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CN110291167B - Adhesive composition for polarizing film, adhesive layer for polarizing film, polarizing film with adhesive layer, liquid crystal panel, and liquid crystal display device - Google Patents

Adhesive composition for polarizing film, adhesive layer for polarizing film, polarizing film with adhesive layer, liquid crystal panel, and liquid crystal display device Download PDF

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Publication number
CN110291167B
CN110291167B CN201880011246.5A CN201880011246A CN110291167B CN 110291167 B CN110291167 B CN 110291167B CN 201880011246 A CN201880011246 A CN 201880011246A CN 110291167 B CN110291167 B CN 110291167B
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polarizing film
adhesive layer
meth
adhesive composition
weight
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CN110291167A (en
Inventor
吉川贵博
中村恒三
森本有
加藤惠
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Nitto Denko Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)
  • Adhesive Tapes (AREA)
  • Liquid Crystal (AREA)
  • Optical Filters (AREA)

Abstract

The invention provides an adhesive composition for a polarizing film, which contains a (meth) acrylic polymer, a pigment, a radical generator and an antioxidant. The adhesive composition for a polarizing film of the present invention has good stability over time, and can maintain a wide color gamut due to a pigment.

Description

Adhesive composition for polarizing film, adhesive layer for polarizing film, polarizing film with adhesive layer, liquid crystal panel, and liquid crystal display device
Technical Field
The present invention relates to an adhesive composition for a polarizing film and an adhesive layer formed from the adhesive composition. The present invention also relates to an optical film with a pressure-sensitive adhesive layer, which has the pressure-sensitive adhesive layer formed on at least one surface of a polarizing film. The present invention also relates to a liquid crystal panel using the optical film with an adhesive layer, and a liquid crystal display device including the liquid crystal panel.
Background
In an image display device or the like, it is essential to dispose polarizing elements on both sides of a liquid crystal cell in view of an image forming method, and a polarizing film is generally bonded thereto. When the polarizing film is attached to the liquid crystal cell, an adhesive is generally used. In order to reduce the loss of light, the polarizing film and the liquid crystal cell are generally adhered to each other by using an adhesive. In this case, since there is an advantage that a drying process for fixing the polarizing film is not required, a polarizing film with a pressure-sensitive adhesive layer is generally used in which a pressure-sensitive adhesive is provided as a pressure-sensitive adhesive layer on one surface of the polarizing film in advance.
In addition, a liquid crystal display having a high contrast ratio has been proposed in which a dye or a pigment is added to the pressure-sensitive adhesive layer to impart an arbitrary color tone to a polarizing film for coloring (patent document 1). In recent years, brightness and vividness (i.e., a wide color gamut) have been demanded for image display devices, and organic EL display devices (OLEDs) have attracted attention, and a wide color gamut has also been demanded for liquid crystal display devices. For example, as a method for widening the color gamut of a liquid crystal display device, it has been proposed to laminate a polarizing film on one surface or both surfaces of the liquid crystal cell with an adhesive layer containing a dye exhibiting an absorption maximum wavelength in a specific wavelength range (560 to 610nm) (patent documents 2 and 3).
Documents of the prior art
Patent document
Patent document 1: japanese Doudenton specification No. 3052812
Patent document 2: japanese patent laid-open publication No. 2011-039093
Patent document 3: japanese patent laid-open publication No. 2014-092611
Disclosure of Invention
Problems to be solved by the invention
In general, as an adhesive composition for forming an adhesive layer for a polarizing film, an acrylic adhesive composition containing a (meth) acrylic polymer as a base polymer is used. In the above-mentioned acrylic pressure-sensitive adhesive composition, a pressure-sensitive adhesive layer crosslinked by radicals may be formed using a radical generator (e.g., a peroxide) as a crosslinking agent in addition to the (meth) acrylic polymer. In the case where the (meth) acrylic polymer in the acrylic pressure-sensitive adhesive composition is prepared by curing the monomer components by heat or radiation, a radical polymerization initiator is contained in the pressure-sensitive adhesive composition.
However, it is known that when a binder composition containing the radical generator further contains a coloring matter, the radical generator generates a radical, and the radical decomposes the coloring matter. As a result, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition gradually fades even if it is colored by a pigment at first. Thus, when the pigment in the adhesive layer deteriorates with time, it is difficult to maintain the wide color gamut by the pigment.
The purpose of the present invention is to provide an adhesive composition for a polarizing film, which contains a (meth) acrylic polymer, a coloring matter and a radical generator, has good stability over time, and can maintain a wide color gamut due to the coloring matter.
Further, the present invention is directed to a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition for a polarizing film, an optical film with a pressure-sensitive adhesive layer having the pressure-sensitive adhesive layer, a liquid crystal panel using the optical film with a pressure-sensitive adhesive layer, and a liquid crystal image display device using the liquid crystal panel.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems and, as a result, have found the following adhesive composition for polarizing films, thereby completing the present invention.
That is, the present invention relates to an adhesive composition for a polarizing film, which contains a (meth) acrylic polymer, a coloring matter, an antioxidant and a radical generator.
In the adhesive composition for a polarizing film, the dye having a maximum absorption wavelength in at least one wavelength range of 470 to 510nm and 570 to 610nm may be used.
In the pressure-sensitive adhesive composition for a polarizing film, a porphyrazine-based dye may be used as the dye.
The pressure-sensitive adhesive composition for a polarizing film preferably contains 0.01 to 5 parts by weight of the coloring matter per 100 parts by weight of the (meth) acrylic polymer.
In the pressure-sensitive adhesive composition for a polarizing film, a peroxide may be used as the radical generator.
The pressure-sensitive adhesive composition for a polarizing film preferably contains 0.01 to 2 parts by weight of the radical generator per 100 parts by weight of the (meth) acrylic polymer.
In the adhesive composition for a polarizing film, a phenolic antioxidant may be used as the antioxidant.
The pressure-sensitive adhesive composition for a polarizing film preferably contains 0.1 to 5 parts by weight of the antioxidant per 100 parts by weight of the (meth) acrylic polymer.
In the pressure-sensitive adhesive composition for polarizing films, the weight ratio (a/B) of the amount (a) of the radical generator to the amount (B) of the antioxidant is preferably 4 or less.
The adhesive composition for a polarizing film may further contain a crosslinking agent.
The present invention also relates to an adhesive layer for a polarizing film, which is formed from the adhesive composition for a polarizing film.
The gel fraction of the pressure-sensitive adhesive layer for a polarizing film is preferably 50 to 98 wt%.
When the thickness of the pressure-sensitive adhesive layer for a polarizing film is 20 μm, the absolute value of the difference (T1-T2) between the transmittance (T1) before storage at 85 ℃ for 500 hours and the transmittance (T2) after storage is preferably 50% or less.
The pressure-sensitive adhesive layer for a polarizing film according to any one of claims 11 to 13, wherein a ratio (T2/T1) of a transmittance (T2) after storage at 85 ℃ for 500 hours to a transmittance (T1) before storage is 2 or less in a case where the thickness of the pressure-sensitive adhesive layer for a polarizing film is 20 μm.
The present invention also relates to a polarizing film with a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer for a polarizing film is formed on at least one side of the polarizing film.
