CN106133079A - Cohesiveness compositions, sticker and adhesive sheet - Google Patents
Cohesiveness compositions, sticker and adhesive sheet Download PDFInfo
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- CN106133079A CN106133079A CN201480077475.9A CN201480077475A CN106133079A CN 106133079 A CN106133079 A CN 106133079A CN 201480077475 A CN201480077475 A CN 201480077475A CN 106133079 A CN106133079 A CN 106133079A
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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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
- 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
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- 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
-
- 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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- 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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
The cohesiveness compositions of the present invention contains active energy ray-curable adhesion composition and light diffusion microgranule, the refractive index of active energy ray-curable adhesion composition is 0.005～0.2 with the difference of the refractive index of light diffusion microgranule, and the mean diameter based on centrifugal sedimentation light transmission method of light diffusion microgranule is 0.8～2.9 μm.According to the sticker obtained by this kind of cohesiveness compositions, it is possible to obtain a kind of optical component with sufficient durability and light diffusing and fine.
Description
Technical field
The present invention relates to a kind of cohesiveness compositions, sticker (making the material that cohesiveness compositions solidifies) and adhesion
Sheet, particularly to a kind of cohesiveness compositions, sticker and adhesive sheet being suitable for the optical components such as polaroid.
Background technology
Typically, in liquid crystal panel, in order to polaroid or polarizer being adhered to the glass substrate etc. of liquid crystal cells, make
Situation with the adhering agent layer formed by cohesiveness compositions is more.But, due to the optical component such as polaroid or polarizer
Easily shrink because of heat etc., therefore produce contraction by hot resume, its result, stress-retained in being layered on optical component
Adhering agent layer, produce on surface because of this stress and peel off the problem of durability of (so-called tilting, peeling) and be noted.
On the other hand, liquid crystal panel has slim and consumes the advantage that electric power is less, has on the contrary in brightness or the visual field
The problem that angle aspect is insufficient.From the viewpoint of improving this problem points from utilizing adhering agent layer, as gluing for optical component
Oxidant layer, sometimes require that there is light diffusing.
In order to adhering agent layer being given light diffusing, in adhering agent layer, generally add microgranule.But, when at adhering agent layer
During middle interpolation microgranule, due to the thermal expansivity in microgranule and sticker or the difference etc. of heat-shrinkable, by hot resume micro-
Grain deviates with the surface of sticker, and the problem producing bubble is troubling.
Further, as it has been described above, when for the optical component of thermal contraction, adhering agent layer deforms the most therewith, as foreign body
Microgranule deviates with the surface of sticker, and the problem producing bubble is the most troubling.It is true that when by fine-grained for interpolation viscous
Oxidant layer for optical component time, compared with the situation being not added with microgranule, hot resume the tilting caused and peeling can deteriorate, tool
There is the tendency that durability declines.
In contrast, patent documentation 1 and patent documentation 2 have been attempted as light diffusing sticker, it is suitable for and stores elasticity
The sticker that modulus is higher, thus utilizes the thermal contraction of adhering agent layer suppression optical component itself, the most also prevents by hot resume
Cause with deformation and deviate on sticker and the surface of microgranule.Further, thoroughly solve the light diffusing in optical component to glue
The problem of agent namely the tilting caused by hot resume and the generation of peeling.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2007-332341 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2008-260813 publication
Summary of the invention
The technical problem to be solved in the present invention
But, in recent years, along with the prosperity of the various mobile communication electronic equipment such as smart mobile phone and panel computer, gradually want
The image seeking fine shows.By this kind of requirement, show to contribute to the image of fine, the sticker of optical component
In, the necessity that can obtain having the sticker of the optical component of sufficient light diffusing and high-precision refinement is gradually increased.
The present invention completes in view of this practical situation, and its purpose can obtain as light diffusing sticker for providing one
Cohesiveness compositions, sticker and adhesive sheet to the optical component with sufficient durability and light diffusing and fine.
Solve the technological means of technical problem
To achieve these goals, first, the present invention provides a kind of cohesiveness compositions, it is characterised in that it contains: live
Property energy ray-curable adhesion composition；And light diffusion microgranule, the refractive index of described active energy ray-curable adhesion composition
Be 0.005～0.2 with the difference of refractive index of described light diffusion microgranule, described light diffusion microgranule based on centrifugal sedimentation light transmission method
Mean diameter be 0.8～2.9 μm (inventions 1).
In foregoing invention (invention 1), by containing active energy ray-curable adhesion composition and light diffusion microgranule, playing
Sufficiently durability and light diffusing.Further, by active energy ray-curable defined above adhesion composition refractive index with
The difference of the refractive index of light diffusion microgranule and the mean diameter of light diffusion microgranule, can obtain the fine that dazzle is inhibited
Optical component.
In foregoing invention (invention 1), described active energy ray-curable adhesion composition preferably comprises (methyl) propylene
Acid ester polymer and active energy ray-curable compound (invention 2).
In foregoing invention (invention 2), described active energy ray-curable compound is preferably molecular weight less than 1000
Polyfunctional acrylic ester class monomer (invention 3).
In foregoing invention (invention 2,3), possibly together with cross-linking agent in the most described active energy ray-curable adhesion composition,
In described (methyl) acrylate polymer, as the monomeric unit of this polymer of composition, anti-with described cross-linking agent containing having
The monomer (invention 4) of the functional group answered.
In foregoing invention (invention 1～4), the most described light diffusion microgranule is by having inorganic and organic intermediate structure
The microgranule (invention 5) that silicon-containing compound is constituted.
Second, the present invention provides a kind of sticker, and described sticker is by described cohesiveness compositions (invention 1～5) solidification
Form (invention 6).
In foregoing invention (invention 6), haze value is preferably 10～80% (invention 7).
3rd, the present invention provides a kind of adhesive sheet, and it possesses base material and adhering agent layer, it is characterised in that described sticker
Layer is constituted (invention 8) by described sticker (invention 6,7).
4th, the present invention provides a kind of adhesive sheet, it is characterised in that it possesses: two panels stripping film；And adhering agent layer, with
The mode contacted with the release surface of described two panels stripping film is clamped by described stripping film, and wherein, described adhering agent layer is by described viscous
Agent (invention 6,7) and constitute (invention 9).
Invention effect
Cohesiveness compositions, sticker and adhesive sheet according to the present invention, it is possible to obtain that there is sufficient durability and light
Diffusibility and the optical component of fine.
Accompanying drawing explanation
Fig. 1 is the sectional view of the adhesive sheet of first embodiment of the present invention；
Fig. 2 is the sectional view of the adhesive sheet of second embodiment of the present invention.
Detailed description of the invention
Hereinafter, embodiments of the present invention are illustrated.
(cohesiveness compositions)
The cohesiveness compositions (hereinafter referred to as " cohesiveness compositions P ") of present embodiment contains active energy ray-curable
Property adhesion composition and light diffusion microgranule.Further, the refractive index of active energy ray-curable adhesion composition and light diffusion microgranule
The difference of refractive index is 0.005～0.2, and the mean diameter based on centrifugal sedimentation light transmission method of light diffusion microgranule is 0.8～2.9 μ
m.Possessing the optical component of the adhering agent layer making described cohesiveness compositions P solidify, particularly in polaroid, permissible
There is sufficient durability, and the fine that light diffusing is excellent and dazzle is inhibited.
