WO2018110447A1 - 光学積層体 - Google Patents

光学積層体 Download PDF

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Publication number
WO2018110447A1
WO2018110447A1 PCT/JP2017/044181 JP2017044181W WO2018110447A1 WO 2018110447 A1 WO2018110447 A1 WO 2018110447A1 JP 2017044181 W JP2017044181 W JP 2017044181W WO 2018110447 A1 WO2018110447 A1 WO 2018110447A1
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WO
WIPO (PCT)
Prior art keywords
hard coat
resin film
coat layer
layer
meth
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PCT/JP2017/044181
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English (en)
French (fr)
Japanese (ja)
Inventor
康隆 石原
岸　敦史
貴之 足立
正紀 二宮
Original Assignee
日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020197016590A priority Critical patent/KR102342375B1/ko
Priority to KR1020217011570A priority patent/KR20210046838A/ko
Priority to CN201780077092.5A priority patent/CN110073248B/zh
Publication of WO2018110447A1 publication Critical patent/WO2018110447A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Definitions

  • the present invention relates to an optical laminate.
  • Image display devices such as liquid crystal display (LCD), cathode ray tube display device (CRT), plasma display (PDP), electroluminescence display (ELD), etc. are visible when the surface is damaged by external contact. May decrease. For this reason, an optical laminate including a base film and a hard coat layer is used for the purpose of protecting the surface of the image display device.
  • the base film of the optical laminate typically, triacetyl cellulose (TAC) is used.
  • TAC triacetyl cellulose
  • the base film made of TAC has high moisture permeability. Therefore, when an optical laminate including such a substrate film is used in an LCD, moisture is transmitted through the optical laminate under high temperature and high humidity, resulting in a problem that the optical characteristics of the polarizer are deteriorated.
  • LCDs are also frequently used for outdoor use devices such as car navigation systems and personal digital assistants. Even under severe conditions such as high temperature and high humidity, There is a need for a reliable LCD that does not cause problems.
  • Patent Document 1 an optical laminate in which a composition for forming a hard coat layer is applied to a low moisture permeability cycloolefin base film has been proposed.
  • a cycloolefin base film has a problem of poor adhesion to the hard coat layer.
  • the use of a (meth) acrylic resin film having low moisture permeability as a base material film has been studied.
  • the present invention has been made in order to solve the above-described conventional problems.
  • the object of the present invention is to provide excellent adhesion between the resin film (base film) and the hard coat layer, and scratches on the resin film.
  • An object of the present invention is to provide an optical layered body that is excellent in appearance without becoming apparent.
  • the optical layered body of the present invention includes a base material layer formed from a resin film, a hard coat layer formed by coating the resin film with a composition for forming a hard coat layer, the base material layer and the hard layer.
  • a refractive index of a molded article formed only from the composition for forming a hard coat layer, the composition for forming a hard coat layer formed between the coat layer and a penetration layer formed by penetrating the resin film.
  • the resin film includes an antiblock layer on one side.
  • a resin film after a pressure of 0.2 kgf / mm 2 to 1.0 kgf / mm 2 is applied in the thickness direction is used as the resin film.
  • a length of 4000 m or more and a roll-shaped resin film is used as the resin film.
  • the resin film has a portion having an arithmetic average surface roughness Ra of 10 nm or more.
  • a base layer and a hard coat layer formed by applying a hard coat layer forming composition on a resin film (base film), and a hard coat layer forming composition on a resin film are provided.
  • an infiltration layer formed by infiltration by appropriately controlling the degree of infiltration of the composition for forming a hard coat layer, excellent adhesion between the resin film (base film) and the hard coat layer, and An optical laminate having an excellent appearance can be obtained without causing scratches on the resin film.
  • an optical laminate that is significantly less affected by the scratches and excellent in appearance can be obtained.
  • (A) is a schematic sectional drawing of the optical laminated body by preferable embodiment of this invention
  • (b) is an example of the schematic sectional drawing of the optical laminated body which has the conventional general hard-coat layer.
  • FIG. 1A is a schematic cross-sectional view of an optical laminate according to a preferred embodiment of the present invention
  • FIG. 1B is an optical laminate having a conventional general hard coat layer.
  • FIG. The optical laminated body 100 shown to Fig.1 (a) is equipped with the base material layer 10 formed from the resin film, the osmosis
  • the hard coat layer 30 is formed by applying a composition for forming a hard coat layer to a resin film.
  • the osmotic layer 20 is formed by osmosis
  • the osmotic layer 20 is a portion where a hard coat layer component is present in the resin film.
  • the base material layer 10 is a portion where the hard coat layer forming composition does not reach (penetrate) in the resin film when the hard coat layer forming composition penetrates into the resin film as described above.
  • the permeation layer is not formed in the optical laminated body 200 shown in FIG. 1B.
  • the boundary A shown in FIGS. 1A and 1B is a boundary defined by the hard coat layer forming composition coating surface of the resin film.
  • the boundary A is the boundary between the osmotic layer 20 and the hard coat layer 30 in the optical laminate 100, and the base layer 10 ′ (that is, a resin film) in the optical laminate 200 in which the osmotic layer is not formed. And the hard coat layer 30 ′.
  • the resin film component may be present in the hard coat layer by eluting the component forming the resin film (for example, resin; hereinafter, also simply referred to as resin film component) into the hard coat layer forming composition. .
  • the relationship between the refractive index R HC of the molded body formed only from the hard coat layer forming composition, the refractive index R sub of the resin film, and the refractive index R surface of the hard coat layer surface is expressed by the formula (1). It is represented by The refractive index is measured by a prism coupler method. 0.1 ⁇ (R HC ⁇ R surface ) / (R HC ⁇ R sub ) ⁇ 0.4 (1)
  • “Refractive index R HC of a molded body formed only from the hard coat layer forming composition” means that the resin film component is not eluted in the hard coat layer forming composition when the hard coat layer is formed. It corresponds to a hard coat layer.
  • the “refractive index R HC of a molded body formed only from the hard coat layer forming composition” is, for example, a molded body formed from only the hard coat layer forming composition as an evaluation molded body different from the optical laminate. And the refractive index of the molded body is measured.
  • the molded body formed only from the hard coat layer forming composition is formed, for example, by applying the hard coat layer forming composition onto a base film on which a compatible layer cannot be formed.