The present invention also relates to a liquid crystal panel, wherein the pressure-sensitive adhesive layer-attached polarizing film and the liquid crystal cell are bonded to each other through the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film on at least one surface of the liquid crystal cell.
The present invention also relates to a liquid crystal display device having the liquid crystal panel.
ADVANTAGEOUS EFFECTS OF INVENTION
The pressure-sensitive adhesive composition for a polarizing film of the present invention contains a pigment in addition to a (meth) acrylic polymer as a base polymer. By absorbing a part of the wavelength of light with the pigment, the color tone of the entire liquid crystal display device can be adjusted, and the brightness can be improved by widening the color range. In particular, the coloring matter having the maximum absorption wavelength in at least one of the wavelength ranges of 470 to 510nm and 570 to 610nm absorbs the unnecessary light emission expressed by the color in the wavelength range other than RGB (the wavelength ranges of 470 to 510nm and 570 to 610nm), thereby suppressing the unnecessary light emission and being effective for the wide color gamut.
The pressure-sensitive adhesive composition for a polarizing film of the present invention contains a radical generator such as a peroxide. The radical generator can function as a crosslinking agent for a (meth) acrylic polymer, for example, and can control the gel fraction of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition for a polarizing film to a desired range, thereby forming a pressure-sensitive adhesive layer having a good appearance.
As described above, since the pressure-sensitive adhesive composition for a polarizing film of the present invention contains both a coloring matter and a radical generator, there is a risk that the coloring matter may be discolored by radicals generated from the radical generator. However, when the adhesive composition for polarizing films of the present invention contains an antioxidant, the antioxidant can trap radicals, thereby suppressing discoloration (decomposition) of the pigment, and thus, the adhesive composition can stably maintain a wide color range over time.
Detailed Description
The adhesive composition for a polarizing film of the present invention contains a (meth) acrylic polymer, a coloring matter, an antioxidant, and a radical generator. These components are explained below.
[ meth (acrylic) Polymer ]
The pressure-sensitive adhesive composition for an optical film of the present invention contains a (meth) acrylic polymer as a base polymer as a main component. The main component is a component contained in the largest proportion in the total solid content of the adhesive composition, and for example, it means a component accounting for more than 50% by weight, more specifically, an ingredient accounting for more than 70% by weight of the total solid content of the adhesive composition.
Examples of the alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer include linear or branched alkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl group. They may be used alone or in combination. The average number of carbon atoms of these alkyl groups is preferably 3 to 9.
Examples of the alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer include linear or branched alkyl (meth) acrylates having an alkyl group of 1 to 18 carbon atoms. These alkyl groups may be used alone or in combination. The average number of carbon atoms of these alkyl groups is preferably 3 to 9.
In addition, from the viewpoint of adhesion characteristics, durability, adjustment of retardation, adjustment of refractive index, and the like, alkyl (meth) acrylates containing an aromatic ring such as phenoxyethyl (meth) acrylate and benzyl (meth) acrylate can be used.
In order to improve adhesiveness and heat resistance, 1 or more kinds of comonomers having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group may be introduced into the (meth) acrylic polymer by copolymerization. Specific examples of such comonomers include: hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl acrylate; carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; sulfonic acid group-containing monomers such as styrenesulfonic acid, allylsulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, and (meth) acryloyloxynaphthalenesulfonic acid; phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate, and the like.
Examples of the monomer for modification include: (N-substituted) amide monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide and N-methylol propane (meth) acrylamide; alkylaminoalkyl (meth) acrylate monomers such as aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; alkoxyalkyl (meth) acrylate monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; succinimide monomers such as N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxohexamethylene succinimide, N- (meth) acryloyl-8-oxooctamethylene succinimide, and N-acryloylmorpholine; maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide and N-phenylmaleimide; and itaconimide monomers such as N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexyl itaconimide, N-cyclohexylitaconimide, and N-laurylitaconimide.
Further, as the modifying monomer, vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyl group
Figure BDA0002161655300000051
Vinyl monomers such as oxazole, vinyl morpholine, N-vinylcarboxylic acid amides, styrene, alpha-methylstyrene, and N-vinylcaprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate(ii) a Glycol acrylate monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate; acrylic ester monomers such as tetrahydrofurfuryl (meth) acrylate, fluorine-containing (meth) acrylate, silicone (meth) acrylate, and 2-methoxyethyl acrylate. Mention may also be made of: isoprene, butadiene, isobutylene, vinyl ether, and the like.
Examples of the copolymerizable monomer other than those described above include silane-based monomers containing a silicon atom. Examples of the silane monomer include: 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloxydecyltrimethoxysilane, 10-acryloxydecyltrimethoxysilane, 10-methacryloxydecyltriethoxysilane, 10-acryloxydecyltriethoxysilane, and the like.
Further, as the comonomer, there may be used a polyfunctional monomer having 2 or more unsaturated double bonds such as 2 or more (meth) acryloyl groups and vinyl groups, such as an esterified product of a polyol and (meth) acrylic acid, such as tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, bisphenol a diglycidyl ether di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and a (meth) acryloyl group obtained by adding 2 or more functional groups, which are the same as those of the monomer component, to the skeleton of a polyester, epoxy, urethane, or the like, Polyester (meth) acrylates, epoxy (meth) acrylates, urethane (meth) acrylates, and the like obtained by unsaturated double bonds such as vinyl groups.
The (meth) acrylic polymer contains, as a main component, an alkyl (meth) acrylate in a weight ratio of all constituent monomers, and the proportion of the comonomer in the (meth) acrylic polymer is not particularly limited, and the proportion of the comonomer is preferably about 0 to 20%, preferably about 0.1 to 15%, and more preferably about 0.1 to 10% in a weight ratio of all constituent monomers.
Among these comonomers, a hydroxyl group-containing monomer and a carboxyl group-containing monomer are preferably used from the viewpoint of adhesiveness and durability. The hydroxyl group-containing monomer and the carboxyl group-containing monomer may be used in combination. These comonomers become reaction sites with the crosslinking agent when the adhesive composition contains the crosslinking agent. The hydroxyl group-containing monomer, carboxyl group-containing monomer, or the like is preferably used because it has a strong reactivity with the intermolecular crosslinking agent and can improve the cohesive property and heat resistance of the resulting pressure-sensitive adhesive layer. The hydroxyl group-containing monomer is preferable from the viewpoint of reworkability, and the carboxyl group-containing monomer is preferable from the viewpoint of compatibility between durability and reworkability.
When a hydroxyl group-containing monomer is contained as the comonomer, the proportion thereof is preferably 0.01 to 15% by weight, more preferably 0.03 to 10% by weight, and still more preferably 0.05 to 7% by weight. When a carboxyl group-containing monomer is contained as the comonomer, the proportion thereof is preferably 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, and still more preferably 0.2 to 6% by weight.
The (meth) acrylic polymer of the present invention is generally a polymer having a weight average molecular weight in the range of 50 to 300 ten thousand. In view of durability, particularly heat resistance, a polymer having a weight average molecular weight of 70 to 270 ten thousand is preferably used, and more preferably 80 to 250 ten thousand. When the weight average molecular weight is less than 50 ten thousand, it is not preferable from the viewpoint of heat resistance. When the weight average molecular weight is more than 300 ten thousand, a large amount of a diluting solvent is required to adjust the viscosity for coating, which is not preferable because the cost increases. The weight average molecular weight is a value calculated by GPC (gel permeation chromatography) measurement and polystyrene conversion.