1. active energy ray-curable adhesion composition
Containing active energy ray-curable adhesion composition in cohesiveness compositions P.In this specification " active-energy is penetrated
Line curable adhesion composition " refer to solidified by the irradiation of active energy beam and show adhesive composition, can be by single
Composition is constituted, it is also possible to be made up of multiple compositions (compositions).When it is the latter, the photograph by active energy beam can be comprised
The composition penetrated and solidify and will not be solidified by the irradiation of active energy beam and show adhesive composition.
As it has been described above, when the sticker containing light diffusion microgranule is applicable to the optical components such as polaroid, in durability etc.
The situation of generation problem is more.But, above-mentioned cohesiveness compositions P containing active energy ray-curable adhesion composition is durable
Property excellent.Further, generally, the cohesiveness of the sticker containing light diffusion microgranule can decline, when peeling off stripping film from adhering agent layer
Time, adhering agent layer is sometimes drawn towards stripping film side, but contains the above-mentioned cohesiveness group of active energy ray-curable adhesion composition
Compound P is difficult to occur as above problem by solidification, and obtained adhering agent layer operability is excellent.
As active energy ray-curable adhesion composition, preferably comprise (methyl) acrylate polymer and active-energy
Ray-curable compound.It addition, in this specification, (methyl) acrylate refer to acrylate and methacrylate this two
Person.Other similar terms are the most identical.Further, " polymer " also comprises the concept of " copolymer ".Hereinafter, mainly to containing (first
Base) the active energy ray-curable adhesion composition of acrylate polymer and active energy ray-curable compound says
Bright.
(1) (methyl) acrylate polymer
In (methyl) acrylate polymer (hereinafter sometimes referred to " (methyl) acrylate polymer (A) "), as structure
Become the monomer of this polymer, preferably comprise (methyl) alkyl acrylate that carbon number is 1～20 of alkyl.Thus, gained
To sticker can manifest more preferably cohesiveness.Further, (methyl) acrylate polymer (A) is particularly preferably alkyl
Carbon number is (methyl) alkyl acrylate of 1～20, has the monomer of reactive functional group (containing reactive functional group list
Body) and the copolymer of other monomers that uses as required.By (methyl) acrylate polymer (A) containing containing reaction
Property functional group monomer as the monomer constituting this polymer, it is possible to improve and the adhesiveness of the glass surfaces such as liquid crystal cells, and,
Can also react with cross-linking agent described later (C) and form cross-linked structure.
As (methyl) alkyl acrylate that carbon number is 1～20 of alkyl, such as, can enumerate (methyl) acrylic acid
Methyl ester, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid n-pentyl ester,
The most own ester of (methyl) acrylic acid, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid positive last of the ten Heavenly stems
Ester, (methyl) acrylic acid dodecyl ester, (methyl) acrylic acid myristyl ester, (methyl) aliphatic acrylate, (first
Base) octadecyl acrylate etc..Wherein, from the viewpoint of improving cohesiveness further, the preferably carbon number of alkyl is 1
～(methyl) acrylate of 8, particularly preferably (methyl) n-butyl acrylate.It addition, these materials can be used alone, it is possible to group
Close use two or more.
In (methyl) acrylate polymer (A), as the monomeric unit of this polymer of composition, preferably comprise the carbon of alkyl
Atomic number is (methyl) alkyl acrylate 50～99 mass % of 1～20, particularly preferably containing 65～97 mass %, further
Preferably comprise 80～95 mass %.
As above-mentioned containing reactive functional group monomer, can preferably enumerate and in intramolecular, there is the monomer of hydroxyl and (contain
Carboxylic monomer), there is the monomer (carboxyl group-containing monomer) of carboxyl in intramolecular, there is the monomer of amino (containing amino list in intramolecular
Body) etc..These monomers Han reactive functional group can be used alone one, it is also possible to is applied in combination two or more.
As the monomer containing hydroxyl, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-can be included such as
Hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxybutyl, (methyl) acrylic acid 3-hydroxyl fourth
(methyl) hydroxyalkyl acrylates etc. such as ester, (methyl) acrylic acid 4-hydroxybutyl.Wherein, from (methyl) propylene obtained
The reactivity of the hydroxyl in acid ester polymer (A) and cross-linking agent (C) and with the copolymerizable of other monomers from the standpoint of, preferably
(methyl) acrylic acid 2-hydroxy methacrylate.These materials can be used alone, it is possible to is applied in combination two or more.
As carboxyl group-containing monomer, such as, can enumerate acrylic acid, methacrylic acid .beta.-methylacrylic acid, maleic acid, itaconic acid, lemon
The ethylenically unsaturated carboxylic acids such as health acid.Wherein, the carboxyl from obtained (methyl) acrylate polymer (A) and cross-linking agent
(C) reactivity and with the copolymerizable of other monomers from the viewpoint of, preferably acrylic acid.These materials can be used alone, also
Can be applied in combination two or more.
As emulsion stability, such as, can enumerate (methyl) acrylate, (methyl) acrylic acid normal-butyl ammonia
Base ethyl ester etc..These materials may be used alone, can also be used in combination two or more.
In (methyl) acrylate polymer (A), as the monomeric unit of this polymer of composition, preferably comprise 1～25 matter
Amount % containing reactive functional group monomer, particularly preferably containing 2～15 mass %, further preferably containing 3～10 mass %.
As other monomers above-mentioned, such as, can enumerate (methyl) methoxyethyl acrylate, (methyl) acrylic acid ethoxy
(methyl) alkoxyalkyl acrylates such as base ethyl ester, (methyl) cyclohexyl acrylate etc. have (methyl) propylene of aliphatic ring
The acrylamide of non-crosslinked, (methyl) the acrylic acid N such as acid esters, acrylamide, Methacrylamide, N-dimethylaminoethyl
Ester, (methyl) acrylic acid N, the non-crosslinked such as N-dimethylamino propyl ester there is (methyl) acrylate of tertiary amino, acetic acid
Vinyl acetate, styrene etc..These materials may be used alone, can also be used in combination two or more.
The polymeric species of (methyl) acrylate polymer (A) can be random copolymer, it is also possible to for block copolymer.
Further, since (methyl) acrylate polymer (A) is for giving adhesive composition, the most active energy-ray
Curable.
The weight average molecular weight of (methyl) acrylate polymer (A) be preferably 400,000～2,500,000, particularly preferred 1,000,000～
2200000, further preferred 1,400,000～2,000,000.By relatively improving the weight average molecular weight of (methyl) acrylate polymer (A),
Durability can be made more excellent.It addition, the weight average molecular weight system in this specification is measured by gel permeation chromatography (GPC) method
The value of polystyrene conversion.
It addition, in cohesiveness compositions P, (methyl) acrylate polymer (A) can be used alone one, it is also possible to group
Close use two or more.
(2) active energy ray-curable compound
The active energy ray-curable adhesion in present embodiment active energy ray-curable contained by composition
Compound (hereinafter sometimes referred to " active energy ray-curable compound (B) "), as long as containing this active energy ray-curable
In the range of the active energy ray-curable adhesion composition of compound (B) is described with the refractivity entrance of light diffusion microgranule i.e.
Can, can be any one in monomer, oligomer or polymer, it is also possible to be the mixture of these materials.Wherein it is possible to relatively
Preferably enumerate the multifunctional propylene of the molecular weight less than 1000 of excellent compatibility with (methyl) acrylate polymer (A) etc.
Esters of gallic acid monomer.