  • the refractive indexes R HC , R sub , and R surface preferably have a relationship of 0.15 ⁇ (R HC ⁇ R surface ) / (R HC ⁇ R sub ), more preferably 0.19 ⁇ (R HC More preferably, it has a relationship of -R surface ) / (R HC -R sub ).
  • the refractive index R surface of the hard coat layer surface is R HC ⁇ 0.1 ⁇ (R HC ⁇ R sub ) or less, preferably R HC ⁇ 0.15 ⁇ (R HC ⁇ R sub ) or less. More preferably, R HC ⁇ 0.19 ⁇ (R HC ⁇ R sub ) or less.
  • the resin film component is eluted in the composition for forming a hard coat layer, and a resin is contained in the hard coat layer. Film components may be present.
  • the refractive index R surface on the surface of the hard coat layer is decreased as compared with the “refractive index R HC of the molded body formed only from the hard coat layer forming composition”. If the hard coat layer is formed so that the degree of reduction is 0.1 ⁇ (R HC -R sub ) or more, an optical laminate excellent in appearance can be obtained without causing scratches on the resin film. . Such an effect is considered to be obtained when the permeation layer is formed into a uniform layer so as to alleviate unevenness caused by scratches on the resin film.
  • the refractive indexes R HC , R sub , and R surface have a relationship of (R HC -R surface ) / (R HC -R sub ) ⁇ 0.4.
  • the refractive indexes R HC , R sub , and R surface preferably have a relationship of (R HC ⁇ R surface ) / (R HC ⁇ R sub ) ⁇ 0.25, and (R HC ⁇ R surface ) More preferably, the relationship of / (R HC -R sub ) ⁇ 0.2 is satisfied.
  • the refractive index R surface of the hard coat layer surface is R HC ⁇ 0.4 ⁇ (R HC ⁇ R sub ) or more, preferably R HC ⁇ 0.25 ⁇ (R HC ⁇ R sub ) or more. More preferably, it is R HC ⁇ 0.2 ⁇ (R HC ⁇ R sub ) or more. If it is such a range, the optical laminated body excellent in an external appearance as mentioned above can be obtained, suppressing a abrasion-resistant fall.
  • the lower limit of the thickness of the permeation layer is 1.2 ⁇ m or more, preferably 2 ⁇ m or more, more preferably 2.2 ⁇ m or more.
  • the thickness of the osmotic layer is the thickness of the portion where the hard coat layer component is present in the resin film. Specifically, as shown in FIG. 1 (a), the hard coat layer component is present in the resin film. The distance between the boundary A and the boundary A between the existing part (penetrating layer) and the non-existing part (base material layer).
  • the thickness of the osmotic layer can be measured by reflection spectrum of the hard coat layer or observation with an electron microscope such as SEM or TEM. Details of the method for measuring the thickness of the osmotic layer based on the reflection spectrum will be described later as an evaluation method in Examples.
  • the present invention by forming a permeation layer having a thickness of 1.2 ⁇ m or more, an optical laminate having excellent adhesion between the resin film and the hard coat layer and suppressing interference unevenness can be obtained. it can.
  • the present invention even when a material having a large refractive index difference is selected as the material for forming the resin film and the hard coat layer, the occurrence of interference unevenness can be prevented.
  • the absolute value of the difference between the refractive index of the base material layer (resin film) and the refractive index of the hard coat layer can be set to 0.01 to 0.15. Of course, it is also possible to set the absolute value of the difference in refractive index to less than 0.01.
  • the upper limit of the thickness of the osmotic layer 20 is defined by the thickness ratio between the osmotic layer and the hard coat layer (the thickness of the osmotic layer / the thickness of the hard coat layer). (Thickness of osmotic layer / thickness of hard coat layer) is 0.7 or less, preferably 0.65 or less, and more preferably 0.6 or less.
  • the thickness of the hard coat layer is the distance between the interface C (the air interface of the hard coat layer) and the boundary A shown in FIG.
  • the resin film component When forming the hard coat layer, if there are too many resin film components transferred to the hard coat layer forming composition, the resin film component may not be sufficiently compatible with the hard coat layer forming composition.
  • the resin film component and the hard coat layer forming composition are formed by forming the permeation layer and the hard coat layer so that the thickness of the permeation layer / the thickness of the hard coat layer is 0.7 or less. Thus, an optical laminate having an excellent appearance can be obtained without causing scratches on the resin film.
  • the amplitude of the reflection spectrum of the hard coat layer in the wavelength region of 500 nm to 600 nm of the optical layered body of the present invention is preferably 0.5% or less, more preferably 0.3% or less, and still more preferably 0.8. 1% or less. According to the present invention, it is possible to obtain an optical laminated body having a small reflection spectrum amplitude, that is, having little interference unevenness.
  • any appropriate other layer may be disposed outside the hard coat layer 30 as necessary.
  • the other layers are typically disposed via an adhesive layer (not shown).
  • the optical laminate of the present invention is applied to, for example, a polarizing film (also referred to as a polarizing plate).
  • a polarizing film also referred to as a polarizing plate.
  • the optical laminate of the present invention is provided on one or both sides of a polarizer in a polarizing film, and can be suitably used as a protective material for the polarizer.
  • the base material layer is formed of a resin film. More specifically, as described above, when the hard coat layer forming composition is applied to the resin film, the base layer reaches (penetrates) the hard coat layer forming composition in the resin film. This is the part that did not exist.
  • the thickness of the resin film is preferably 10 ⁇ m to 200 ⁇ m, more preferably 20 ⁇ m to 100 ⁇ m. There exists a possibility that intensity
  • the resin film has a portion having an arithmetic average surface roughness Ra (more specifically, an arithmetic average surface roughness Ra of the hard coat layer forming composition coating surface) of 10 nm or more. Preferably, it has a portion having an arithmetic average surface roughness Ra of 50 nm to 1000 nm. According to the present invention, even when a resin film having a scratch and having such an uneven surface is used, it is possible to prevent the appearance defect due to the scratch. In addition, it cannot be overemphasized that the resin film which does not have a damage
  • a long resin film is used as the resin film.
  • a long resin film is prepared in a roll shape, and an optical laminate is obtained by applying a hard coat layer forming composition onto a resin film fed out from the roll.