Known production methods such as solution polymerization, radiation polymerization such as UV polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations can be appropriately selected for the production of such a (meth) acrylic polymer. The obtained (meth) acrylic polymer may be any copolymer such as a random copolymer, a block copolymer, or a graft copolymer.
In the solution polymerization, for example, ethyl acetate, toluene, or the like can be used as a polymerization solvent. As a specific example of the solution polymerization, a polymerization initiator is added to the reaction under an inert gas stream such as nitrogen, and the reaction is usually carried out at a temperature of about 50 to 70 ℃ for about 5 to 30 hours.
The polymerization initiator, chain transfer agent, emulsifier, and the like used in the radical polymerization are not particularly limited and may be appropriately selected and used. The weight average molecular weight of the (meth) acrylic polymer can be controlled by the amount of the polymerization initiator, the amount of the chain transfer agent, the reaction conditions, and the like, and the amount of the polymerization initiator, the amount of the chain transfer agent, the reaction conditions, and the like can be appropriately adjusted depending on the kind of the (meth) acrylic polymer.
Examples of the radical polymerization initiator include: 2,2 '-azobisisobutyronitrile, 2' -azobis (2-amidinopropane) dihydrochloride, 2 '-azobis [2- (5-methyl-2-imidazolin-2-yl) propane ] dihydrochloride, 2' -azobis (2-methylpropionamidine) disulfate, 2 '-azobis (N, N' -dimethyleneisobutylamidine), 2 '-azobis [ N- (2-carboxyethyl) -2-methylpropionamidine ] hydrate (manufactured by Wako pure chemical industries, Ltd., VA-057) and other azo initiators, potassium persulfate, persulfate such as ammonium persulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di (2-ethyl-2-methyl-2-amidinopropane) dihydrochloride, di (2-methyl-propionamidine) sulfate, di (2, 2-methyl-propionamidine) sulfate, 2' -azobis (2-methyl-propionamidine) disulfide, 2 '-azobis, 2' -azobis, and the like, Di-sec-butyl peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,3, 3-tetramethylbutyl peroxy2-ethylhexanoate, bis (4-methylbenzoyl) peroxide, dibenzoyl peroxide, tert-butyl peroxyisobutyrate, peroxide initiators such as 1, 1-di (tert-hexylperoxy) cyclohexane, tert-butyl hydroperoxide, and hydrogen peroxide, redox initiators comprising a combination of a peroxide such as a combination of a persulfate and sodium bisulfite, and a combination of a peroxide and sodium ascorbate, and a reducing agent, and the like, but the present invention is not limited thereto.
The radical polymerization initiator may be used alone or in combination of 2 or more, and the total content thereof is preferably about 0.005 to 1 part by weight, more preferably about 0.02 to 0.5 part by weight, based on 100 parts by weight of the monomer.
Examples of the chain transfer agent include: dodecyl mercaptan, glycidyl mercaptan, thioglycolic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2, 3-dimercapto-1-propanol, and the like. The chain transfer agent may be used alone or in combination of 2 or more, and the total content thereof is preferably about 0.1 part by weight or less based on 100 parts by weight of the total amount of the monomer components.
Examples of the emulsifier used in the emulsion polymerization include: anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate and sodium polyoxyethylene alkylphenyl ether sulfate, nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester and polyoxyethylene-polyoxypropylene block polymer, and the like. These emulsifiers may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Further, as the reactive emulsifier, emulsifiers having a radical polymerizable functional group such as an acryl group or an allyl ether group introduced thereto include, for example: AQUALON HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (all manufactured by first Industrial pharmaceutical Co., Ltd.), ADEKA REASOAP SE10N (manufactured by Asahi electro chemical Co., Ltd.), and the like. The reactive emulsifier is preferably incorporated into the polymer chain after polymerization, thereby improving water resistance. The amount of the emulsifier used is preferably 0.3 to 5 parts by weight, and more preferably 0.5 to 1 part by weight, based on 100 parts by weight of the total amount of the monomer components, from the viewpoint of polymerization stability and mechanical stability.
< coloring matter >
Various pigments can be used as the pigment to be blended in the adhesive composition of the present invention. Examples of the coloring agent include: porphyrins, cyanines, and azosMethylene pyrroles (pyrromethenes) and squaric acids
Figure BDA0002161655300000081
Various compounds such as (squarylium), xanthene, oxonol, squaraine and the like. The pigment is preferably a porphyrazine-based pigment, a porphyrin-based pigment, a cyanine-based pigment, or a squaraine dye from the viewpoint of widening the color range
Figure BDA0002161655300000082
The retinoid or squarylium cyanine dye is particularly preferably a porphyrazine retinoid. Specifically, the coloring matter is disclosed in Japanese patent laid-open publication No. 2011-116818 and the like. The above-mentioned coloring matters may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The dye preferably has a maximum absorption wavelength in at least one wavelength range of 470 to 510nm and 570 to 610 nm. The dye having the maximum absorption wavelength in the above wavelength range absorbs light unnecessary for color expression to suppress the light emission, and is effective for widening the color gamut. As the dye having the maximum absorption wavelength in the above wavelength range, a porphyrazine dye can be preferably used. For example, as the dye showing the maximum absorption wavelength in the wavelength range of 570 to 610nm, there can be mentioned, for example: tetraazaporphyrins (trade name: PD-320, PD311) manufactured by Shanghai chemical Co., Ltd, tetraazaporphyrins (trade name: FDG-007) manufactured by Shantian chemical industry Co., Ltd, and the like. The maximum absorption wavelength of the dye was measured by a spectrophotometer (V-570 manufactured by Nippon Kagaku Co., Ltd.).
The content of the coloring matter in the adhesive composition of the present invention may be adjusted depending on the absorption wavelength range, the light absorption coefficient, and the type of the (meth) acrylic polymer of the coloring matter, and is usually preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and still more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the (meth) acrylic polymer. In particular, when a porphyrazine dye is used, the above range is preferable.
< free radical generating agent >
Examples of the radical generator to be blended in the pressure-sensitive adhesive composition of the present invention include radical polymerization initiators used in the production of the above (meth) acrylic polymer. Among the radical polymerization initiators mentioned above, the radical generator to be blended in the adhesive composition is preferably a peroxide.
The radical generator can generate radical active species by heating or light irradiation to crosslink the (meth) acrylic polymer in the adhesive composition. The radical generator is preferably a peroxide having a 1-minute half-life temperature of 80 to 160 ℃ and more preferably a peroxide having a 1-minute half-life temperature of 90 to 140 ℃ in view of handling and stability.