In cohesiveness compositions P in present embodiment, by the irradiation of active energy beam, active energy ray-curable
Property compound (B) mutually forms chemical bond, thus generates tridimensional network.Further, by catching (methyl) in the structure shown here
Acrylate polymer (A), cohesiveness is improved, its result, excellent in te pins of durability.
As the polyfunctional acrylic ester class monomer of molecular weight less than 1000, such as, can enumerate BDO two (first
Base) acrylate, 1,6-HD two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Polyethylene Glycol two (first
Base) acrylate, neopentyl glycol adipic acid two (methyl) acrylate, hydroxy new pentane acid neopentyl glycol two (methyl) acrylic acid
Ester, bicyclo-pentyl ester two (methyl) acrylate, caprolactone modification dicyclopentenyl two (methyl) acrylate, ethylene-oxide-modified phosphorus
Acid two (methyl) acrylate, two (acryloyl-oxyethyl) isocyanuric acid ester, allylation cyclohexyl two (methyl) acrylic acid
Ester etc. two functional-type；Trimethylolpropane tris (methyl) acrylate, dipentaerythritol three (methyl) acrylate, propanoic acid are modified
Dipentaerythritol three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, epoxy pronane modification trimethylolpropane
Three (methyl) acrylate, three (acryloyl-oxyethyl) isocyanuric acid ester, 6-caprolactone modification three-(2-(methyl) acryloyl
Epoxide ethyl) the trifunctional type such as isocyanuric acid ester；Two glycerol four (methyl) acrylate, tetramethylolmethane four (methyl) acrylate
Deng four functional-type；Five functional-type such as propanoic acid modification dipentaerythritol five (methyl) acrylate；Dipentaerythritol six (methyl) third
Six functional-type etc. such as olefin(e) acid ester, caprolactone modification dipentaerythritol six (methyl) acrylate.Wherein, these materials can be independent
Use one, it is also possible to be applied in combination two or more.
The content of active energy ray-curable compound (B) is relative to (methyl) acrylate polymer (A) 100 mass
Part is preferably 1～50 mass parts, particularly preferred 5～30 mass parts, further preferred 10～20 mass parts.Penetrated by active-energy
Within the above range, obtained sticker durability is more excellent for the content of line curable compound (B), and, obtained
Adhering agent layer operability excellent.And, cohesiveness based on (methyl) acrylate polymer (A) is maintained well.
(3) cross-linking agent
In cohesiveness compositions P, preferably comprise cross-linking agent (C) as active energy ray-curable adhesion composition.When viscous
Containing comprising containing reactive functional group monomer as the monomeric unit constituting polymer in the adhesion composition of the property compositions P
When (methyl) acrylate polymer (A) and cross-linking agent (C), if this cohesiveness compositions P is carried out heating etc., then cross-linking agent
(C) react with the reactive functional group containing reactive functional group monomer constituting (methyl) acrylate polymer (A).By
This, form the structure that (methyl) acrylate polymer (A) is cross-linked, the cohesiveness of obtained sticker by cross-linking agent (C)
It is improved.
It addition, in cohesiveness compositions P in present embodiment, by described active energy ray-curable compound
(B) cohesiveness of the sticker obtained by improving realizes the raising of durability.But, from the suitable adhesion maintaining sticker
Power, and improve cohesiveness further, and from the viewpoint of durability is more excellent, be more highly preferred to use cross-linking agent (C) simultaneously.
As cross-linking agent (C), as long as the reactive functional group being had with (methyl) acrylate polymer (A) is reacted i.e.
Can, such as can enumerate isocyanates cross-linking agent, epoxies cross-linking agent, amine cross-linking agent, melamine class cross-linking agent, nitrogen third
Pyridine class cross-linking agent, hydrazine cross-linking agent, aldehyde crosslinking agent, oxazoline class cross-linking agent, metal alkoxide class cross-linking agent, metal-chelating class are handed over
Connection agent, metallic salt cross-linking agent, ammonium salt class cross-linking agent etc..When (methyl) acrylate polymer (A) has hydroxyl as reaction
Property functional group time, above-mentioned in, reactive excellent isocyanates cross-linking agent with hydroxyl is preferably used.It addition, cross-linking agent (C)
Can be used alone one, or be applied in combination two or more.
Isocyanates cross-linking agent at least contains polyisocyanate compounds.As polyisocyanate compounds, such as, can
Include the aromatic poly-isocyanates such as toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, XDI, six
The aliphatic polymeric isocyanates such as methylene diisocyanate, isophorone diisocyanate, hydrogenation diphenylmethane diisocyanate
The ester ring type polyisocyanate etc. such as ester, and the biuret body of described material, isocyanuric acid ester body, and ethylene glycol, propylene glycol,
The reactant of the low molecule activity hydrogen-containing compounds such as neopentyl glycol, trimethylolpropane, Oleum Ricini namely add adult etc..Wherein,
From with the reactivity of hydroxyl from the viewpoint of, the aromatic poly-isocyanate that preferably trimethylolpropane is modified, particularly preferred three
Hydroxymethyl-propane modified toluene diisocyanate.
The content of cross-linking agent (C) is relative to (methyl) acrylate polymer (A) 100 mass parts, preferably 0.01～10
Mass parts, particularly preferred 0.05～5 mass parts, further preferred 0.1～1 mass parts.
(4) various additives
Active energy ray-curable adhesion composition can contain various additives, such as photopolymerization as required to be caused
Agent, silane coupler, refractive index adjusters, antistatic additive, viscosifier, antioxidant, UV absorbent, light stabilizer, soft
Agent, filler etc..
When using ultraviolet as the active energy beam making cohesiveness compositions P solidify, active energy ray-curable
Property adhesion composition in preferably comprise Photoepolymerizationinitiater initiater.By containing Photoepolymerizationinitiater initiater, it is possible to make active energy ray-curable
Property adhesion composition effectively solidify, and the irradiation dose of polymerizing curable time and active energy beam can be reduced.
As Photoepolymerizationinitiater initiater, such as, can enumerate Benzoinum, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl
Ether, Benzoinum-n-butyl ether, benzoin isobutyl ether, 1-Phenylethanone., dimethylamino benzoylformaldoxime, 2,2-dimethoxy-2-phenyl benzene second
Ketone, 2,2-diethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenylpropyl alcohol alkane-1-ketone, 1-hydroxycyclohexylphenylketone,
2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino-propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2-(hydroxyl-2-
Propyl group) ketone, benzophenone, to phenyl benzophenone, 4,4 '-diethylamino benzophenone, dichloro benzophenone, 2-methyl anthracene
Quinone, 2-ethyl-anthraquinone, 2-tert-butyl group anthraquinone, 2-amino anthraquinones, 2-methyl thiaxanthone, 2-ethyl thiaxanthone, CTX, 2,
4-diformazan thiaxanthone, 2,4-diethyl thiaxanthone, benzil dimethyl ketal, 1-Phenylethanone. dimethyl ketal, to dimethylamino pacify
Breath fragrant acid esters, oligomerization [2-hydroxy-2-methyl-1 [4-(1-methyl ethylene) phenyl] acetone], 2,4,6-trimethylbenzoyl
Base-diphenyl-phosphineoxide etc..These materials may be used alone, can also be used in combination two or more.
About Photoepolymerizationinitiater initiater, relative to the active energy ray-curable in active energy ray-curable adhesion composition
Property compound (B) 100 mass parts, preferably use with the amount of 0.1～20 mass parts scopes, particularly preferably with 1～12 mass parts models
The amount enclosed uses.
