CN107001890A - Adherence composition, sticker and adhesive sheet - Google Patents
Adherence composition, sticker and adhesive sheet Download PDFInfo
- Publication number
- CN107001890A CN107001890A CN201580064801.7A CN201580064801A CN107001890A CN 107001890 A CN107001890 A CN 107001890A CN 201580064801 A CN201580064801 A CN 201580064801A CN 107001890 A CN107001890 A CN 107001890A
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- Prior art keywords
- methyl
- active energy
- energy ray
- fine particles
- agent layer
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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
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular 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
- 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
- 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
Abstract
A kind of adherence composition, the adherence composition contains active energy ray-curable adhesion composition and organic fine particles, and active energy ray-curable adhesion composition contains (methyl) acrylate polymer, active energy ray-curable compound and crosslinking agent, the refractive index of organic fine particles is 1.50~2.00, and the poor absolute value of the refractive index of active energy ray-curable adhesion composition and the refractive index of organic fine particles is 0.02~0.50.By the sticker obtained by the adherence composition, the optical module with abundant durability and light diffusivity can be obtained.
Description
Technical field
The present invention relates to a kind of adherence composition, sticker (material for solidifying adherence composition) and adhesion
Piece, more particularly to a kind of adherence composition, sticker and adhesive sheet suitable for optical modules such as polarizers.
Background technology
In general, in liquid crystal panel, when polarizer and polarizer to be bonded in glass substrate of liquid crystal cells etc.,
It is use the adhering agent layer formed by adherence composition more.But because the optical modules such as polarizer and polarizer are easily because of warm
Deng shrinking, therefore, contraction is produced because of accumulation heat, as a result, being noted stress-retained in the adhesion being layered on optical module
In oxidant layer, the problem of interface is peeling durability such as (so-called to float, peel off) is made because of the stress.
On the other hand, though liquid crystal panel has the advantages that slim and power consumption is small, have in terms of brightness or visual angle and do not fill
The problem of dividing.From the angle of this problem points is improved using adhering agent layer, the adhering agent layer for optical module, quilt are used as
It is required that need to have light diffusivity.
In order to assign adhering agent layer light diffusivity, particulate is generally added in adhering agent layer, but added in adhering agent layer
In the case of particulate, worry because the factors such as the thermal expansivity or the difference of heat-shrinkable in particulate and sticker cause, because
Accumulation heat makes to produce dislocation on the interface of particulate and sticker, the problem of producing bubble.
In addition, as described above, in the case of the optical module of thermal contraction, worrying that adhering agent layer can also make with its deformation
The problem of being misplaced as generation on the particulate of foreign matter and the interface of sticker and produce bubble.In fact, compared with without micro-
In the case of grain, in the case where fine-grained adhering agent layer will be added for optical module, because floating caused by accumulation heat
Or deterioration is peeled off, there is the tendency for reducing durability.
In this regard, in patent document 1, to provide a kind of sticker as problem, the sticker can durability bond well, together
When foaming or brightness disproportionation will not be also produced even across a period of time, in adhesion coating, liquid crystal display device has uniform bright
Degree, discloses gluing containing the adherence resin containing acrylic copolymer and active energy ray-curable compound and particulate
Agent.
Prior art literature
Patent document
Patent document 1：No. 4953717 publications of Japanese Patent No.
The content of the invention
The technical problem to be solved in the present invention
However, with the prosperity of the various mobile electron machines such as recent smart mobile phone and tablet terminal machine, liquid crystal display dress
Put and be required slimming.Require according to this, in optical module sticker, in the case of also forming thin adhering agent layer, tool
The necessity more and more higher of the sticker of standby sufficient light diffusivity and durability.
The present invention completes in view of the foregoing, it is therefore intended that offer it is a kind of as light diffusivity sticker, can obtain
Adherence composition, sticker and the adhesive sheet of optical module with excellent light diffusivity and durability.
Solve the technological means of technical problem
To achieve these goals, first, the present invention provides a kind of adherence composition, and it contains active energy line curing
Property adhesion composition and organic fine particles, it is characterised in that the active energy ray-curable adhesion composition contains (methyl) acrylic acid
Ester polymer, active energy ray-curable compound and crosslinking agent, the refractive index of the organic fine particles is 1.50~2.00, institute
It is 0.02 to state the refractive index of active energy ray-curable adhesion composition and the poor absolute value with the refractive index of the organic fine particles
~0.50 (invention 1).