Examples of the peroxide include: di (4-t-butylcyclohexyl) peroxydicarbonate (1-minute half-life temperature: 92.1 ℃ C.), di-sec-butyl peroxydicarbonate (1-minute half-life temperature: 92.4 ℃ C.), t-butyl peroxyneodecanoate (1-minute half-life temperature: 103.5 ℃ C.), t-hexyl peroxypivalate (1-minute half-life temperature: 109.1 ℃ C.), t-butyl peroxypivalate (1-minute half-life temperature: 110.3 ℃ C.), dilauroyl peroxide (1-minute half-life temperature: 116.4 ℃ C.), di-n-octanoyl peroxide (1-minute half-life temperature: 117.4 ℃ C.), 1,3, 3-tetramethylbutyl peroxy-2-ethylhexanoate (1-minute half-life temperature: 124.3 ℃ C.), di (4-methylbenzoyl) peroxide (1-minute half-life temperature: 128.2 ℃ C.), dibenzoyl peroxide (1-minute half-life temperature: 130.0 ℃ C.) T-butyl peroxyisobutyrate (1-minute half-life temperature: 136.1 ℃ C.), 1-bis (t-hexylperoxy) cyclohexane (1-minute half-life temperature: 149.2 ℃ C.), and the like. Among them, bis (4-t-butylcyclohexyl) peroxydicarbonate (1-minute half-life temperature: 92.1 ℃ C.), dilauroyl peroxide (1-minute half-life temperature: 116.4 ℃ C.), dibenzoyl peroxide (1-minute half-life temperature: 130.0 ℃ C.) and the like are preferably used, particularly, from the viewpoint of excellent crosslinking reaction efficiency.
The half-life of the peroxide is an index for the decomposition rate of the peroxide, and means the time until the residual amount of the peroxide becomes half. Regarding the decomposition temperature at which the half-life is obtained at an arbitrary time or the half-life time at an arbitrary temperature, it is described in a product catalog of manufacturers and the like, for example, in "catalog of organic peroxide products (anion カタログ) of japan grease corporation, version 9 (month 5 2003), and the like.
The content of the radical generator (particularly, peroxide) in the pressure-sensitive adhesive composition of the present invention can be determined in consideration of the gel fraction and the like in order to adjust the processability, reworkability, crosslinking stability, releasability and the like of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition. In general, the content of the radical generator is preferably 0.01 to 2 parts by weight, more preferably 0.04 to 1.5 parts by weight, and still more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the (meth) acrylic polymer.
In the above-mentioned (meth) acrylic polymer, a radical polymerization initiator (radical generator) that is not used in the polymerization reaction in the production of the (meth) acrylic polymer may remain in some cases. The residual radical generator can be used as a radical generator in the adhesive composition. In this case, the amount of the residual radical generating agent can be quantified, and the radical generating agent can be appropriately blended in accordance with the content of the residual radical generating agent.
The amount of peroxide decomposition remaining after the reaction treatment can be measured by, for example, HPLC (high performance liquid chromatography).
More specifically, for example, the adhesive composition after the reaction treatment may be taken out about 0.2g each time, immersed in 10mL of ethyl acetate, extracted with a shaker at 25 ℃ for 3 hours at 120rpm, and then allowed to stand at room temperature for 3 days. Subsequently, 10mL of acetonitrile was added, the mixture was shaken at 120rpm for 30 minutes at 25 ℃, and about 10. mu.L of the extract obtained by filtration through a membrane filter (0.45 μm) was injected into HPLC and analyzed as the amount of peroxide after the reaction treatment.
< antioxidant >
Examples of the antioxidant to be blended in the adhesive composition of the present invention include: at least one antioxidant selected from the group consisting of phenolic, phosphorus, sulfur and amine antioxidants is used. Among them, a phenol antioxidant is preferable.
Specific examples of the phenolic antioxidant include: 2, 6-di-t-butyl-p-cresol, 2, 6-di-t-butyl-4-ethylphenol, 2, 6-dicyclohexyl-4-methylphenol, 2, 6-diisopropyl-4-ethylphenol, 2, 6-di-t-amyl-4-methylphenol, 2, 6-di-t-octyl-4-n-propylphenol, 2, 6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, 2, 6-di-t-butyl-4-ethylphenol and the like as monocyclic phenol compounds, Styrenated mixed cresols, DL- α -tocopherol, β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid stearyl ester, and the like; 2,2 '-methylenebis (4-methyl-6-tert-butylphenol), 4' -butylidenebis (3-methyl-6-tert-butylphenol), 4 '-thiobis (3-methyl-6-tert-butylphenol), 2' -thiobis (4-methyl-6-tert-butylphenol), 4 '-methylenebis (2, 6-di-tert-butylphenol), 2' -methylenebis [6- (1-methylcyclohexyl) p-cresol ], 2 '-ethylenebis (4, 6-di-tert-butylphenol), 2' -butylidenebis (2-tert-butyl-4-methylphenol), 3, 6-dioxaoctamethylenebis [3- (3-tert-butyl-4-hydroxy- 5-methylphenyl) propionate ], triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2' -thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and the like; 1,1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3, 5-tris (2, 6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, 1,3, 5-tris [ (3, 5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl ] isocyanurate, tris (4-t-butyl-2, 6-dimethyl-3-hydroxybenzyl) isocyanurate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, and the like as the tricyclic phenol compound; tetrakis [ methylene-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] methane as a tetracyclophenol compound, and the like; calcium bis (ethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate) and nickel bis (ethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate) are examples of the phosphorus-containing phenol compound.
Specific examples of the phosphorus antioxidant include: trioctyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, triisodecyl phosphite, phenyldiisooctyl phosphite, phenyldiisodecyl phosphite, phenylditridecyl phosphite, diphenylisooctyl phosphite, diphenylisodecyl phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tris (butoxyethyl) phosphite, tetrakis (tridecyl) -4,4 ' -butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, 4 ' -isopropylidenediphenol alkyl phosphite (in which the number of carbon atoms in the alkyl group is about 12 to 15), 4 ' -isopropylidenebis (2-tert-butylphenyl) bis (nonylphenyl) phosphite, Tris (biphenyl) phosphite, tetrakis (tridecyl) -1,1, 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane bisphosphite, tris (3, 5-di-tert-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4, 4 ' -isopropylidenediphenyl phosphite, bis (octylphenyl) bis [4,4 ' -butylidenebis (3-methyl-6-tert-butylphenyl) ]1, 6-hexanediol bisphosphite, hexa (tridecyl) -1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) bisphosphite, tris [4,4 ' -isopropylidenebis (2-tert-butylphenyl) ] phosphite, and mixtures thereof, Tris (1, 3-distearoyloxyisopropyl) phosphite, 9, 10-dihydro-9-phosphaphenanthrene-10-oxide, tetrakis (2, 4-di-t-butylphenyl) -4,4 '-biphenylene diphosphonite, distearyl pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, phenyl 4, 4' -isopropylidenediphenol pentaerythritol diphosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, phenyl bisphenol-A-pentaerythritol diphosphite, and the like.
As the sulfur antioxidant, a dialkyl thiodipropionate and a polyol ester of an alkylthiopropionic acid are preferably used. The dialkyl thiodipropionate used herein is preferably a dialkyl thiodipropionate having an alkyl group having 6 to 20 carbon atoms, and the polyol ester of an alkylthiopropionic acid is preferably a polyol ester of an alkylthiopropionic acid having an alkyl group having 4 to 20 carbon atoms. In this case, examples of the polyol constituting the polyol ester include: glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate, and the like. Examples of such dialkyl thiodipropionate include: dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and the like. On the other hand, as the polyol ester of alkylthiopropionic acid, for example: glycerol tributylthiopropionate, glycerol trioctylthiopropionate, glycerol trilaurylthiopropionate, glycerol tristearylthiopropionate, trimethylolethane tributylthiopropionate, trimethylolethane trioctylthiopropionate, trimethylolethane trilaurylthiopropionate, trimethylolethane tristearylthiopropionate, pentaerythritol tetrabutylthiopropionate, pentaerythritol tetraoctylthiopropionate, pentaerythritol tetralaurylthiopropionate, pentaerythritol tetrastearylthiopropionate, and the like.