Further, from the viewpoint of the adhesion strength with glass surface etc. of the sticker obtained by improving, active energy beam
Curable adhesion composition preferably comprises silane coupler.As silane coupler, it preferably has at least 1 alkane in intramolecular
The organo-silicon compound of epoxide silicyl and good with the compatibility of adhesion composition and there is photopermeability.
As described silane coupler, such as, can enumerate vinyltrimethoxy silane, VTES, first
The silicon compound containing polymerism unsaturated group such as base acryloxypropyl trimethoxy silane, 3-glycidyl ether propyl group trimethoxy
Base silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc. has the silicon compound of epoxy construction, 3-mercaptopropyi
Trimethoxy silane, 3-Mercaptopropyltriethoxysilane, 3-mercaptopropyi dimethoxymethylsilane etc. close containing sulfydryl silication
Thing, 3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino second
Base)-3-amino propyl methyl dimethoxysilane etc. is containing aminosilicon compounds, 3-r-chloropropyl trimethoxyl silane, 3-Carbimide.
Ester propyl-triethoxysilicane or they at least one are with MTES, ethyl triethoxysilane, methyl
Trimethoxy silane, ethyl trimethoxy silane etc. are containing the condensation substance etc. of alkyl silicon compound.Those materials can be used alone one
Kind, it is possible to it is applied in combination two or more.
The content of silane coupler is preferably 0.01～10 relative to (methyl) acrylate polymer (A) 100 mass parts
Mass parts, particularly preferred 0.05～5 mass parts, further preferred 0.1～1 mass parts.
2. light diffusion microgranule
Light contained by the cohesiveness compositions P diffusion microgranule of present embodiment with the refractivity of above-mentioned adhesion composition is
0.005～0.2, mean diameter based on centrifugal sedimentation light transmission method is 0.8～2.9 μm.
Spread microgranule as above-mentioned light, such as, can enumerate silicon dioxide, calcium carbonate, aluminium hydroxide, magnesium hydroxide, glue
The mineral-type microgranules such as soil, Talcum, titanium dioxide；Acrylic resin, polystyrene resin, polyvinyl resin, epoxy resin etc. have
The light transmission microgranule of machine class；As silicone resin by having the inorganic microgranule constituted with organic intermediate structure silicon-containing compound
(the TOSPEARL series of such as Japan Momentive Performance Materials Inc.) etc..Wherein, from answering
From the viewpoint of the high-precision refinement of adhering agent layer, preferred acrylic resins microgranule and inorganic with organic centre by having
The microgranule that the silicon-containing compound of structure is constituted.Further, even if adding a small amount of by having containing of inorganic and organic intermediate structure
The microgranule that silicon compound is constituted, also plays its effect, and the cohesiveness of active energy ray-curable adhesion composition obtains well
Maintain, the most particularly preferably.Above light diffusion microgranule can be used alone one, it is also possible to is applied in combination two or more.
As aforesaid propylene acid resin microgranule, such as, can enumerate the homopolymer by methyl methacrylate or methyl-prop
The copolymers of the monomers such as e pioic acid methyl ester and vinyl acetate, styrene, methacrylate, ethyl methacrylate etc. are constituted
Microgranule.
Uniform spheroidal particle is spread as the shape of light diffusion microgranule, preferably light.Sinking based on centrifugal of light diffusion microgranule
The mean diameter of fall light transmission method is required to be 0.8～2.9 μm, preferably 1～2.7 μm, particularly preferred 1.2～2.2 μm.Spread by light
The mean diameter of microgranule is the least, by described active energy ray-curable adhesion composition and the refractive index of light diffusion microgranule
The interaction of difference, can obtain having sufficient light diffusing and the band adhering agent layer optics of fine that dazzle is inhibited
Component.If the mean diameter of light diffusion microgranule is more than 2.9 μm, then the band adhering agent layer optics structure of the sticker obtained by being suitable for
Part produces dazzle.On the other hand, if the mean diameter of light diffusion microgranule is less than 0.8 μm, then light diffusing becomes insufficient.
It addition, above-mentioned mean diameter based on centrifugal sedimentation light transmission method, microgranule 1.2g and isopropanol will be sufficiently stirred for
98.8g person is as test sample, and uses centrifugal automatic particle size distribution device (HORIBA, Ltd. system, CAPA-
700) measure.
The content of the light diffusion microgranule in cohesiveness compositions P is relative to above-mentioned active energy ray-curable adhesion composition
100 mass parts, preferably 1～30 mass parts, particularly preferred 2～15 mass parts, further preferred 6～12 mass parts.By light
The content of diffusion microgranule within the above range, has sufficient light diffusing, and dazzle is inhibited effectively, and, the most not
The cohesiveness of active energy ray-curable adhesion composition can be hindered.
3. refractivity
In cohesiveness compositions P of present embodiment, from the viewpoint of taking into account light diffusing and high-precision refinement, activity energy
The refractive index of amount ray-curable adhesion composition is required to be 0.005～0.2, preferably 0.007 with the difference of the refractive index of light diffusion microgranule
～0.1, particularly preferred 0.01～0.08.Refractivity by active energy ray-curable adhesion composition with light diffusion microgranule
The least, can easily realize high-precision refinement.
It addition, the refractive index of active energy ray-curable adhesion composition is preferably 1.40～1.55, particularly preferred 1.42
～1.50, further preferred 1.44～1.49.Further, the refractive index of light diffusion microgranule is preferably 1.40～1.55, particularly preferably
1.41～1.52, further preferred 1.42～1.45.
Here, the refractive index of active energy ray-curable adhesion composition is for using Abbe refractometer to survey according to JISK0062
Fixed value.It addition, the refractive index of active energy ray-curable adhesion composition will not change before and after it solidifies, therefore may be used
The value measured before thinking solidification, it is also possible to for the value measured after solidification.On the other hand, shown in test example as be described hereinafter, light spreads
The refractive index of microgranule is the value using refractive index titer to measure.
4. the preparation method of cohesiveness compositions
Cohesiveness compositions P can be by mixed active energy ray-curable adhesion composition and light diffusion microgranule system
Standby.When in active energy ray-curable adhesion composition containing (methyl) acrylate polymer (A), first prepare (methyl) third
Olefine acid ester polymer (A), then add active energy ray-curable compound (B), and be added as needed on cross-linking agent (C) and add
Add agent.
By utilizing common radical polymerization to be polymerized the mixture of the monomeric unit constituting polymer such that it is able to
Preparation (methyl) acrylate polymer (A).As required, use polymerization initiator and can be carried out by solution polymerization process etc.
The polymerization of (methyl) acrylate polymer (A).As polymer solvent, such as, can enumerate ethyl acetate, n-butyl acetate, acetic acid
Isobutyl ester, toluene, acetone, hexane, butanone etc., it is possible to and with two or more.
As polymerization initiator, azo compound, organic peroxide etc. can be enumerated, it is possible to and with two or more.Make
For azo compound, such as, 2,2'-azodiisobutyronitriles, 2,2'-azo double (2-methylbutyronitrile), 1, the double (ring of 1'-azo
Hexane-1-carboxylic nitrile), 2,2'-azo double (2,4-methyl pentane nitrile), the double (2,4-dimethyl-4-methoxyl group penta of 2,2'-azo
Nitrile), dimethyl 2,2'-azo double (2 Methylpropionic acid ester), 4,4'-azo double (4-cyanopentanoic acid), double (the 2-hydroxyl of 2,2'-azo
Methyl propionitrile), 2,2'-azo double [2-(2-imidazoline-2-base) propane] etc..