  • a length of 4000 m or more and a roll-shaped resin film is used.
  • the length of the resin film is increased.
  • the pressure inside the roll inside the roll
  • problems such as film breakage and winding slip are likely to occur.
  • the resin film in which the anti-blocking layer was formed may be used for productivity improvement and cost reduction (protection film-less).
  • a resin film after a pressure of 0.2 kgf / mm 2 to 1.0 kgf / mm 2 is applied in the thickness direction is used.
  • a resin film for example, an in-winding portion of a resin film wound up in a roll shape can be mentioned.
  • Resin films having such a load history often have visible scratches and / or non-visible scratches that cause poor appearance. In the present invention, even if such a resin film is used, the appearance is improved. An excellent optical laminate can be obtained.
  • an anti-blocking layer is formed on one side of the resin film.
  • the anti-blocking layer is formed by any appropriate method.
  • the resin film having the anti-block layer is prevented from blocking and can be formed into a long roll.
  • the resin film which has an anti-blocking layer can be used effectively.
  • the surface tension of the resin film is preferably 40 mN / m or more, more preferably 50 mN / m or more, and further preferably 55 mN / m or more.
  • the surface wetting tension is at least 40 mN / m or more, the adhesion between the resin film and the hard coat layer is further improved.
  • Any suitable surface treatment can be applied to adjust the surface wetting tension. Examples of the surface treatment include corona discharge treatment, plasma treatment, ozone spraying, ultraviolet irradiation, flame treatment, and chemical treatment. Of these, corona discharge treatment and plasma treatment are preferable.
  • the moisture permeability of the resin film is preferably 200 g / m 2 ⁇ 24 hr or less, and more preferably 80 g / m 2 ⁇ 24 hr or less.
  • the resin film having a low moisture permeability include (meth) acrylic resin films and cycloolefin resin films. According to the present invention, even when a (meth) acrylic resin film having a low moisture permeability is used, the adhesion between the (meth) acrylic resin film and the hard coat layer is excellent, and interference unevenness is suppressed. An optical laminate can be obtained.
  • the moisture permeability can be measured under the test conditions of 40 ° C. and a relative humidity of 92%, for example, by a method according to JIS Z 0208.
  • the light transmittance at a wavelength of 380 nm of the resin film is preferably 15% or less, more preferably 12% or less, and further preferably 9% or less. If the transmittance of light with a wavelength of 380 nm is a (meth) acrylic resin film in such a range, an excellent ultraviolet absorbing ability is exhibited, so that deterioration of ultraviolet rays due to external light or the like of the optical laminate can be prevented.
  • any appropriate material can be used as long as the effects of the present invention can be obtained.
  • a material constituting the resin film for example, a (meth) acrylic resin film is used.
  • the (meth) acrylic resin film is obtained, for example, by extruding a molding material containing a resin component containing a (meth) acrylic resin as a main component.
  • the in-plane retardation Re of the (meth) acrylic resin film is preferably 10 nm or less, more preferably 7 nm or less, still more preferably 5 nm or less, particularly preferably 3 nm or less, and most preferably 1 nm or less.
  • the thickness direction retardation Rth of the (meth) acrylic resin film is preferably 15 nm or less, more preferably 10 nm or less, further preferably 5 nm or less, particularly preferably 3 nm or less, and most preferably 1 nm. It is as follows. If the in-plane retardation and the thickness direction retardation are within such ranges, the adverse effect on the display characteristics of the image display apparatus due to the phase difference can be remarkably suppressed.
  • a (meth) acrylic resin film having in-plane retardation and thickness direction retardation in such a range can be obtained by using, for example, a (meth) acrylic resin having a glutarimide structure described later.
  • nx is the refractive index in the slow axis direction of the (meth) acrylic resin film
  • ny is the refractive index in the fast axis direction of the (meth) acrylic resin film
  • nz is the (meth) acrylic system.
  • the slow axis refers to the direction in which the in-plane refractive index is maximized
  • the fast axis refers to the direction perpendicular to the slow axis in the plane.
  • Re and Rth are measured using light having a wavelength of 590 nm.
  • any appropriate (meth) acrylic resin can be adopted as the (meth) acrylic resin.
  • poly (meth) acrylate such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester -(Meth) acrylic acid copolymer, (meth) acrylic acid methyl-styrene copolymer (MS resin, etc.), polymer having alicyclic hydrocarbon group (for example, methyl methacrylate-cyclohexyl methacrylate copolymer) And methyl methacrylate- (meth) acrylate norbornyl copolymer).
  • poly (meth) acrylate such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid
  • poly (meth) acrylate C 1-6 alkyl such as poly (meth) acrylate methyl is used. More preferred is a methyl methacrylate resin containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight).
  • the weight average molecular weight of the (meth) acrylic resin is preferably 10,000 to 500,000. If the weight average molecular weight is too small, the mechanical strength when formed into a film tends to be insufficient. When the weight average molecular weight is too large, the viscosity at the time of melt extrusion is high, the molding processability is lowered, and the productivity of the molded product tends to be lowered.
  • the glass transition temperature of the (meth) acrylic resin is preferably 110 ° C. or higher, more preferably 120 ° C. or higher. When the glass transition temperature is in such a range, a (meth) acrylic resin film excellent in durability and heat resistance can be obtained.
  • the upper limit of the glass transition temperature is not particularly limited, but is preferably 170 ° C. or less from the viewpoint of moldability and the like.
  • the (meth) acrylic resin preferably has a structural unit that exhibits positive birefringence and a structural unit that exhibits negative birefringence. If these structural units are included, the abundance ratio can be adjusted to control the retardation of the (meth) acrylic resin film, and a (meth) acrylic resin film having a low retardation can be obtained. it can.
  • the structural unit exhibiting positive birefringence include a structural unit constituting a lactone ring, polycarbonate, polyvinyl alcohol, cellulose acetate, polyester, polyarylate, polyimide, polyolefin, etc., and a general formula (1) described later. Examples include structural units.
  • Examples of the structural unit exhibiting negative birefringence include a structural unit derived from a styrene monomer, a maleimide monomer, a structural unit of polymethyl methacrylate, a structural unit represented by the general formula (3) described later, and the like. Can be mentioned.