Specific examples of the amine antioxidant include: bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, polycondensates of dimethyl succinate with 1- (2-hydroxyethyl) -4-hydroxy-2, 2,6, 6-tetramethylpiperidineethanol, N ', N ", N '" -tetrakis- (4, 6-bis (butyl- (N-methyl-2, 2,6, 6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4, 7-diazacyclodecane-1, 10-diamine, dibutylamine-1, 3, 5-triazine-N, N ' -bis (2,2,6, 6-tetramethyl-4-piperidyl-1, 6-hexamethylenediamine with N- (2, polycondensates of 2,6, 6-tetramethyl-4-piperidyl) butylamine, poly [ {6- (1,1,3, 3-tetramethylbutyl) amino-1, 3, 5-triazine-2, 4-diyl } { (2,2,6, 6-tetramethyl-4-piperidyl) imino } hexamethylene { (2,2,6, 6-tetramethyl-4-piperidyl) imino } ], tetrakis (2,2,6, 6-tetramethyl-4-piperidyl) -1,2,3, 4-butane tetracarboxylic acid ester, 2,6, 6-tetramethyl-4-piperidyl benzoate, bis (1,2,6, 6-pentamethyl-4-piperidyl) -2- (3, 5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid Esters, bis (N-methyl-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, 1 ' - (1, 2-ethanediyl) bis (3,3,5, 5-tetramethylpiperazinone), (mixed 2,2,6, 6-tetramethyl-4-piperidyl/tridecyl) -1,2,3, 4-butanetetracarboxylate, (mixed 1,2,2,6, 6-pentamethyl-4-piperidyl/tridecyl) -1,2,3, 4-butanetetracarboxylate, mixed [2,2,6, 6-tetramethyl-4-piperidyl/β, β, β ', β ' -tetramethyl-3, 9- [2,4,8, 10-tetraoxaspiro (5,5) undecane ] diethyl ] -1,2,3, 4-butanetetracarboxylate, mixed [1,2,2,6, 6-pentamethyl-4-piperidinyl/β, β, β ', β ' -tetramethyl-3, 9- [2,4,8, 10-tetraoxaspiro (5,5) undecane ] diethyl ] -1,2,3, 4-butanetetracarboxylate, N ' -bis (3-aminopropyl) ethylenediamine-2, 4-bis [ N-butyl-N- (1,2,2,6, 6-pentamethyl-4-piperidinyl) amino ] -6-chloro-1, 3, 5-triazine condensate, poly [ 6-N-morpholino-1, 3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperidyl) imino ] hexamethylene [ (2,2,6, 6-tetramethyl-4-piperidyl) imide ], a condensate of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 1, 2-dibromoethane, [ N- (2,2,6, 6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6, 6-tetramethyl-4-piperidyl) imino ] propionamide, and the like.
The content of the antioxidant in the adhesive composition of the present invention is determined from the viewpoint of preventing color fading due to the above-mentioned radical generator. In general, the content of the antioxidant is preferably in the range of 0.1 part by weight or more based on 100 parts by weight of the (meth) acrylic polymer. On the other hand, if the content of the antioxidant is too large, the ratio of radicals generated from the radical generator is increased. As a result, crosslinking of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is easily inhibited, and the gel fraction of the pressure-sensitive adhesive layer is reduced, which tends to cause appearance defects. From this viewpoint, the content of the antioxidant is preferably 5 parts by weight or less, and more preferably 1.5 parts by weight or less, based on 100 parts by weight of the (meth) acrylic polymer. From the viewpoint of ensuring the gel fraction and preventing discoloration of the pigment, the content of the antioxidant is preferably 0.1 to 1.5 parts by weight, more preferably 0.2 to 1.0 part by weight, and still more preferably 0.3 to 0.8 part by weight, based on 100 parts by weight of the (meth) acrylic polymer.
In addition, from the viewpoint of ensuring the gel fraction of the pressure-sensitive adhesive layer and preventing discoloration of the pigment, the weight ratio (a/B) of the amount (a) of the radical generator to the amount (B) of the antioxidant is usually preferably 4 or less, more preferably 2 or less, and still more preferably 1.5 or less. On the other hand, the weight ratio (a/B) is usually preferably 0.01 or more, more preferably 0.05 or more, and further preferably designed to satisfy 0.1 or more.
< crosslinking agent >
In the present invention, the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer may contain a crosslinking agent (other than the radical generator). As the crosslinking agent, an organic crosslinking agent or a polyfunctional metal chelate compound can be used. Examples of the organic crosslinking agent include: isocyanate crosslinking agents, epoxy crosslinking agents, imine crosslinking agents, and the like. The multifunctional metal chelate is formed by covalent bonding or coordination bonding of polyvalent metal and organic compound. As the polyvalent metal atom, there may be mentioned: al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, etc. Examples of the atom in the covalently or coordinately bonded organic compound include an oxygen atom, and examples of the organic compound include: alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, ketone compounds, and the like.
The crosslinking agent is preferably an isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include: isocyanate monomers such as toluene diisocyanate, chlorophenylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane diisocyanate, isocyanate compounds obtained by adding these isocyanate monomers to trimethylolpropane, etc., isocyanurate compounds, biuret compounds, and urethane prepolymer type isocyanates obtained by subjecting polyether polyol, polyester polyol, acrylic polyol ester, polybutadiene polyol, polyisoprene polyol, and the like to addition reaction. Particularly preferred is a polyisocyanate compound such as one selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate and isophorone diisocyanate or a polyisocyanate compound derived therefrom. Here, the polyisocyanate compound selected from one or derived from hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate includes hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, polyol-modified hexamethylene diisocyanate, polyol-modified hydrogenated xylylene diisocyanate, trimer-type hydrogenated xylylene diisocyanate, and polyol-modified isophorone diisocyanate. The polyisocyanate compounds exemplified are particularly preferable because the reaction with hydroxyl groups proceeds rapidly by using an acid or a base contained in the polymer as a catalyst, and this contributes particularly to the acceleration of the crosslinking speed.
In the present invention, when an isocyanate-based crosslinking agent is used in combination as the crosslinking agent, inhibition of radical crosslinking by oxygen can be more effectively suppressed by the antioxidant, and a three-dimensional crosslinked network of the adhesive layer can be efficiently formed by the radical generator (e.g., peroxide). As a result, appearance abnormality at the end of the polarizing film can be more effectively prevented.
In the adhesive composition, the amount of the crosslinking agent is preferably 20 parts by weight or less, more preferably 0.01 to 20 parts by weight, and still more preferably 0.03 to 10 parts by weight, based on 100 parts by weight of the (meth) acrylic polymer. When the amount of the crosslinking agent is more than 20 parts by weight, the moisture resistance is insufficient, and peeling is likely to occur in a reliability test or the like.