As organic peroxide, such as, can enumerate benzoyl peroxide, TBPB tertiary butyl perbenzoate, cumene peroxidating
Hydrogen, diisopropyl peroxydicarbonate, two-n-pro-pyl peroxydicarbonate, two (2-ethoxyethyl group) peroxydicarbonate, mistake
Oxidation the neodecanoic acid tert-butyl ester, tert-Butyl peroxypivalate, (3,5,5-trimethyl acetyl base) peroxide, peroxidating dipropyl
Acyl, diacetyl peroxide etc..
It addition, in above-mentioned polymerization process, by adding the chain-transferring agents such as 2 mercapto ethanol, the polymer obtained can be regulated
Weight average molecular weight.
After obtaining (methyl) acrylate polymer (A), add in the solution of (methyl) acrylate polymer (A)
Active energy ray-curable compound (B) and light diffusion microgranule, and it is added as needed on cross-linking agent (C) and additive fully
Mixing, thus obtains by cohesiveness compositions P (coating solution) of solvent dilution.
It is made the retarder thinner of coating solution as being used for diluting cohesiveness compositions P, such as, can use hexane, heptan
Halogenated hydrocarbons, methanol, the second such as the aromatic hydrocarbons such as the aliphatic hydrocarbon such as alkane, hexamethylene, toluene, dimethylbenzene, dichloromethane, dichloroethylene
Ketone, the acetic acid such as alcohol, acetone, butanone, 2 pentanone, isophorone, Ketohexamethylene such as alcohol, propanol, butanol, 1-methoxy-2-propanol
The cellosolve type solvents etc. such as the ester such as ethyl ester, butyl acetate, ethyl cellosolve.
As concentration, the viscosity of thus prepared coating solution, as long as in the scope that can be coated with, there is no particularly limit
System, can suitably select according to situation.Such as, it is diluted to make the concentration of cohesiveness compositions P become 10～40 matter
Amount %.It addition, when obtaining coating solution, the interpolation not necessarily condition of retarder thinner etc., if cohesiveness compositions P is for being coated with
The viscosity etc. of cloth, the most also can be without retarder thinner.
(sticker)
Cohesiveness compositions P, for making the solidification of cohesiveness compositions P form, is coated and is wished by the sticker of present embodiment
The object hoped after being dried, is made by the irradiation of active energy beam cohesiveness compositions P solidify, it is possible to
Preferably obtain sticker.
Being dried of cohesiveness compositions P can be carried out by air-drying, but generally by heat treated (preferably hot air drying
Dry) carry out.When carrying out heat treated, heating-up temperature is preferably 50～150 DEG C, particularly preferred 70～120 DEG C.Further, add
The heat time is preferably 10 seconds～10 minutes, particularly preferred 50 seconds～2 minutes.
As active energy beam, ultraviolet, electron ray etc. generally can be used.The irradiation dose of active energy beam because of
The kind of energy-ray and different, for example, during ultraviolet, preferably 50～1000mJ/cm2Light quantity, particularly preferred 100～
500mJ/cm2.Further, when for electron ray, preferably 10～about 1000krad.
Containing (methyl) acrylate polymer in the active energy ray-curable of cohesiveness compositions P adheres composition
(A), active energy ray-curable compound (B) and during cross-linking agent (C), being dried (at heating by cohesiveness compositions P
Reason), (methyl) acrylate polymer (A) is cross-linked by cross-linking agent (C) and forms cross-linked structure.Further, by cohesiveness
The irradiation of the active energy beam of compositions P, multiple active energy ray-curable compounds (B) are mutually bonded and form three-dimensional
Network structure, such that it is able to be inferred as catching (methyl) acrylate polymer (A) cross-linked by cross-linking agent (C) in this three
In dimension network structure.
The haze value (value measured according to JISK7105) preferably 10～80% of the sticker of present embodiment, the most excellent
Select 20～70%, further preferred 25～66%.By haze value within the above range, the sticker light diffusion of present embodiment
Property excellent and dazzle inhibition is more excellent.
Further, from the viewpoint of durability, the sticker of present embodiment storage elastic modulus at 80 DEG C (G ')
Preferably 0.2～5MPa, particularly preferred 0.2～2MPa, further preferred 0.3～1MPa.
It addition, above-mentioned storage elastic modulus (G ') it is the value utilizing following method to measure.
The assay method ＞ of ＜ storage elastic modulus (G ')
Stacking adhering agent layer is also punched out, and thus makes the columned test film of diameter 8mm × thickness 3mm, passes through
Torsional shear method measures storage elastic modulus (G ') under the following conditions.
Determinator: Rheometric Scientific, Inc. dynamic determination of viscoelasticity device " DYNAMIC
ANALYZER RDAII”
Frequency: 1Hz
Temperature: 80 DEG C
(adhesive sheet)
As it is shown in figure 1, the adhesive sheet 1A of the first embodiment under successively by stripping film 12, the stripping that is laminated in stripping film 12
Adhering agent layer 11 from face and be laminated in the base material 13 of adhering agent layer 11 and constitute.
Further, as in figure 2 it is shown, the adhesive sheet 1B of the second embodiment by two panels stripping film 12a, 12b and with this two
The adhering agent layer 11 that the mode of the release surface contact of sheet stripping film 12a, 12b is clamped by this two panels stripping film 12a, 12b is constituted.Separately
Outward, the release surface of the stripping film in this specification refers to the surface in stripping film with fissility, also comprises enforcement lift-off processing
Surface and even if lift-off processing be not carried out display that any one in the surface of fissility.
In any one adhesive sheet 1A, 1B, adhering agent layer 11 is by the adhesion making described cohesiveness compositions P solidify
Agent is constituted.
The thickness of adhering agent layer 11 suitably can determine according to the application target of adhesive sheet 1A, 1B, but typically 5～
100 μm, the scope of preferably 10～60 μm, such as, when as the adhering agent layer of functional film, is 10～50 μm, especially
Preferably 15～30 μm.
Being not particularly limited as base material 13, the base material of the substrate sheets being typically used as adhesive sheet all can make
With.Such as, in addition to desired optical component, it is also possible to that enumerates the fibers such as use staple fibre, acrylic acid, polyester spins cloth
Or non-woven fabrics；Good quality paper, cellophane, containing impregnated paper, the coating stationery such as paper；The metal forming such as aluminum, copper；Urethane foaming body, polyethylene are sent out
The foaming bodies such as foam；Pet film, polybutylene terephthalate (PBT) thin film, poly-naphthalenedicarboxylic acid second two
The celluloses such as polyolefin film, Triafol T such as the mylars such as alcohol ester film, polyethylene film, polypropylene film are thin
Film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, vinyl-vinyl acetate copolymer thin film, poly-ammonia
Ester film, polystyrene film, polycarbonate film, acrylic resin films, norbornene resin thin film, cyclic olefin resins
The plastic sheetings such as thin film；And the two or more duplexer etc. of these materials.Plastic sheeting can carry out uniaxial extension or two
Axle extends.