  • a structural unit that exhibits positive birefringence is a case where a resin having only the structural unit exhibits positive birefringence characteristics (that is, a slow axis appears in the stretching direction of the resin). Means a structural unit.
  • a structural unit that develops negative birefringence is when a resin having only the structural unit exhibits negative birefringence characteristics (that is, when a slow axis appears in a direction perpendicular to the stretching direction of the resin).
  • a (meth) acrylic resin having a lactone ring structure or a glutarimide structure is preferably used as the (meth) acrylic resin.
  • a (meth) acrylic resin having a lactone ring structure or a glutarimide structure is excellent in heat resistance. More preferred is a (meth) acrylic resin having a glutarimide structure. If a (meth) acrylic resin having a glutarimide structure is used, a (meth) acrylic resin film having low moisture permeability and a small retardation and ultraviolet transmittance can be obtained as described above.
  • Examples of (meth) acrylic resins having a glutarimide structure include, for example, JP-A-2006-309033, JP-A-2006-317560, JP-A-2006-328329, and JP-A-2006-328329.
  • the glutarimide resin includes a structural unit represented by the following general formula (1) (hereinafter also referred to as a glutarimide unit) and a structural unit represented by the following general formula (2) (hereinafter referred to as (meta)). Also referred to as an acrylate unit).
  • R 1 and R 2 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms
  • R 3 is hydrogen, an alkyl group having 1 to 18 carbon atoms, or 3 to 3 carbon atoms.
  • 12 a cycloalkyl group or a substituent containing an aromatic ring having 5 to 15 carbon atoms.
  • R 4 and R 5 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms
  • R 6 is hydrogen, an alkyl group having 1 to 18 carbon atoms, or 3 to 3 carbon atoms.
  • 12 a cycloalkyl group or a substituent containing an aromatic ring having 5 to 15 carbon atoms.
  • the glutarimide resin may further contain a structural unit represented by the following general formula (3) (hereinafter also referred to as an aromatic vinyl unit) as necessary.
  • R 7 is hydrogen or an alkyl group having 1 to 8 carbon atoms
  • R 8 is an aryl group having 6 to 10 carbon atoms.
  • R 1 and R 2 are each independently hydrogen or a methyl group
  • R 3 is hydrogen, a methyl group, a butyl group, or a cyclohexyl group, and more preferably , R 1 is a methyl group, R 2 is hydrogen, and R 3 is a methyl group.
  • the glutarimide resin may include only a single type as a glutarimide unit, or may include a plurality of types in which R 1 , R 2 , and R 3 in the general formula (1) are different. Good.
  • the glutarimide unit can be formed by imidizing the (meth) acrylic acid ester unit represented by the general formula (2).
  • the glutarimide unit may be an acid anhydride such as maleic anhydride, or a half ester of such an acid anhydride and a linear or branched alcohol having 1 to 20 carbon atoms; acrylic acid, methacrylic acid, maleic acid It can also be formed by imidizing an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid such as maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid and citraconic acid.
  • R 4 and R 5 are each independently hydrogen or a methyl group
  • R 6 is hydrogen or a methyl group
  • R 4 is hydrogen
  • R 5 is a methyl group
  • R 6 is a methyl group
  • the glutarimide resin may contain only a single type as a (meth) acrylic acid ester unit, or a plurality of types in which R 4 , R 5 and R 6 in the general formula (2) are different. May be included.
  • the glutarimide resin preferably contains styrene, ⁇ -methylstyrene, and more preferably styrene as the aromatic vinyl unit represented by the general formula (3).
  • aromatic vinyl unit By having such an aromatic vinyl unit, the positive birefringence of the glutarimide structure can be reduced, and a (meth) acrylic resin film having a lower retardation can be obtained.
  • the glutarimide resin may contain only a single type as an aromatic vinyl unit, or may contain a plurality of types in which R 7 and R 8 are different.
  • the content of the glutarimide unit in the glutarimide resin is preferably changed depending on, for example, the structure of R 3 .
  • the content of the glutarimide unit is preferably 1% by weight to 80% by weight, more preferably 1% by weight to 70% by weight, even more preferably 1% by weight, based on the total structural unit of the glutarimide resin. -60% by weight, particularly preferably 1-50% by weight.
  • a (meth) acrylic resin film having a low retardation excellent in heat resistance can be obtained.
  • the content of the aromatic vinyl unit in the glutarimide resin can be appropriately set according to the purpose and desired characteristics. Depending on the application, the content of the aromatic vinyl unit may be zero.
  • the content thereof is preferably 10% by weight to 80% by weight, more preferably 20% by weight to 80% by weight, based on the glutarimide unit of the glutarimide resin. More preferably, it is 20% by weight to 60% by weight, and particularly preferably 20% by weight to 50% by weight.
  • a (meth) acrylic resin film having a low retardation, excellent heat resistance and mechanical strength can be obtained.
  • the glutarimide resin may be further copolymerized with other structural units other than the glutarimide unit, the (meth) acrylic acid ester unit, and the aromatic vinyl unit, if necessary.
  • other structural units include structures composed of nitrile monomers such as acrylonitrile and methacrylonitrile, and maleimide monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. Units are listed. These other structural units may be directly copolymerized or graft copolymerized in the glutarimide resin.
  • the (meth) acrylic resin film contains an ultraviolet absorber.
  • the ultraviolet absorber any appropriate ultraviolet absorber can be adopted as long as the desired characteristics are obtained.
  • Representative examples of the above UV absorbers include triazine UV absorbers, benzotriazole UV absorbers, benzophenone UV absorbers, cyanoacrylate UV absorbers, benzoxazine UV absorbers, and oxadiazole UV absorbers. Agents. These ultraviolet absorbers may be used alone or in combination.
  • the content of the ultraviolet absorber is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin. .
  • the content of the ultraviolet absorber is in such a range, ultraviolet rays can be absorbed effectively and the transparency of the film during film formation does not deteriorate.
  • the content of the ultraviolet absorber is less than 0.1 parts by weight, the ultraviolet blocking effect tends to be insufficient.
  • there is more content of a ultraviolet absorber than 5 weight part there exists a tendency for coloring to become intense or the haze of the film after shaping
  • the (meth) acrylic resin film may contain any appropriate additive depending on the purpose.