The adhesive composition of the present invention may contain a silane coupling agent. By using the silane coupling agent, durability can be improved. Specific examples of the silane coupling agent include: (meth) acrylic-containing silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, as well as aminosilane-containing coupling agents such as 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethylbutylidene) propylamine and N-phenyl-gamma-aminopropyltrimethoxysilane, as well as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane, as well as (meth) acrylic-containing silane coupling agents, Isocyanate-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane, and the like.
The silane coupling agent may be used alone or in combination of 2 or more, and the total content thereof is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, even more preferably 0.02 to 1 part by weight, and even more preferably 0.05 to 0.6 part by weight, based on 100 parts by weight of the (meth) acrylic polymer. This is an amount to improve durability and appropriately maintain adhesion to an optical member such as a liquid crystal cell.
In the present invention, a polyether-modified silicone may be blended in the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer. Examples of the polyether-modified silicone include compounds disclosed in jp 2010-275522 a.
In the present invention, other known additives may be contained in the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer, and for example, powders such as coloring agents and pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, granules, foils, and the like may be added as appropriate depending on the application. In addition, redox species to which a reducing agent is added may be used within a controllable range.
When the pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition, it is preferable to adjust the amounts of the radical generator (e.g., peroxide) and the crosslinking agent to be added and to take the influences of the crosslinking temperature and the crosslinking time into consideration.
The crosslinking temperature and the crosslinking time can be adjusted depending on the crosslinking agent used. The crosslinking treatment temperature is preferably 170 ℃ or lower.
The crosslinking treatment may be performed at a temperature at the time of the drying step of the pressure-sensitive adhesive layer, or may be performed after the drying step by separately designing the crosslinking treatment step.
The crosslinking treatment time may be set in consideration of productivity and workability, but is usually about 0.2 to 20 minutes, preferably about 0.5 to 10 minutes.
In general, it is preferable to control the crosslinking so that the gel fraction of the pressure-sensitive adhesive layer is 50 wt% or more. From the viewpoint of high-temperature durability, the gel fraction of the pressure-sensitive adhesive layer is preferably controlled to 60% by weight or more. The gel fraction is preferably 75% by weight or more, and more preferably 80% by weight or more. On the other hand, if the gel fraction is too large, peeling is likely to occur in the durability test, and therefore, the gel fraction is preferably 98 wt% or less, and more preferably 95 wt% or less. The gel fraction was measured according to the method described in examples.
In addition, when the thickness of the pressure-sensitive adhesive layer is 20 μm, the absolute value of the difference (T1-T2) between the transmittance (T1) before storage at 85 ℃ for 500 hours and the transmittance (T2) after storage is preferably 50% or less, more preferably 40% or less, still more preferably 30% or less, still more preferably 10% or less, and most preferably 5% or less. In general, the value of (T1-T2) is a value of "-" due to discoloration of the dye. On the other hand, when the value is "+", it means that the color is not substantially faded.
The ratio (T2/T1) of the transmittance (T2) to the transmittance (T1) of the pressure-sensitive adhesive layer is preferably 2 or less, more preferably 1.5 or less, even more preferably 1.3 or less, even more preferably 1.2 or less, and even more preferably 1.1 or less. In general, the value of the ratio (T2/T1) is 1 or more due to fading of the pigment. On the other hand, when the value is less than 1, it means that the color is not substantially faded.
The polarizing film with an adhesive layer of the present invention has an adhesive layer formed from the adhesive composition on at least one side of the polarizing film.
As a method for forming the pressure-sensitive adhesive layer, the following method can be used: for example, a method in which the pressure-sensitive adhesive composition is applied to a separator or the like subjected to a peeling treatment, and then dried to remove a polymerization solvent or the like to form a pressure-sensitive adhesive layer, followed by transfer to a polarizing film; or a method of applying the pressure-sensitive adhesive composition to a polarizing film, and drying the composition to remove the polymerization solvent and the like to form a pressure-sensitive adhesive layer on the polarizing film. In the case of applying the adhesive, one or more solvents other than the polymerization solvent may be added newly as appropriate.
As the separator subjected to the peeling treatment, a silicone release liner can be preferably used. In the step of forming the pressure-sensitive adhesive layer by applying the adhesive composition of the present invention to such a liner and drying the applied adhesive composition, a suitable method can be appropriately employed as a method for drying the pressure-sensitive adhesive according to the purpose. The method of drying the coating film by heating is preferably used. The heating and drying temperature is preferably 40 to 200 ℃, more preferably 50 to 180 ℃, and particularly preferably 70 to 170 ℃. By setting the heating temperature in the above range, an adhesive having excellent adhesive characteristics can be obtained.
The drying time may be suitably employed as appropriate. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.
In addition, an adhesion promoting layer may be formed on the surface of the polarizing film, or an adhesive layer may be formed after various easy adhesion treatments such as corona treatment and plasma treatment. In addition, the surface of the pressure-sensitive adhesive layer may be subjected to an easy-adhesion treatment.
As a method for forming the pressure-sensitive adhesive layer, various methods can be employed. Specific examples thereof include: roll coating, roll and lick coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, blade coating, air knife coating, curtain coating, lip coating, extrusion coating using a die coater, and the like.
The thickness of the adhesive layer is not particularly limited, and is, for example, about 1 to 100. mu.m, preferably 2 to 50 μm, more preferably 2 to 40 μm, and still more preferably 5 to 35 μm.
In the case where the above adhesive layer is exposed, the adhesive layer may be protected with a sheet (separator) subjected to a peeling treatment until it is ready for practical use.
Examples of the constituent material of the separator include: plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabrics, and suitable sheets such as nets, foamed sheets, metal foils, and laminates thereof, are preferably used from the viewpoint of excellent surface smoothness.
The plastic film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and examples thereof include: polyethylene films, polypropylene films, polybutylene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films, polyethylene terephthalate films, polybutylene terephthalate films, polyurethane films, ethylene-vinyl acetate copolymer films, and the like.
The thickness of the separator is usually 5 to 200 μm, preferably about 5 to 100 μm. The separator may be subjected to release and anti-fouling treatment using a release agent such as silicone, fluorine-containing, long-chain alkyl or fatty acid amide, or silica powder, or subjected to antistatic treatment such as coating type, mixing type, or vapor deposition type, as required. In particular, the surface of the separator may be appropriately subjected to a release treatment such as a silicone treatment, a long-chain alkyl treatment, or a fluorine treatment, thereby further improving the releasability from the pressure-sensitive adhesive layer.
The pressure-sensitive adhesive layer-attached polarizing film of the present invention can be produced by a method of producing a pressure-sensitive adhesive layer-attached polarizing film, and a method of producing a pressure-sensitive adhesive layer-attached polarizing film.
As the polarizing film, a polarizing film having a transparent protective film on one surface or both surfaces of a polarizer is generally used.
The polarizer is not particularly limited, and various polarizers can be used. Examples of the polarizer include films obtained by uniaxially stretching hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene-vinyl acetate copolymer partially saponified films, and polyene oriented films such as polyvinyl alcohol dehydrated products and polyvinyl chloride desalted products, and the like. Among them, a polarizer made of a dichroic material such as a polyvinyl alcohol film and iodine is preferable. The thickness of these polarizers is not particularly limited, but is usually about 80 μm or less.