As optical component, such as can enumerate polaroid (polarizing coating), polarizer, polarizer (phase retardation film),
Compensation film for angular field of view, brightness enhancement film, contrast improve film, liquid crystal polymer film, diffusion barrier, semipermeable reflection film etc..Wherein, polarization
Sheet (polarizing coating) easily shrinks, and change in size is relatively big, therefore from the viewpoint of durability, is suitable as forming this embodiment party
The object of the sticker (above-mentioned adhering agent layer 11) of formula.
The thickness of base material 13 is also different, for example, during optical component because of its kind, it is common that 10～500 μm, and preferably 50
～300 μm, particularly preferred 80～150 μm.
As stripping film 12,12a, 12b, such as, polyethylene film, polypropylene film, polybutene thin film, poly-fourth can be used
Diene thin film, poly-methyl pentene film, polyvinyl chloride film, vinyl chloride copolymer thin film, polyethylene terephthalate are thin
Film, PEN thin film, polybutylene terephthalate (PBT) thin film, polyurethane film, ethylene vinyl acetate
Thin film, ionomer resin thin film, ethylene-(methyl) acrylic copolymer thin film, ethylene-(methyl) acrylate copolymer is thin
Film, polystyrene film, polycarbonate film, Kapton, fluorine resin film etc..And, it is possible to use these materials
Crosslinked film.It addition, be alternatively the laminate film of these materials.
The release surface (face particularly contacted with adhering agent layer 11) of above-mentioned stripping film is preferably carried out lift-off processing.As
It is used in the remover of lift-off processing, such as, alcohol acids, silicone, fluorine class, unsaturated polyester esters, TPO, wax can be enumerated
The removers such as class.It addition, in stripping film 12a, 12b, preferably side's stripping film is set to the peeling force exfoliated stripping of bigger weight
Sheet, is set to the light exfoliated stripping film that peeling force is less by the opposing party's stripping film.
About the thickness of stripping film 12,12a, 12b, there is no particular restriction, usually about 20～150 μm.
In order to prepare above-mentioned adhesive sheet 1A, the release surface at stripping film 12 is coated with the solution comprising cohesiveness compositions P and (is coated with
Cloth solution) and be dried, after forming the film layer of adhesion agent composition P, laminated substrate 13 on this film layer.Further,
Make it solidify by irradiating active energy beam across stripping film 12 to above-mentioned film layer, thus form adhering agent layer 11.Separately
Outward, the irradiation condition about active energy beam is described above.
Further, in order to prepare above-mentioned adhesive sheet 1B, the release surface of a stripping film 12a (or 12b) is coated with and comprises
State the coating solution of cohesiveness compositions P and be dried, after forming the film layer of cohesiveness compositions P, at this film layer
Upper stacking another stripping film 12b (or 12a).Further, by irradiating alive to above-mentioned film layer across stripping film 12a (or 12b)
Property energy-ray and make it solidify, thus form adhering agent layer 11.
Further, replace irradiating active energy beam across stripping film as described above and form adhering agent layer 11, it is also possible to
Stripping film is formed the film layer of cohesiveness compositions P, irradiates active energy beam when this film layer exposes
After forming adhering agent layer 11, laminated substrate or stripping film on this adhering agent layer 11.Furthermore it is also possible on base material direct shape
Become the film layer of cohesiveness compositions P, irradiate active energy beam to this film layer and form adhering agent layer 11.
As the method being coated with above-mentioned coating fluid, such as, can utilize rod coating method, scraper for coating method, roller rubbing method, scrape
Plate rubbing method, die coating methods, gravure coating process etc..
Here, such as, in order to prepare the liquid crystal indicator being made up of liquid crystal cells and polaroid, use polaroid conduct
The base material 13 of adhesive sheet 1A, peels off the stripping film 12 of this adhesive sheet 1A, and the adhering agent layer 11 exposed and liquid crystal cells is fitted
?.
Further, such as, in order to prepare the liquid crystal indicator of configuration phase difference plate between liquid crystal cells and polaroid, make
It is an example, first peels off a stripping film 12a (or 12b) of adhesive sheet 1B, by adhering agent layer 11 He exposed of adhesive sheet 1B
Polarizer is fitted.Then, the stripping film 12 using polaroid as the adhesive sheet 1A of base material 13 is peeled off, by the dew of adhesive sheet 1A
The adhering agent layer 11 gone out and the laminating of above-mentioned polarizer.It addition, peel off another stripping from the adhering agent layer 11 of above-mentioned adhesive sheet 1B
From sheet 12b (or 12a), by the adhering agent layer 11 exposed and the liquid crystal cells laminating of adhesive sheet 1B.
According to above adhesive sheet 1A, 1B, it is possible to obtain playing light diffusing by adhering agent layer 11 and dazzle is pressed down
The optical component of the fine of system.Further, owing to the morphological stability of adhering agent layer 11 is the most excellent, the most such as, it is applicable to partially
During sheet bonding of shaking, it is also possible to utilize adhering agent layer 11 to suppress the deformation of polaroid, thus may infer that as playing higher durable
Property.Thus, even if applying in the environment of hot resume, it is also possible to optical component is given fine, excellent through time stable
Property and light diffusing.
Embodiments described above, for the ease of understanding that the present invention records, is not intended to limit the present invention and record.
Thus, each key element disclosed in above-mentioned embodiment also comprises all design alterations and the equivalent of the technical scope belonging to the present invention
Thing.
For example, it is possible to omit the stripping film 12 of adhesive sheet 1A, it is also possible to omit in stripping film 12a, the 12b in adhesive sheet 1B
Any one.
Embodiment
Hereinafter, by embodiment etc., the present invention is carried out the brightest, but the scope of the present invention non-limiting
In these material embodiments etc..
(embodiment 1)
1. the preparation of (methyl) acrylate polymer
Make n-butyl acrylate 94.5 mass parts, acrylic acid 5 mass parts and acrylic acid 2-hydroxy methacrylate 0.5 mass parts copolymerization
And prepare (methyl) acrylate polymer (A).Utilize method described later to measure and be somebody's turn to do dividing of (methyl) acrylate polymer (A)
The result of son amount, weight average molecular weight is 1,800,000.
2. the preparation of cohesiveness compositions
Mix (methyl) acrylate polymer (A) 83.5 mass parts (the solid constituent scaled value obtained in above-mentioned operation；
The most identical), as three (acrylyl oxy-ethyl) isocyanuric acid ester of active energy ray-curable compound (B)
(TOAGOSEI CO., LTD. system, ProductName " ARONIX M-315 "；Molecular weight 423) 15 mass parts and as cross-linking agent
Trimethylolpropane modified toluene diisocyanate (C) (Nippon Polyurethane Industry Co., Ltd. system,
ProductName " CORONATE L ") after 0.3 mass parts, add as the benzophenone of Photoepolymerizationinitiater initiater and 1-hydroxy cyclohexylphenyl
Base phenyl ketone with the quality of 1:1 than mixture (Chiba Speciality Chemicals Corporation system, ProductName
" IRGACURE500 ") 1.5 mass parts, 3-glycidyl ether oxygen propyl trimethoxy silicane (Shin-as silane coupler
Etsu Chemical Co., Ltd. system, ProductName " KBM-403 ") 0.2 mass parts (more than, active energy ray-curable glues
Composition) and as light diffusion microgranule by having the inorganic microgranule constituted with organic intermediate structure silicon-containing compound
(Japan Momentive Performance Materials Inc. system, ProductName " TOSPEARL120 ", mean diameter:
2.0 μm, refractive index: 1.43) 2.5 mass parts (are 2.5 matter relative to active energy ray-curable adhesion composition 100 mass parts
Amount part) and be sufficiently stirred for, and dilute with ethyl acetate, thus obtain the coating solution of cohesiveness compositions.
