.) after being bonded to an adherend. In addition, if it is permissible depending on the constituent material of the adhesive sheet (for example, the material of the base material) and the type of the adherend, after bonding to the adherend, at the time of bonding, and before bonding, The heat treatment may be performed at at least any timing. 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 may be appropriately set within an allowable range depending on the constituent material of the pressure-sensitive adhesive sheet and the type of the adherend, in consideration of the surface condition of the adherend and the like so as to obtain a desired effect. It can be, for example, 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 sheet is attached (in the case of a double-sided adhesive sheet, at least one adherend) may have light transmission. 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 pressure-sensitive adhesive sheet 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.

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.

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.

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 pressure-sensitive adhesive sheet 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 (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.

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.). 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.

The pressure-sensitive adhesive disclosed here 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 pressure-sensitive adhesive disclosed herein can be preferably used as a pressure-sensitive adhesive that can meet 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.

The pressure-sensitive adhesive sheet disclosed herein is preferably used in a mode in which it is attached to an adherend having a high refractive index (which may be a layer or a member having a high refractive index), and has an interfacial reflection with the adherend. It can be suppressed. As described above, the pressure-sensitive adhesive sheet 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.

Further, since the pressure-sensitive adhesive sheet disclosed herein is suitable for increasing the refractive index, it is preferable that the pressure-sensitive adhesive sheet is attached to a light-emitting layer such as an optical semiconductor (for example, a high-refraction light-emitting layer mainly composed of an inorganic material). Can be used. 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 adhesive sheet 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 pressure-sensitive adhesive sheet is preferably low in color. This can also be advantageous from the viewpoint of suppressing unintentional coloring caused by the pressure-sensitive adhesive sheet.

The adhesive disclosed herein is used in 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), a packing layer filled between the lens surface and the member, Etc., it can be preferably used. 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.

The mode in which the optical members are bonded using the pressure-sensitive adhesive sheet disclosed herein is not particularly limited, and examples thereof include (1) a mode in which the optical members are bonded to each other via the pressure-sensitive adhesive sheet disclosed here, and (2). ) The optical member may be attached to a member other than the optical member via the pressure-sensitive adhesive sheet disclosed here, or (3) the pressure-sensitive adhesive sheet disclosed here includes the optical member. The adhesive sheet may be attached to an optical member or a member other than the optical member. In the aspect of (3) above, the pressure-sensitive adhesive sheet including the optical member may be, for example, a pressure-sensitive adhesive sheet in which the support is an optical member (for example, an optical film). As described above, the pressure-sensitive adhesive sheet including the optical member as the support can also be grasped as a pressure-sensitive optical member (for example, a pressure-sensitive optical film). Further, when the pressure-sensitive adhesive sheet disclosed here is a type of pressure-sensitive adhesive sheet having a support and the above-mentioned functional film is used as the above-mentioned support, the pressure-sensitive adhesive sheet disclosed here is a functional film. It can also be grasped as a "adhesive type functional film" having an adhesive layer disclosed herein on at least one side.

From the above, according to the technique disclosed herein, a laminate including the pressure-sensitive adhesive sheet disclosed here and a member to which the pressure-sensitive adhesive sheet is attached is provided. The member to which the pressure-sensitive adhesive sheet is attached may have the refractive index of the adherend material described above. Further, the difference between the refractive index of the pressure-sensitive adhesive sheet and the refractive index of the member (refractive index difference) may be the difference in refractive index between the adherend and the pressure-sensitive adhesive sheet 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.

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], wherein the peel strength (adhesive strength) with respect to the glass plate is 3N / 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 laminate containing the pressure-sensitive adhesive layer and a light-transmitting base material.
[7] The pressure-sensitive adhesive sheet according to [6] above, wherein the light-transmitting base material 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.
[10] The pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet according to any one of the above [1] to [8].

[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] The pressure-sensitive adhesive composition according to any one of [11] to [18] above, which is used for forming the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet according to any one of [1] to [8] 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] 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.

Hereinafter, some examples of the present invention will be described, but the present invention is not intended to be limited to those shown in such specific examples. In the following description, "parts" and "%" representing the amount used and the content are based on weight unless otherwise specified.

<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.

(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.

(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.

<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.

<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.

<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.

<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.

<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.

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.

<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.

(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.

(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. The water absorption rate of Example 13 has not been measured.

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.

<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.

<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.

(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

(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.

(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.

The pressure-sensitive adhesive sheets of Examples 1 to 13 shown in Table 1 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%.
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.

<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.

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.

<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.

<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.

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.

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 adhesive sheets of Examples 1 to 13, Examples 16 and 17 to 23 (base-less double-sided adhesive sheets composed of an adhesive layer) have a high refractive index while suppressing deterioration of optical characteristics. , Suitable for applications such as bonding optical members (eg, optical films having at least one function of waveguideing, condensing, and diffracting light).

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, 2 Adhesive sheet 10 Adhesive layer 10A First surface (adhesive surface)
10B 2nd surface 20 Support base material 20A 1st surface 20B 2nd surface (back surface)
30, 31, 32 Peeling liner 50 Adhesive sheet with peeling liner 70 Optical member 100 Member with adhesive sheet

Claims

An adhesive sheet containing an adhesive layer,
It has an adhesive surface composed of the 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.
The pressure-sensitive adhesive sheet according to claim 1, wherein the pressure-sensitive adhesive layer has a thickness of 5 μm or more.
The adhesive sheet according to claim 1 or 2, wherein the peel strength with respect to the glass plate is 3 N / 25 mm or more.
The adhesive sheet according to any one of claims 1 to 3, wherein the adhesive surface has an arithmetic mean roughness Ra of 100 nm or less.
The pressure-sensitive adhesive sheet 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.
The pressure-sensitive adhesive sheet according to any one of claims 1 to 5, which is configured as a laminate containing the pressure-sensitive adhesive layer and a light-transmitting base material.
The pressure-sensitive adhesive sheet according to claim 6, wherein the light-transmitting base material is a resin film.
The pressure-sensitive adhesive sheet according to any one of claims 1 to 5, which is a double-sided adhesive pressure-sensitive adhesive sheet composed of the pressure-sensitive adhesive layer.
The adhesive sheet according to any one of claims 1 to 8 and the adhesive sheet.
With a release liner arranged on the adhesive surface of the adhesive sheet,
Adhesive sheet with release liner, including.