The polarizer obtained by uniaxially stretching the polyvinyl alcohol film dyed with iodine can be produced, for example, by dyeing the polyvinyl alcohol film by immersing it in an aqueous iodine solution and stretching it to 3 to 7 times the original length. The sheet may be immersed in an aqueous solution of potassium iodide or the like optionally containing boric acid, zinc sulfate, zinc chloride, or the like as necessary. Further, the polyvinyl alcohol film may be immersed in water and washed with water before dyeing, if necessary. By washing the polyvinyl alcohol film with water, it is possible to wash off dirt and an anti-blocking agent on the surface of the polyvinyl alcohol film, and also to swell the polyvinyl alcohol film and prevent unevenness such as uneven dyeing. The stretching may be performed after the dyeing with iodine, or may be performed while dyeing, or may be performed after the stretching with iodine. Stretching may be carried out in an aqueous solution or water bath of boric acid, potassium iodide, or the like.
Further, as the polarizer, a thin polarizer having a thickness of 10 μm or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizer is preferable in that it has excellent durability because of its small thickness unevenness, excellent visibility, and small dimensional change, and can be made thin as the thickness of the polarizing film.
Typical thin polarizers include thin polarizing films described in JP 51-069644 a, JP 2000-338329 a, WO2010/100917 a, and PCT/JP2010/001460 a, and also in JP 2010-269002 a and JP 2010-263692 a. These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol resin (hereinafter, also referred to as PVA-based resin) layer and a stretching resin base material in a state of a laminate, and a step of dyeing. With this production method, even if the PVA-based resin layer is thin, it can be stretched without causing troubles such as breakage due to stretching, because it is supported by the resin base material for stretching.
As the thin polarizing film, in a manufacturing method including a step of stretching in a state of a laminate and a step of dyeing, from the viewpoint of being capable of stretching at a high magnification to improve polarizing performance, thin polarizers obtained by a manufacturing method including a step of stretching in an aqueous boric acid solution as described in WO2010/100917 pamphlet, PCT/JP2010/001460 pamphlet, japanese patent application 2010-269002 pamphlet, and japanese patent application 2010-263692 pamphlet are preferable, and in particular, thin polarizers obtained by a manufacturing method including a step of stretching in an auxiliary gas atmosphere before stretching in an aqueous boric acid solution as described in japanese patent application 2010-269002 pamphlet and japanese patent application 2010-263692 pamphlet are preferable.
As a material constituting the transparent protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like can be used. Specific examples of such thermoplastic resins include cellulose resins such as cellulose triacetate, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, cyclic polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof. A transparent protective film may be bonded to one side of the polarizer via an adhesive layer, and a thermosetting resin or an ultraviolet-curable resin such as a (meth) acrylic resin, a urethane resin, an acrylic urethane resin, an epoxy resin, or a silicone resin may be used as the transparent protective film on the other side. The transparent protective film may contain 1 or more kinds of any suitable additives. Examples of the additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, coloring inhibitors, flame retardants, nucleating agents, antistatic agents, pigments, and coloring agents. The content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, even more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. When the content of the thermoplastic resin in the transparent protective film is 50 wt% or less, high transparency and the like originally possessed by the thermoplastic resin may not be sufficiently exhibited.
The thickness of the transparent protective film is not particularly limited as long as the total thickness of the polarizing film is 100 μm or less, and is, for example, about 10 to 90 μm, preferably 15 to 60 μm, and more preferably 20 to 50 μm.
The surface of the transparent protective film to which the polarizer is not bonded may be provided with a functional layer (surface layer) such as a hard coat layer, an antireflection layer, an antisticking layer, a diffusion layer, or an antiglare layer.
The adhesive used for bonding the polarizer and the transparent protective film is not particularly limited as long as it is optically transparent, and various types of adhesives such as aqueous, solvent, hot melt, radical curing, and cation curing adhesives can be used, and an aqueous adhesive or a radical curing adhesive is preferred.
< liquid Crystal Panel >
The polarizing film with an adhesive layer of the present invention is bonded to at least one surface of a liquid crystal cell via the adhesive layer of the polarizing film with an adhesive layer, thereby forming a liquid crystal panel. The polarizing film with an adhesive layer of the present invention can be preferably used for the viewing side of a liquid crystal cell.
The liquid crystal cell may be any type of liquid crystal cell such as TN type, STN type, pi type, VA type, IPS type, etc., and the liquid crystal panel of the present invention preferably uses an IPS mode liquid crystal cell.
In addition to the polarizing film, other optical layers may be used in the formation of the liquid crystal panel. The optical layer is not particularly limited, and for example, optical layers used for forming a liquid crystal panel such as 1 or 2 or more layers of a reflective sheet, a semi-transmissive sheet, a retardation sheet (including a wave plate such as 1/2 or 1/4), a visual compensation film, and a brightness enhancement film may be used on the visible side and/or the back side of the liquid crystal cell.
< liquid Crystal display device >
The liquid crystal display device can be formed by appropriately assembling the components such as the above-described liquid crystal panel and the lighting system used as necessary and introducing them into a driver circuit. In forming a liquid crystal display device, for example, a 1-layer or 2-layer or more diffusion sheet, an antiglare layer, an antireflection film, a protective sheet, a prism array, a lens array sheet, a light diffusion sheet, a backlight, and other suitable members may be disposed at appropriate positions. Further, a liquid crystal display device such as a liquid crystal display device using a backlight or a reflector in a lighting system can be suitably formed.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In each example, parts and% are on a weight basis. The following conditions of standing at room temperature are not particularly limited, and are 23 ℃ and 65% RH.
< measurement of weight average molecular weight of (meth) acrylic Polymer >
The weight average molecular weight (Mw) of the (meth) acrylic polymer was measured by GPC (gel permeation chromatography). Mw/Mn was measured in the same manner as described above.
An analysis device: HLC-8120GPC, manufactured by Tosoh corporation
Column: G7000H, manufactured by Tosoh corporationXL+GMHXL+GMHXL
Column size: each 7.8mm phi x 30cm for a total of 90cm
Column temperature: 40 deg.C
Flow rate: 0.8mL/min
Injection amount: 100 μ L
Eluent: tetrahydrofuran (THF)
The detector: differential Refractometer (RI)
Standard sample: polystyrene
< preparation of polarizing film >
A polyvinyl alcohol film having a thickness of 80 μm was stretched 3-fold in an iodine solution having a concentration of 0.3% at 30 ℃ between rolls having different speed ratios while dyeing for 1 minute. Then, the resultant was immersed in an aqueous solution at 60 ℃ containing boric acid at a concentration of 4% and potassium iodide at a concentration of 10% for 0.5 minute, and stretched to a total stretching ratio of 6 times. Next, the plate was washed by immersing the plate in an aqueous solution of potassium iodide at 30 ℃ containing 1.5% concentration for 10 seconds, and then dried at 50 ℃ for 4 minutes to obtain a polarizer having a thickness of 30 μm. A cellulose triacetate film having a thickness of 80 μm and subjected to saponification treatment was bonded to both surfaces of the polarizer with a polyvinyl alcohol adhesive to prepare a polarizing film.