  • additives include hindered phenol-based, phosphorus-based and sulfur-based antioxidants; light-resistant stabilizers, weather-resistant stabilizers, heat stabilizers and other stabilizers; reinforcing materials such as glass fibers and carbon fibers; Infrared absorbers; flame retardants such as tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide; antistatic agents such as anionic, cationic and nonionic surfactants; coloring of inorganic pigments, organic pigments, dyes, etc.
  • organic fillers and inorganic fillers resin modifiers; organic fillers and inorganic fillers; plasticizers; lubricants; antistatic agents; flame retardants;
  • the kind, combination, content, and the like of the additive to be contained can be appropriately set according to the purpose and desired characteristics.
  • (meth) acrylic-type resin film Although it does not specifically limit as a manufacturing method of the said (meth) acrylic-type resin film,
  • (meth) acrylic-type resin, an ultraviolet absorber, and other polymers, additives, etc. as needed Can be sufficiently mixed by any appropriate mixing method to obtain a thermoplastic resin composition in advance, and then formed into a film.
  • a (meth) acrylic resin, an ultraviolet absorber, and if necessary, other polymers and additives are mixed in separate solutions to form a uniform mixed solution, and then film forming May be.
  • the film raw material is pre-blended with any suitable mixer such as an omni mixer, and then the obtained mixture is extruded and kneaded.
  • the mixer used for extrusion kneading is not particularly limited, and for example, any suitable mixer such as an extruder such as a single screw extruder or a twin screw extruder or a pressure kneader may be used. Can do.
  • the film forming method examples include any appropriate film forming methods such as a solution casting method (solution casting method), a melt extrusion method, a calendar method, and a compression molding method.
  • a melt extrusion method is preferred. Since the melt extrusion method does not use a solvent, it is possible to reduce the manufacturing cost and the burden on the global environment and work environment due to the solvent.
  • melt extrusion method examples include a T-die method and an inflation method.
  • the molding temperature is preferably 150 to 350 ° C, more preferably 200 to 300 ° C.
  • a T-die is attached to the tip of a known single-screw extruder or twin-screw extruder, and the film extruded into a film is wound to obtain a roll-shaped film Can do.
  • simultaneous biaxial stretching, sequential biaxial stretching, and the like can be performed by stretching the film in a direction perpendicular to the extrusion direction.
  • the (meth) acrylic resin film may be either an unstretched film or a stretched film as long as the desired retardation is obtained.
  • a stretched film either a uniaxially stretched film or a biaxially stretched film may be used.
  • a biaxially stretched film either a simultaneous biaxially stretched film or a sequential biaxially stretched film may be used.
  • the stretching temperature is preferably in the vicinity of the glass transition temperature of the thermoplastic resin composition which is a film raw material, and more preferably, (glass transition temperature ⁇ 30 ° C.) to (glass transition temperature + 30 ° C.) Preferably, it is within the range of (glass transition temperature ⁇ 20 ° C.) to (glass transition temperature + 20 ° C.). If the stretching temperature is less than (glass transition temperature ⁇ 30 ° C.), the haze of the resulting film may increase, or the film may be torn or cracked, resulting in failure to obtain a predetermined stretching ratio.
  • the stretching ratio is preferably 1.1 to 3 times, more preferably 1.3 to 2.5 times.
  • the mechanical properties such as the film elongation, tear propagation strength, and fatigue resistance can be greatly improved.
  • the above (meth) acrylic resin film can be subjected to a heat treatment (annealing) or the like after the stretching treatment in order to stabilize its optical isotropy and mechanical properties.
  • Arbitrary appropriate conditions can be employ
  • the penetration layer is formed by the penetration of the composition for forming a hard coat layer into the resin film as described above.
  • the osmotic layer can correspond to a part of the compatibilized region of the resin film component and the component forming the hard coat layer.
  • the concentration of the resin film component is preferably continuously increased from the hard coat layer side to the base material layer side. Interfacial reflection can be suppressed by the fact that the concentration of the resin film component changes continuously, that is, the interface resulting from the concentration change of the resin film component is not formed, and an optical laminate having little interference unevenness is obtained. Because you can.
  • the hard coat layer is formed by applying the composition for forming a hard coat layer on the resin film.
  • the composition for forming a hard coat layer includes, for example, a curable compound that can be cured by heat, light (such as ultraviolet rays), or an electron beam.
  • the composition for forming a hard coat layer contains a photocurable curable compound.
  • the curable compound may be any of a monomer, an oligomer and a prepolymer.
  • the formation state of the osmotic layer is controlled by the composition of the hard coat layer forming composition.
  • the composition for forming a hard coat layer preferably contains urethane (meth) acrylate and / or urethane (meth) acrylate oligomer as the curable compound. If the composition for forming a hard coat layer contains urethane (meth) acrylate and / or urethane (meth) acrylate oligomer, it is excellent in flexibility and adhesion to a resin film (preferably a (meth) acrylic resin film). A hard coat layer can be formed.
  • the urethane (meth) acrylate can be obtained, for example, by reacting hydroxy (meth) acrylate obtained from (meth) acrylic acid or (meth) acrylic acid ester and polyol with diisocyanate. Urethane (meth) acrylates and urethane (meth) acrylate oligomers may be used alone or in combination.
  • Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.
  • polyol examples include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1, 6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, neopentyl hydroxypivalate Glycol ester, tricyclodecane dimethylol, 1,4-cyclohexanediol, spiroglycol, hydrogenated bisphenol A, ethylene oxide added bisphenol A, propylene oxide added bisphenol A, trimethylol ethane, trimethylol Propane, glycerin, 3-methylpentane-1,3,5-triol, pentaeryth
  • diisocyanate for example, various aromatic, aliphatic or alicyclic diisocyanates can be used. Specific examples of the diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 4,4-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 3,3-dimethyl-4,4. -Diphenyl diisocyanate, xylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, and hydrogenated products thereof.
  • the molecular weight (theoretical molecular weight) of urethane (meth) acrylate and / or urethane (meth) acrylate oligomer is preferably 500 to 5000, more preferably 1000 to 4000.
  • the total content of the urethane (meth) acrylate and urethane (meth) acrylate oligomers is preferably 5 parts by weight with respect to 100 parts by weight of the total amount of monomers, oligomers and prepolymers in the hard coat layer forming composition.