Here, the interpolation of this cohesiveness compositions is shown in table 1.It addition, the detailed content of contracted notation etc. described in table 1 is such as
Under.
[(methyl) acrylate polymer (A)]
BA: n-butyl acrylate
AA: acrylic acid
HEA: acrylic acid 2-hydroxy methacrylate
[light diffusion microgranule]
Silicone microgranule (2 μm): by having the inorganic microgranule (Japan constituted with organic intermediate structure silicon-containing compound
Momentive Performance Materials Inc. system, ProductName " TOSPEARL120 ", mean diameter: 2.0 μm, folding
Penetrate rate: 1.430)
Silicone microgranule (4.5 μm): by having the inorganic microgranule constituted with organic intermediate structure silicon-containing compound
(Japan Momentive Performance Materials Inc. system, ProductName " TOSPEARL145 ", mean diameter:
4.5 μm, refractive index: 1.430)
PMMA microgranule (2.5 μm): resin bead (the SEKISUI PLASTICS being made up of the methacrylate polymer cross-linked
CO., LTD. system, ProductName " SSX102 ", mean diameter: 2.5 μm, refractive index: 1.490)
PMMA microgranule (4 μm): resin bead (the SEKISUI PLASTICS being made up of the methacrylate polymer cross-linked
CO., LTD. system, ProductName " SSX104 ", mean diameter: 4.0 μm, refractive index: 1.490)
Styrene/acrylic acid co-polymer microgranule (3.5 μm): the tree being made up of the copolymer of styrene and acrylic monomer
Fat pearl (SEKISUI PLASTICS CO., LTD. system, mean diameter: 3.5 μm, refractive index: 1.555)
3. the preparation of band adhering agent layer polaroid
Use scraper type coating machine, the coating solution of the cohesiveness compositions obtained in above-mentioned operation is coated by poly-benzene
The one side silicone remover of naphthalate thin film carries out stripping film (the LINTEC Corporation of lift-off processing
System, SP-PET3811, thickness: 38 μm) lift-off processing face after, heat treated 1 minute at 90 DEG C, thus form cohesiveness
The film layer of compositions.
Then, be made up of the polarizing coating of band discotic liquid crystal layer, polarizing coating and angle of visibility expansion film are integrally forming is inclined
The sheet that shakes fits in the exposed surface side of above-mentioned film layer.Thereafter, across stripping film irradiation ultraviolet radiation under the following conditions by above-mentioned
Film layer is made adhering agent layer, thus obtains band adhering agent layer polaroid.It addition, the thickness of the adhering agent layer formed is 25 μ
m。
＜ ultraviolet irradiates condition ＞
Fusion Communication Corp. electrodeless lamp uses H bulb
Illumination 600mW/cm2, light quantity 150mJ/cm2
UV illumination/quantometer uses EYE GRAPHICS Co.Ltd. system " UVPF-36 "
(embodiment 2～11, comparative example 1～6)
The most like that, change (methyl) acrylate polymer (A), active energy ray-curable compound (B)
And the addition of Photoepolymerizationinitiater initiater, the light diffusion kind of microgranule and addition and the thickness of adhering agent layer, in addition,
Prepare band adhering agent layer polaroid similarly to Example 1.
Here, described weight average molecular weight (Mw) is for utilizing gel permeation chromatography (GPC) to measure (GPC mensuration) in following condition
The weight average molecular weight of polystyrene conversion.
＜ condition determination ＞
GPC determinator: Tosoh Corporation system, HLC-8020
GPC post (passes through) in the following order: Tosoh Corporation system
TSK guard column HXL-H
TSK gel GMHXL(×2)
TSK gel G2000HXL
Mensuration solvent: oxolane
Mensuration temperature: 40 DEG C
(test example 1) (calculating of refractive index)
Measure the refractive index of the light diffusion microgranule used in embodiment and comparative example by the following method.Microgranule is placed in
In sliding glass, and dripping on microgranule by refractive index titer, close the lid glass, makes sample.This sample is observed with microscope
Product, will be most difficult to the refractive index observing the refractive index titer of the profile of the microgranule refractive index as microgranule.
On the other hand, the refractive index of the adhesion composition used in embodiment and comparative example is measured by the following method.In reality
Execute in example and comparative example respective cohesiveness compositions, be not added with light diffusion microgranule, and replace the system of band adhering agent layer polaroid
Polaroid used in work, uses and is peeled off by the one side silicone remover of pet film
The stripping film (LINTEC Corporation system, SP-PET3801, thickness: 38 μm) processed, and adhering agent layer is set to thickness
25 μm, other the most similarly set and make by stripping film (SP-PET3801)/adhering agent layer (thickness: 25 μm)/stripping film
(SP-PET3811) adhesive sheet that structure is constituted.
The adhering agent layer of the monolayer obtained peeling two panels stripping film from above-mentioned adhesive sheet is as measuring sample.For this
Measure sample, use Abbe refractometer, measure refractive index according to JIS K0062-1992, using this as active energy ray-curable
Property adhesion composition refractive index.
Refractivity by above measurement result calculated activity energy ray-curable adhesion composition with light diffusion microgranule.
Show the result in table 2.
(test example 2) (mensuration of haze value)
Replacing the polaroid used in the making of band adhering agent layer polaroid in embodiment and comparative example, using will be poly-
The one side silicone remover of ethylene glycol terephthalate thin film carries out the stripping film (LINTEC of lift-off processing
Corporation system, SP-PET3801, thickness: 38 μm), make by stripping film (SP-PET3801)/adhering agent layer/stripping film
(SP-PET3811) adhesive sheet that structure is constituted.
For the adhering agent layer of obtained adhesive sheet, use mist degree analyzer (NIPPON DENSHOKU
INDUSTRIES Co., Ltd. system, NDH2000), measure haze value (%) according to JIS K7105.Show the result in table 2.
(test example 3) (evaluation of fineness)
Metal vapor deposition layer is set on a glass and carries out chromating and etch processes, be consequently formed have 60ppi (as
Element/inch) lattice-shaped pattern of light transmissive portion of size.The glass plate being provided with this lattice-shaped pattern is placed in backlight
On (Kingbright Electronic Co., Ltd. system, BRIGHT BOX 5000).
Then, the stripping film of the band adhering agent layer polaroid obtained in embodiment and comparative example is peeled, in above-mentioned clathrate
On pattern, the unilateral side that polarizes by band adhering agent layer polaroid loads in the way of down, confirms the generating unit of dazzle.Further, make
Above-mentioned band adhering agent layer polaroid moves, when the dazzle confirmed in advance along the direction parallel with glass plate on lattice-shaped pattern
When generating unit and above-mentioned band adhering agent layer polaroid together move, it is judged that the generation for this dazzle is inclined by above-mentioned band adhering agent layer
The sheet that shakes causes.