< preparation of (meth) acrylic Polymer >
A monomer mixture containing 100 parts of butyl acrylate, 0.01 part of 2-hydroxyethyl acrylate and 5 parts of acrylic acid was charged into a reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer and a stirrer. Further, 0.1 part of 2, 2' -azobisisobutyronitrile as a polymerization initiator was added to 100 parts of the monomer mixture together with 100 parts of ethyl acetate, nitrogen gas was introduced while slowly stirring the mixture to replace nitrogen gas, and then the liquid temperature in the flask was kept near 55 ℃ to perform polymerization for 8 hours, thereby preparing a solution (solid content concentration: 30 wt%) of an acrylic polymer having a weight average molecular weight (Mw) of 180 ten thousand and an Mw/Mn of 4.1.
Example 1
(preparation of adhesive composition)
An adhesive composition was obtained by mixing 0.23 part of a radical generator (benzoyl peroxide, trade name NYPER BMT manufactured by Nippon fat and oil Co., Ltd.), 1 part of an isocyanate-based crosslinking agent (trade name Coronate L manufactured by Tosoh corporation), 0.25 part of a porphyrazine dye (trade name PD-320 manufactured by Shanben chemical Co., Ltd.: having a maximum absorption wavelength at 595 nm), and 0.25 part of a phenol-based antioxidant (trade name IRGANOX 1010 manufactured by BASF JAPAN) with respect to 100 parts of the solid content of the acrylic polymer solution manufactured as described above.
(preparation of adhesive layer)
The adhesive composition was uniformly applied to the surface of a polyethylene terephthalate film (PET substrate) treated with a silicone-based release agent using a spray coater (fountain coater), and dried in an air circulation oven at 155 ℃ for 2 minutes to form an adhesive layer having a thickness of 20 μm on the surface of the PET substrate, and then the same PET substrate was bonded to the adhesive layer to obtain an adhesive film having a PET substrate on both surfaces of the adhesive layer.
Examples 2 to 12 and comparative examples 1 to 3
An adhesive film was produced in the same manner as in example 1, except that the amounts of the coloring agent, the radical generator, and the antioxidant used in the preparation of the adhesive composition in example 1 were changed as shown in table 1.
The adhesive films (adhesive layers) obtained in the above examples and comparative examples were evaluated as follows. The evaluation results are shown in table 1.
< measurement of gel fraction >
Each of the adhesive compositions before the adhesive films in examples and comparative examples were applied to a polyethylene terephthalate film treated with a silicone-based release agent so that the thickness after drying was 20 μm, and after application, the adhesive layer was formed by curing under the same drying conditions (temperature and time) as in each example, and further left to stand at 23 ℃ and 65% RH for 1 hour, and then the gel fraction was measured with respect to the adhesive layer.
The gel fraction was measured by wrapping 0.2g of the above pressure-sensitive adhesive layer in a fluororesin (Wa, manufactured by Nissan electric corporation, TEMISH NTF-1122) having a predetermined weight and binding the pressure-sensitive adhesive layer so that the optical pressure-sensitive adhesive did not leak, and then measuring the weight (Wb) of the adhesive layer and placing the adhesive layer in a sample bottle. Ethyl acetate (40 cc) was added thereto, and the mixture was left for 1 hour or 7 days. Then, the fluororesin was taken out and dried at 130 ℃ for 2 hours in an aluminum cup, and the weight (Wc) of the fluororesin including the sample was measured to determine the gel fraction by the following formula (I).
Formula (I): gel fraction (W)c-Wa)/(Wb-Wa) X 100 (wt%)
< measurement of transmittance >
After one PET substrate was peeled from the adhesive films obtained in examples and comparative examples, the adhesive layer side was bonded to alkali-free glass. Then, another PET was peeled off, and an acrylic film having a thickness of 60 μm was laminated on the exposed adhesive layer to prepare a sample. The sample was put into an oven at 85 ℃ for 1000 hours, subjected to a durability test, and then taken out. The transmittance before the durability test (T1) and the transmittance after the durability test (T2) were measured for this sample. The transmittance was measured in a state where the sample was at 23 ℃. The transmittance of the above sample was measured. The acrylic film does not affect the transmittance.
The results are shown in Table 1. The differences (T1 to T2) between the transmittances (T1) and (T2), their ratios (T2/T1), are shown together in table 1. The transmittance was measured using a spectral transmittance measuring instrument with an integrating sphere (Dot-3 c, institute of color technology in village).
Figure BDA0002161655300000231

Claims (15)

1. An adhesive composition for a polarizing film, comprising a (meth) acrylic polymer, a coloring matter, a radical generator and an antioxidant,
the (meth) acrylic polymer comprises (meth) acrylic acid alkyl ester and a comonomer as constituent monomers, the comonomer being a hydroxyl group-containing monomer and a carboxyl group-containing monomer,
the adhesive composition for a polarizing film comprises 0.01 to 2 parts by weight of the radical generator per 100 parts by weight of the (meth) acrylic polymer,
the antioxidant is contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic polymer,
the pigment is selected from tetraazaporphyrins, porphyrins, cyanines, azos, methylenepyrroles and squaraines
Figure FDA0003133035350000011
Compounds of the class, xanthene class, oxonol class, squarylium class.
2. The adhesive composition for a polarizer film according to claim 1, wherein the dye has a maximum absorption wavelength in at least one wavelength range of a wavelength range of 470 to 510nm and a wavelength range of 570 to 610 nm.
3. The adhesive composition for a polarizing film according to claim 1, wherein the pigment is a porphyrazine-based pigment.
4. The adhesive composition for a polarizing film according to claim 1, wherein the coloring matter is contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic polymer.
5. The adhesive composition for a polarizing film according to claim 1, wherein the radical generator is a peroxide.
6. The adhesive composition for a polarizing film according to claim 1, wherein the antioxidant is a phenolic antioxidant.
7. The adhesive composition for a polarizing film according to claim 1, wherein a weight ratio (a/B) of the amount (a) of the radical generator to the amount (B) of the antioxidant is 4 or less.
8. The adhesive composition for a polarizing film according to any one of claims 1 to 7, further comprising a crosslinking agent.
9. An adhesive layer for a polarizing film, which is formed from the adhesive composition for a polarizing film according to any one of claims 1 to 8.
10. The adhesive layer for a polarizing film according to claim 9, having a gel fraction of 50 to 98 wt%.
11. The adhesive layer for a polarizing film according to claim 9 or 10, wherein an absolute value of a difference (T1-T2) between a transmittance (T1) before preservation at 85 ℃ for 500 hours and a transmittance (T2) after preservation is 50% or less in the case where the adhesive layer has a thickness of 20 μm.
12. The adhesive layer for a polarizing film according to claim 9 or 10, wherein the adhesive layer has a ratio (T2/T1) of a transmittance (T2) after storage at 85 ℃ for 500 hours to a transmittance (T1) before storage of 2 or less in a thickness of 20 μm.
13. A polarizing film with an adhesive layer, wherein the adhesive layer for polarizing film according to any one of claims 10 to 12 is formed on at least one side of the polarizing film.
14. A liquid crystal panel, wherein a liquid crystal cell and the adhesive layer-attached polarizing film according to claim 13 are bonded to at least either one side of the liquid crystal cell via the adhesive layer of the adhesive layer-attached polarizing film.
15. A liquid crystal display device having the liquid crystal panel according to claim 14.
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