  • the amount is less than 70 parts by weight, more preferably 10 to 60 parts by weight, still more preferably 20 to 50 parts by weight, and particularly preferably 30 to 50 parts by weight. If it is such a range, the optical laminated body with the favorable formation state of the osmosis
  • a hard coat layer having an excellent balance of hardness, flexibility and adhesion can be formed.
  • the hard coat layer forming composition preferably contains a curable compound having two or more (meth) acryloyl groups.
  • the upper limit of the number of (meth) acryloyl groups contained in the curable compound having two or more (meth) acryloyl groups is preferably 100. Since the curable compound having two or more (meth) acryloyl groups is excellent in compatibility with a resin film (preferably a (meth) acrylic resin film), it easily penetrates and diffuses into the resin film during coating.
  • curable compound having two or more (meth) acryloyl groups examples include tricyclodecane dimethanol diacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane triacrylate, Pentaerythritol tetra (meth) acrylate, dimethylolpropanthate tetraacrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol diacrylate, 1,10-decanediol (Meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, dipropylene glycol diacrylate, isocyanuric acid Examples include li (meth) acrylate, ethoxylated gly,
  • the curable compound having two or more (meth) acryloyl groups preferably has a hydroxyl group. If the composition for forming a hard coat layer contains such a curable compound, the heating temperature at the time of forming the hard coat layer can be set lower, the heating time can be set shorter, and deformation due to heating can be suppressed.
  • the produced optical laminate can be produced efficiently. Moreover, the optical laminated body which is excellent in the adhesiveness of a resin film (preferably (meth) acrylic-type resin film) and a hard-coat layer can be obtained.
  • the curable compound having a hydroxyl group and two or more (meth) acryloyl groups include pentaerythritol tri (meth) acrylate and dipentaerythritol pentaacrylate.
  • the content of the curable compound having two or more (meth) acryloyl groups is preferably 30 parts by weight with respect to 100 parts by weight of the total amount of the monomer, oligomer and prepolymer in the composition for forming a hard coat layer. More than 95 parts by weight, more preferably 40 parts by weight to 90 parts by weight, still more preferably 50 parts by weight to 80 parts by weight, and particularly preferably 50 parts by weight to 70 parts by weight. If it is such a range, the optical laminated body with the favorable formation state of the osmosis
  • a resin film preferably a (meth) acrylic resin film
  • the hard coat layer forming composition includes urethane (meth) acrylate and / or urethane (meth) acrylate oligomer and a curable compound having two or more (meth) acryloyl groups.
  • the compounding ratio (a: b, based on weight) of urethane (meth) acrylate and / or urethane (meth) acrylate oligomer a and curable compound b having two or more (meth) acryloyl groups is preferably 5 : 95 to 70:30, more preferably 10:90 to 60:40, still more preferably 20:80 to 50:50, and particularly preferably 30:70 to 50:50. If it is such a range, the optical laminated body with the favorable formation state of the osmosis
  • the hard coat layer forming composition may contain a monofunctional monomer as a curable compound.
  • the monofunctional monomer easily penetrates into the resin film. Therefore, if the monofunctional monomer is contained, an optical laminate having excellent adhesion between the resin film and the hard coat layer and suppressing interference unevenness can be obtained. Can do. Further, if the hard coat layer-forming composition contains a monofunctional monomer, the heating temperature at the time of forming the hard coat layer can be set low, the heating time can be set short, and the optical laminate in which deformation due to heating is suppressed. Can be produced efficiently.
  • the content ratio of the monofunctional monomer is preferably 40% by weight or less with respect to the total curable compound in the hard coat layer forming composition, More preferably, it is 30 weight% or less, Most preferably, it is 20 weight% or less. When the content ratio of the monofunctional monomer is more than 40% by weight, desired hardness and scratch resistance may not be obtained.
  • the weight average molecular weight of the monofunctional monomer is preferably 500 or less. With such a monofunctional monomer, it easily penetrates and diffuses into the resin film.
  • monofunctional monomers include ethoxylated o-phenylphenol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-ethylhexyl acrylate, lauryl acrylate, isooctyl acrylate, Isostearyl acrylate, cyclohexyl acrylate, isophoryl acrylate, benzyl acrylate, 2-hydroxy-3-phenoxy acrylate, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminopropylacrylamide, N- (2-hydroxyethyl) (meth) acrylamide and the like can be mentioned.
  • the monofunctional monomer preferably has a hydroxyl group.
  • the heating temperature at the time of forming the hard coat layer can be set lower, the heating time can be set shorter, and an optical laminate in which deformation due to heating is suppressed can be efficiently produced. it can.
  • the said composition for hard-coat layer formation contains the monofunctional monomer which has a hydroxyl group, the optical laminated body excellent in the adhesiveness of a resin film and a hard-coat layer can be obtained.
  • Examples of such monofunctional monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxy acrylate, 1,4 -Hydroxyalkyl (meth) acrylates such as cyclohexane methanol monoacrylate; N- (2-hydroxyalkyl) (meth) acrylamides such as N- (2-hydroxyethyl) (meth) acrylamide, N-methylol (meth) acrylamide, etc. Can be mentioned. Of these, 4-hydroxybutyl acrylate and N- (2-hydroxyethyl) acrylamide are preferable.
  • the boiling point of the monofunctional monomer is preferably higher than the heating temperature (described later) of the coating layer when forming the hard coat layer.
  • the boiling point of the monofunctional monomer is, for example, preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and particularly preferably 200 ° C. or higher. If it is such a range, it can prevent that a monofunctional monomer volatilizes by the heating at the time of hard-coat layer formation, and can make a monofunctional monomer fully osmose
  • the hard coat layer forming composition preferably contains any appropriate photopolymerization initiator.
  • the photopolymerization initiator include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, benzoinpropyl ether, benzyldimethyl Ketals, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, thioxanthone compounds, etc. Can be mentioned.
  • the surface of the hard coat layer opposite to the base material layer has an uneven structure. If the surface of the hard coat layer has a concavo-convex structure, antiglare properties can be imparted to the optical laminate.
  • Examples of a method for forming such a concavo-convex structure include a method in which fine particles are contained in the hard coat layer forming composition.