In foregoing invention (invention 1), the average grain diameter that the organic fine particles are obtained by centrifugal sedimentation light transmission method is preferably
0.5~10 μm (invention 2).
In foregoing invention (invention 1,2), the organic fine particles are preferably by being used as structure list comprising methyl methacrylate
The particulate (invention 3) of the polymer formation of body unit.
Second, the present invention provides a kind of sticker, and it is by the way that the adherence composition (invention 1~3) solidification is formed
(invention 4).
In foregoing invention (invention 4), haze value is preferably 20~95% (inventions 5).
3rd, the present invention provides a kind of adhesive sheet (invention 6), and it has base material and adhering agent layer, it is characterised in that described
Adhering agent layer is formed by the sticker (invention 4,5).
4th, the present invention provides a kind of adhesive sheet (invention 7), it is characterised in that with 2 stripping films and with described 2
The adhering agent layer that the mode of the release surface contact of stripping film is clamped by the stripping film is opened, the adhering agent layer is by the sticker
(invention 4,5) is formed.
Invention effect
By adherence composition, sticker and the adhesive sheet of the present invention, it can obtain with abundant durability and light
The optical module of diffusive.
Brief description of the drawings
Fig. 1 is the profile of the adhesive sheet of the first embodiment of the present invention.
Fig. 2 is the profile of the adhesive sheet of second embodiment of the present invention.
Embodiment
Illustrated below for embodiments of the present invention.
[adherence composition]
The adherence composition (hereinafter referred to as " adherence composition P ") of present embodiment contains active energy ray-curable
Adhesion composition and organic fine particles.Active energy ray-curable adhesion composition contains (methyl) acrylate polymer, active-energy
Line curability compound and crosslinking agent.In addition, the refractive index of organic fine particles is 1.50~2.00, active energy ray-curable glues
The poor absolute value for the refractive index of composition and the refractive index of organic fine particles is 0.02~0.50.
In the adherence composition P of present embodiment, the refractive index of organic fine particles is larger, in addition, active energy line curing
Property adhesion composition refractive index and organic fine particles refractive index absolute value it is poor larger.Therefore, by adherence composition P,
High light diffusivity can be achieved.Particularly, in the case of adhering agent layer of the utilization adherence composition p-shaped into thickness of thin,
Also high light diffusivity can fully be realized.Further, since the required organic fine particles for realizing desired light diffusivity can be reduced
Amount, so can suppress because add organic fine particles cause the problem of durability is reduced.In addition, adherence composition P is solidified
Formed by sticker, pass through by active energy ray irradiation formed active energy ray-curable compound stereoscopic graticule
In structure, capture by the way that (methyl) acrylate polymer of cross-linked structure is reacted and be formed with crosslinking agent, and show height
Coagulability.Reduction and high coagulability by the usage amount of such a organic fine particles, can be achieved excellent durability.In addition,
Possess the optical module for the adhering agent layer that this utilization adherence composition P is formed, particularly polarizer, with sufficiently resistance to
Long property, and light diffusivity is excellent.
The composition 1. active energy ray-curable is adhered
Adherence composition P contains active energy ray-curable adhesion composition, active energy ray-curable adhesion composition
Contain (methyl) acrylate polymer (A), active energy ray-curable compound (B) and crosslinking agent (C).In addition, this theory
In bright book, (methyl) acrylate refers to acrylate and (methyl) both acrylate, and other similar terms are also identical.
In addition, also including the concept of " copolymer " in " polymer ".
As previously described, when the sticker containing organic fine particles being used for into the optical modules such as polarizer, can often occur durability
The problems such as.But in the present embodiment, by making adherence composition P contain above-mentioned active energy ray-curable adhesion composition,
Making the durability of obtained sticker becomes excellent.In addition, the usual coagulability reduction of sticker containing organic fine particles, from adhesion
When oxidant layer peels off stripping film, the situation that adhering agent layer sticks at stripping film side occurs sometimes.But it is above-mentioned containing active energy ray by making
The adherence composition P solidifications of curability adhesion composition, are not susceptible to above mentioned problem, the operability change of the adhering agent layer obtained
Obtain excellent.