Further, when the product to the dazzle caused by band adhering agent layer polaroid unconfirmed in the lattice-shaped pattern of 60ppi
Time raw, use the lattice-shaped pattern of 70ppi, the most unconfirmed to the dazzle caused by above-mentioned band adhering agent layer polaroid
Generation time, use the lattice-shaped pattern of 80ppi separately, use the lattice-shaped pattern often increasing 10ppi to carry out the most successively
Identical operation, until confirming the generation of the dazzle caused by band adhering agent layer polaroid.Illustrate in table 2 unconfirmed to by
The generation of the dazzle caused with adhering agent layer polaroid, lattice-shaped pattern (ppi) that ppi is maximum.
Here, about the dazzle caused by band adhering agent layer polaroid, the ppi in lattice-shaped pattern is the biggest, in other words, aobvious
Show that device more becomes fine, the most easily produce.Thus, the value of the ppi shown in table 2 is the biggest, it is meant that more can effectively suppress
The generation of dazzle.It addition, then can be referred to as the polaroid of fine more than 100ppi.
(test example 4) (durability evaluation)
Use Scissoring device (the Ogino Seisakusho Co., Ltd. super cutting machine of system, PN1-600), by embodiment
And the band adhering agent layer polaroid obtained in comparative example is cut to 233mm × 309mm size.From above-mentioned band adhering agent layer polaroid
Peel stripping film, the adhering agent layer exposed is attached at alkali-free glass (Corning Incorporated system, EAGLE XG) it
After, by Kurihara Seisakusho Co., Ltd. autoclave, pressurize 20 minutes at 0.5MPa, at 50 DEG C, this is made
For evaluating sample.
80 DEG C, put into above-mentioned evaluation sample 500 hours in the environment of drying regime (relative humidity be less than 35%) after,
10 times of magnifieres are used to confirm the presence or absence tilting and peeling off.Further, by following metewand, durability is evaluated.Will knot
Fruit is shown in table 2.
◎: unconfirmed to tilting and peeling off.
Zero: confirm tilting and the peeling of the size of below 0.5mm.
×: confirm tilting and the peeling of the size more than 0.5mm.
(test example 5) (mensuration of storage elastic modulus)
With the adhering agent layer that each embodiment or comparative example are identically formed thickness 30 μm.After this adhering agent layer of stacking, enter
Row is die-cut, thus makes the columned test film of diameter 8mm × thickness 3mm.For this test film, existed by torsional shear method
Storage elastic modulus at 80 DEG C (G ') (MPa) is measured under the conditions of following.Show the result in table 2.
Determinator: Rheometric Scientific, Inc. dynamic determination of viscoelasticity device " DYNAMIC
ANALYZER RDAII”
Frequency: 1Hz
Temperature: 80 DEG C
[table 2]
As shown in Table 2, the refractivity of active energy ray-curable adhesion composition and light diffusion microgranule 0.005～
In the range of 0.2, and the band adhering agent layer of the embodiment that the mean diameter of light diffusion microgranule is in the range of 0.8～2.9 μm is inclined
The sheet that shakes can obtain having sufficient durability and have light diffusing, and the optics structure of fine that dazzle is inhibited
Part.
Industrial applicibility
Cohesiveness compositions, sticker and the adhesive sheet of the present invention is adapted to provide for a kind of fine and has light diffusing
Optical component.
Description of reference numerals
1A, 1B: adhesive sheet；11: adhering agent layer；12,12a, 12b: stripping film；13: base material.
Claims (9)
1. a cohesiveness compositions, it is characterised in that contain:
Active energy ray-curable adhesion composition；And
Light diffusion microgranule,
The refractive index of described active energy ray-curable adhesion composition is 0.005 with the difference of the refractive index of described light diffusion microgranule
～0.2,
The mean diameter based on centrifugal sedimentation light transmission method of described light diffusion microgranule is 0.8～2.9 μm.
Cohesiveness compositions the most according to claim 1, it is characterised in that
Described active energy ray-curable adhesion composition contains (methyl) acrylate polymer and active energy beam is solid
The property changed compound.
Cohesiveness compositions the most according to claim 2, it is characterised in that
Described active energy ray-curable compound is the polyfunctional acrylic ester class monomer of molecular weight less than 1000.
4. according to the cohesiveness compositions described in Claims 2 or 3, it is characterised in that
Possibly together with cross-linking agent in described active energy ray-curable adhesion composition,
In described (methyl) acrylate polymer, as the monomeric unit of this polymer of composition, containing having and described crosslinking
The monomer of the functional group of agent reaction.
5. according to the cohesiveness compositions according to any one of Claims 1 to 4, it is characterised in that
Described light diffusion microgranule is by having the inorganic microgranule constituted with organic intermediate structure silicon-containing compound.
6. a sticker, it is formed by the cohesiveness compositions solidification according to any one of Claims 1 to 5.
Sticker the most according to claim 6, it is characterised in that
Haze value is 10～80%.
8. an adhesive sheet, possesses base material and adhering agent layer, it is characterised in that
Described adhering agent layer is made up of the sticker described in claim 6 or 7.
9. an adhesive sheet, it is characterised in that possess:
Two panels stripping film；And
Adhering agent layer, it clamps by described stripping film in the way of the release surface with described two panels stripping film contacts,
Described adhering agent layer is made up of claim 6 or 7 described stickers.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2014/058649 WO2015145633A1 (en) | 2014-03-26 | 2014-03-26 | Adhesive composition, adhesive agent, and adhesive sheet |
Publications (2)
| Publication Number | Publication Date |
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| CN106133079A true CN106133079A (en) | 2016-11-16 |
| CN106133079B CN106133079B (en) | 2020-04-24 |
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| CN201480077475.9A Active CN106133079B (en) | 2014-03-26 | 2014-03-26 | Adhesive composition, adhesive and adhesive sheet |
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|---|---|
| JP (1) | JP6198931B2 (en) |
| KR (1) | KR102232335B1 (en) |
| CN (1) | CN106133079B (en) |
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| WO (1) | WO2015145633A1 (en) |
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| CN107001890A (en) * | 2015-01-27 | 2017-08-01 | 琳得科株式会社 | Adherence composition, sticker and adhesive sheet |
| CN108459365A (en) * | 2017-02-20 | 2018-08-28 | 琳得科株式会社 | Image display with position detecting function |
| CN110643287A (en) * | 2018-06-27 | 2020-01-03 | 琳得科株式会社 | Adhesive sheet and optical laminate |
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| JP7071141B2 (en) * | 2018-02-07 | 2022-05-18 | スリーエム イノベイティブ プロパティズ カンパニー | Thermally stretchable decorative film for light projection and articles to which it is attached |
| JP7164980B2 (en) * | 2018-07-12 | 2022-11-02 | リンテック株式会社 | Adhesive sheet and anti-glare sheet |
| JP6764924B2 (en) * | 2018-12-27 | 2020-10-07 | リンテック株式会社 | Backlight unit manufacturing method |
| JP7340997B2 (en) * | 2019-09-05 | 2023-09-08 | リンテック株式会社 | Adhesive sheets and optical laminates |
| KR102677755B1 (en) * | 2021-08-12 | 2024-06-24 | (주)이녹스첨단소재 | Adhesive film for wafer back grinding |
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Also Published As
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| KR102232335B1 (en) | 2021-03-25 |
| TW201542735A (en) | 2015-11-16 |
| KR20160138154A (en) | 2016-12-02 |
| WO2015145633A1 (en) | 2015-10-01 |
| JPWO2015145633A1 (en) | 2017-04-13 |
| JP6198931B2 (en) | 2017-09-20 |
| CN106133079B (en) | 2020-04-24 |
| TWI670344B (en) | 2019-09-01 |
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