  • the fine particles may be inorganic fine particles or organic fine particles.
  • Examples of the inorganic fine particles include silicon oxide fine particles, titanium oxide fine particles, aluminum oxide fine particles, zinc oxide fine particles, tin oxide fine particles, calcium carbonate fine particles, barium sulfate fine particles, talc fine particles, kaolin fine particles, and calcium sulfate fine particles.
  • organic fine particles examples include polymethyl methacrylate resin powder (PMMA fine particles), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, and polyester resin powder. , Polyamide resin powder, polyimide resin powder, polyfluorinated ethylene resin powder, and the like. These fine particles may be used alone or in combination.
  • any appropriate shape can be adopted as the shape of the fine particles. It is preferably a substantially spherical shape, more preferably a substantially spherical shape having an aspect ratio of 1.5 or less.
  • the weight average particle diameter of the fine particles is preferably 1 ⁇ m to 30 ⁇ m, more preferably 2 ⁇ m to 20 ⁇ m.
  • the weight average particle diameter of the fine particles can be measured by, for example, a Coulter count method.
  • the content ratio of the fine particles is preferably 1% by weight to the total amount of the monomer, oligomer and prepolymer in the hard coat layer forming composition. 60% by weight, more preferably 2% to 50% by weight.
  • the hard coat layer forming composition may further contain any appropriate additive.
  • additives include leveling agents, anti-blocking agents, dispersion stabilizers, thixotropic agents, antioxidants, UV absorbers, antifoaming agents, thickeners, dispersants, surfactants, catalysts, fillers, and lubricants. And antistatic agents.
  • the leveling agent examples include a fluorine-based or silicone-based leveling agent, and a silicone-based leveling agent is preferable.
  • the silicone leveling agent examples include reactive silicone, polydimethylsiloxane, polyether-modified polydimethylsiloxane, and polymethylalkylsiloxane. Of these, reactive silicone is preferable. If reactive silicone is added, the surface of the hard coat layer is provided with slipperiness and the scratch resistance is maintained for a long period of time.
  • the content of the leveling agent is preferably 5% by weight or less, more preferably 0.01% by weight to 5% by weight with respect to the total amount of monomers, oligomers and prepolymers in the hard coat layer forming composition. %.
  • the hard coat layer forming composition may or may not contain a solvent.
  • the solvent include dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, acetone, methyl ethyl ketone (MEK).
  • a permeation layer having a desired thickness can be formed by penetrating into the resin film.
  • the thickness of the hard coat layer is preferably 1 ⁇ m to 20 ⁇ m, more preferably 3 ⁇ m to 10 ⁇ m.
  • the resin film component may be eluted in the hard coat layer forming composition, and the resin film component may be present in the hard coat layer.
  • the concentration of the resin film component is continuously reduced from the base material layer side of the osmotic layer to the hard coat layer.
  • the interface reflection can be suppressed by the fact that the concentration of the resin film component continuously changes, that is, the interface due to the concentration change of the resin film component is not formed. It is possible to obtain an optical layered body with less.
  • any appropriate other layer may be disposed outside the hard coat layer as necessary.
  • Typical examples include an antireflection layer and an antiglare layer.
  • an antireflection layer and an antiglare layer usually used in the art can be adopted.
  • the manufacturing method of the optical laminated body of this invention includes apply
  • the hard coat layer is formed by curing the coating layer after heating.
  • Arbitrary appropriate methods can be employ
  • examples thereof include a bar coating method, a roll coating method, a gravure coating method, a rod coating method, a slot orifice coating method, a curtain coating method, a fountain coating method, and a comma coating method.
  • the heating temperature of the coating layer can be set to an appropriate temperature according to the composition of the hard coat layer forming composition, and is preferably set to be equal to or lower than the glass transition temperature of the resin contained in the resin film. When heated at a temperature not higher than the glass transition temperature of the resin contained in the resin film, an optical laminate in which deformation due to heating is suppressed can be obtained. In one embodiment, the formation state of the penetration layer is controlled by the heating temperature of the coating layer.
  • the heating temperature of the coating layer is, for example, 80 ° C. to 140 ° C., preferably 85 ° C. to 100 ° C.
  • the monomer, oligomer and / or prepolymer in the composition for forming a hard coat layer penetrates and diffuses well into the resin film.
  • the penetration layer is formed by the hard coat layer forming composition and the resin film forming material that has penetrated through the heating and subsequent curing treatment.
  • an optical laminate having excellent adhesion between the resin film and the hard coat layer and suppressing interference unevenness can be obtained.
  • coated composition for hard-coat layer formation can be dried by the said heating.
  • the curing process is performed by ultraviolet irradiation.
  • the integrated light quantity of ultraviolet irradiation is preferably 200 mJ to 400 mJ.
  • the refractive index of the hard coat layer and the base film is measured by a method using a three-dimensional optical refractive index / film thickness measuring device prism coupler (product name: SPA-3DR, manufactured by Sairon Technology, Inc.). Can do.
  • a prism coupler introduces laser light into a thin film via a prism, and detects the state where the intensity of the introduced light increases with a certain periodicity (an angle that matches the thin-film waveguide conditions) at a specific incident angle.
  • the specific incident angle and its periodicity are uniquely determined from the refractive index and film thickness of the thin film.
  • the refractive index and film thickness of the thin film from the incident angle (called mode) can be calculated.
  • the incident angle and periodicity are deviated from the thin-film waveguide conditions. By doing so, the refractive index in the depth direction of the thin film can be obtained quantitatively.
  • the measurement of the refractive index was implemented and evaluated on the following conditions. Measurement conditions Light source: 632.8 nm Mode: TE Angle: -5.00 to 1.00 ⁇ R sub refractive index Analysis method: Bulk The mode (called Knee) was detected by measuring the substrate film.
  • the refractive index obtained by Bulk analysis was Rsbu.
  • ⁇ R HC refractive index Analysis method Single layer The refractive index of the hard coat layer was evaluated using the following laminate (R1). A plurality of modes were detected from the measurement of R1, and a single layer analysis was performed on this mode to calculate the refractive index and film thickness of the hard coat layer.
  • the refractive index obtained here was RHC .