(1) (methyl) acrylate polymer
(methyl) acrylate polymer (A), the carbon number for preferably comprising alkyl is 1~20 (methyl) alkyl acrylate
Base ester is used as the monomer for constituting the polymer.Thus, the sticker of acquisition can embody excellent adherence.In addition, (methyl) third
Olefine acid ester polymer (A) is preferably (methyl) alkyl acrylate of the carbon number 1~20 of alkyl, with reactive functional groups
Monomer (monomer containing reactive functional groups) and the copolymer according to required used other monomers.By making (methyl)
Acrylate polymer (A) contains the monomer containing reactive functional groups as the monomer for constituting the polymer, can improve and liquid crystal
The adaptation of the glass surfaces such as unit, in addition, also cross-linked structure can be formed with crosslinking agent described later (C) reaction.
(methyl) alkyl acrylate for being 1~20 as the carbon number of alkyl, can include (methyl) acrylic acid first
Ester, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid n-pentyl ester,
(methyl) the just own ester of acrylic acid, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid positive last of the ten Heavenly stems
Ester, positive ten diester of (methyl) acrylic acid, (methyl) myristyl ester, (methyl) acrylic acid palm ester, (methyl) acrylic acid
Octadecyl ester etc..Wherein, from the angle for improving adherence, preferably the carbon number of alkyl is 1~8 (methyl) alkyl acrylate
Base ester, more preferably (methyl) n-butyl acrylate or (methyl) 2-EHA.In addition, these (methyl) acrylic acid
Arrcostab can be used alone a kind, and two or more also can be combined and uses.
(methyl) acrylate polymer (A) preferably comprises 50~99 mass %, further preferably 65~97 mass %, spy
The carbon number for not preferably comprising 80~95 mass % alkyl gathers for 1~20 (methyl) alkyl acrylate as this is constituted
The monomeric unit of compound.
As the above-mentioned monomer containing reactive functional groups, preferably including intramolecular has the monomer (hydroxyl of hydroxyl
Monomer), the intramolecular monomer (carboxyl group-containing monomer) and intramolecular with carboxyl there is monomer (emulsion stability) of amino etc..
These monomers containing reactive functional groups can be used alone a kind, and two or more also can be combined and uses.
As hydroxyl monomer, (methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid 2- hydroxypropyl acrylates, (first can be included
Base) acrylic acid 3- hydroxypropyl acrylates, (methyl) acrylic acid 2- hydroxy butyl esters, (methyl) acrylic acid 3- hydroxy butyl esters, (methyl) acrylic acid 4- hydroxyls
Butyl ester etc. (methyl) acrylic acid hydroxy alkyl ester.Wherein, from the hydroxyl in (methyl) acrylate polymer (A) obtained and friendship
Connection agent (C) reactivity and set out with the angle of the copolymerizable of other monomers, preferably (methyl) acrylic acid 2- hydroxyl ethyl esters or
(methyl) acrylic acid 4- hydroxy butyl esters.These hydroxyl monomers can be used alone a kind, and two or more also can be combined and uses.
As carboxyl group-containing monomer, acrylic acid, methacrylic acid, crotonic acid, maleic acid, Yi Kang acid, burnt lemon can be included
The ethylenically unsaturated carboxylic acids such as acid.Wherein, from the carboxyl in (methyl) acrylate polymer (A) obtained and crosslinking agent (C)
Reactivity, and set out with the angle of the copolymerizable of other monomers, preferably acrylic acid.These carboxyl group-containing monomers can be used alone
1 kind, two or more also can be combined and uses.
As emulsion stability, (methyl) acrylate, (methyl) acrylic acid n-butyl amine base ethyl ester can be included
Deng.These emulsion stabilities can be used alone a kind, and two or more also can be combined and uses.
As the monomer containing reactive functional groups, hydroxyl monomer and carboxyl group-containing monomer are preferably used simultaneously, particularly preferably
Use acrylic acid simultaneously.In this case, as crosslinking agent described later (C), isocyanates crosslinking agent is preferably used.Due to containing
The reactivity of carboxylic monomer and isocyanates crosslinking agent is high, can turn into the crosslinking points of (methyl) acrylate polymer (A).Separately
On the one hand, carboxyl group-containing monomer, particularly acrylic acid, while the bonding force of the sticker obtained is improved, can also improve glass
Change transition temperature to improve coagulability.In addition, carboxyl group-containing monomer, particularly acrylic acid also have and promoted from hydroxyl monomer
The effect of cross-linking reaction between hydroxyl and isocyanates crosslinking agent.