  • ⁇ R surface Analysis method Index Profile
  • the refractive index of the resin film is measured in advance by the method using the above-mentioned prism coupler, and the depth at which the refractive index change in the depth direction is the same value as the refractive index of the resin film (hard coat layer + penetrating layer)
  • the thickness was evaluated. The measurement was performed under the following conditions. Measurement conditions Light source: 632.8 nm Mode: TE Angle: -5.00 to 1.00 Analysis mode: Index Profile
  • the thickness of the hard coat layer was evaluated by measuring the reflection spectrum of the laminate (R1) below.
  • the thickness of only the hard coat layer is measured from the peak position of the FFT spectrum obtained from the laminate (R1). .
  • a value calculated from (thickness of (hard coat layer + penetration layer)) ⁇ (thickness of (hard coat layer)) was taken as the thickness of the permeation layer. The measurement was carried out and evaluated under the following conditions.
  • Reflection spectrum measurement conditions Reference: Mirror Algorithm: FFT method Calculation wavelength: 450 nm to 850 nm ⁇ Detection conditions Exposure time: 20 ms Lamp gain: Normal Integration count: 10 times / FFT method Film thickness range: 2 to 15 ⁇ m Film thickness resolution: 24nm (3) Adhesion of hard coat layer Adhesion of the hard coat layer to the substrate film was evaluated according to a cross-cut peel test (number of cross-cuts: 100) of JIS K-5400, and judged by the following indices. .
  • polyester urethane (Daiichi Kogyo Seiyaku, trade name: Superflex 210)
  • crosslinking agent oxazoline-containing polymer, product of Nippon Shokubai, trade name: Epocross WS-700
  • ammonia water 0.3 parts by weight of ammonia water
  • colloidal silica trade name: Quartron PL-3, manufactured by Fuso Chemical Industries
  • an anti-blocking layer forming composition was prepared.
  • the obtained composition was applied to the corona discharge treated surface of the resin film a subjected to the corona discharge treatment so that the thickness after drying was 350 nm to form a coating layer, and the coating layer was formed at 140 ° C.
  • An anti-blocking layer was formed by drying for 5 minutes.
  • the base film A was obtained as described above.
  • the base film A thus obtained had a light transmittance of 8.5% at a wavelength of 380 nm, an in-plane retardation Re of 0.4 nm, and a thickness direction retardation Rth of 0.78 nm.
  • the moisture permeability of the obtained base film A was 61 g / m 2 ⁇ 24 hr.
  • the light transmittance was measured by measuring a transmittance spectrum in a wavelength range of 200 nm to 800 nm using a spectrophotometer (device name: U-4100) manufactured by Hitachi High-Tech Co., Ltd., and reading the transmittance at a wavelength of 380 nm. .
  • the phase difference value was measured at a wavelength of 590 nm and 23 ° C. using a trade name “KOBRA21-ADH” manufactured by Oji Scientific Instruments.
  • the moisture permeability was measured by a method according to JIS K 0208 under conditions of a temperature of 40 ° C. and a relative humidity of 92%.
  • scratching the hard coat coating surface of the base film by rubbing one side of the base film (the hard coat coating planned surface) and the other surface (the surface on which the anti-blocking layer is formed) Formed. Specifically, a base film is attached to a smooth cross section of a cylinder having a diameter of 25 mm so that the antiblocking layer is below, and the sample surface is reciprocated 10 times at a speed of about 100 mm per second with a load of 1.5 kg. Formed. A scratch having a maximum depth of 2000 nm was formed on the surface on which the scratch was formed.
  • the depth of the scratch was determined by applying a three-dimensional optical profiler NewView 7300 (manufactured by ZYGO) for a sample in which a glass plate (thickness: 1.3 ⁇ m) manufactured by MATUNAMI was bonded to the surface opposite to the scratch forming surface with an adhesive. Used to obtain surface shape data and obtained from the data.
  • urethane acrylic oligomer manufactured by Shin-Nakamura Chemical Co., Ltd., product name “UA53H”, molecular weight: 2300, 15 functional
  • PETA pentaerythritol triacrylate
  • 50 Part 50 parts of urethane acrylic oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd., product name “UA53H”, molecular weight: 2300, 15 functional) and pentaerythritol triacrylate (PETA) (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscote # 300) 50 Part, 5 parts of a leveling agent (manufactured by DIC, product name: GRANDIC PC-4100) and 3 parts of a photopolymerization initiator (manufactured by Ciba Japan, product name: Irgacure 907) are mixed at a solid content concentration of 50%.
  • a leveling agent manufactured by DIC, product name: GRANDIC PC-4
  • the hard coat layer forming composition was applied so that the thickness of the hard coat layer was 4.8 ⁇ m, and the coating layer was formed. After forming, the coating layer was heated at 95 ° C. for 1 minute. The coated layer after heating was irradiated with ultraviolet light having an accumulated light amount of 300 mJ / cm 2 with a high-pressure mercury lamp to cure the coated layer to form a base layer, a hard coat layer, and a penetrating layer, thereby obtaining an optical laminate. . This optical laminate was subjected to the evaluations (1) to (5) above. The results are shown in Table 1 below.
  • Example 2 An optical laminate was obtained in the same manner as in Example 1 except that the amount of urethane acrylic oligomer was 30 parts and the amount of PETA was 70 parts. This optical laminate was subjected to the evaluations (1) to (5) above. The results are shown in Table 1 below.
  • Example 3 The same as in Example 1 except that the hard coat layer thickness was 7 ⁇ m, the hard coat layer forming composition was applied to form a coating layer, and the coating layer was heated at 100 ° C. for 1 minute. Thus, an optical laminate was obtained. This optical laminate was subjected to the evaluations (1) to (5) above. The results are shown in Table 1 below.
  • the optical laminate of the present invention has excellent adhesion between the resin film (base film) and the hard coat layer by appropriately controlling the formation state of the permeation layer, and An optical laminate having an excellent appearance can be obtained without causing scratches on the resin film.
  • the optical layered body of the present invention can be suitably used for an image display device.
  • the optical layered body of the present invention can be suitably used as a front plate of an image display device or a protective material for a polarizer, and in particular, can be suitably used as a front plate of a liquid crystal display device.

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PCT/JP2017/044181 2016-12-13 2017-12-08 光学積層体 WO2018110447A1 (ja)

Priority Applications (3)

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