(methyl) acrylate polymer (A) preferably comprises 1~25 mass %, particularly preferably contains 2~15 mass %, enters
One step preferably comprises 3~10 mass % monomer containing reactive functional groups as the monomeric unit for constituting the polymer.Same
When using in the case of hydroxyl monomer and carboxyl group-containing monomer, preferably comprise 0.05~20 mass %, particularly preferably containing 0.1~
10 mass %, further preferably 0.2~2 mass % hydroxyl monomer.Furthermore it is preferred that containing 0.5~20 mass %, spy
1~10 mass %, further preferably 2~8 mass % carboxyl group-containing monomer is not preferably comprised.
As above-mentioned other monomers, (methyl) acrylic acid methoxy ethyl ester, (methyl) acrylic acid ethoxy ethyl ester etc. can be included
(methyl) alkoxyalkyl acrylate, (methyl) cyclohexyl acrylate etc. has (methyl) acrylate of aliphatic ring, third
The acrylamide of the non-crosslinked property such as acrylamide, Methacrylamide, (methyl) acrylic acid N, N- dimethylaminoethyl, (methyl) third
Olefin(e) acid N, N- dimethylamino propyl ester etc. has (methyl) acrylate of the tertiary amino of non-crosslinked property, vinyl acetate, styrene
Deng.These monomers can be used alone a kind, and two or more also can be combined and uses.
The polymerization state of (methyl) acrylate polymer (A) can be random copolymer, or block copolymer.This
Outside, due to (methyl) acrylate polymer (A) to assign the composition of adherence, therefore preferably do not have active energy line curing
Property.
The weight average molecular weight of (methyl) acrylate polymer (A) is preferably 400,000~2,500,000, particularly preferably 1,000,000
~220 ten thousand, more preferably 1,400,000~2,000,000.By make the weight average molecular weight of (methyl) acrylate polymer (A) compared with
Height, can make durability more excellent.In addition, the weight average molecular weight in this specification, to be surveyed by gel permeation chromatography (GPC) method
Fixed polystyrene scaled value.
In addition, in adherence composition P, (methyl) acrylate polymer (A) can be used alone a kind, 2 kinds are also can be combined
It is used above.
(2) active energy ray-curable compound
The active energy ray-curable compound contained by active energy ray-curable adhesion composition in present embodiment
(B), as long as active energy ray-curable adhesion composition and organic fine particles containing the active energy ray-curable compound (B)
The absolute value of refringence can be any of monomer, oligomer or polymer in the scope, or
The mixture of these materials.The molecular weight excellent with the intermiscibility of (methyl) acrylate polymer (A) etc. can wherein be included
For less than 1000 polyfunctional acrylic ester class monomer.
In adherence composition P in present embodiment, pass through the irradiation of active energy ray, active energy ray-curable
Compound (B) forms mutually chemical bond, and then generates space network.In addition, in the structure, by capturing (methyl) acrylic acid
Ester polymer (A), can improve coagulability, as a result, durability becomes excellent.
As the polyfunctional acrylic ester class monomer that molecular weight is less than 1000, BDO two (methyl) can be included
Acrylate, 1,6-HD two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyethylene glycol two (methyl)
Acrylate, neopentyl glycol adipic acid two (methyl) acrylate, hydroxyl trimethylace tonitric neopentyl glycol two (methyl) acrylic acid
It is ester, bicyclopentyl two (methyl) acrylate, caprolactone modification dicyclopentenyl two (methyl) acrylate, ethylene-oxide-modified
Di(2-ethylhexyl)phosphate (methyl) acrylate, two (acryloyl-oxyethyl) isocyanuric acid esters, allylation cyclohexyl two (methyl) propylene
The functional-type of acid esters etc. two；Trimethylolpropane tris (methyl) acrylate, dipentaerythritol three (methyl) acrylate, propionic acid change
Property dipentaerythritol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, epoxy pronane modification trihydroxy methyl third
Alkane three (methyl) acrylate, three (acryloyl-oxyethyl) isocyanuric acid esters, 6-caprolactone are modified 33 (2- (methyl) propylene
Trimethylammonium) the trifunctional type such as isocyanuric acid ester；Two glycerine four (methyl) acrylate, new penta tetrol four (methyl) acrylic acid
The tetrafunctional type such as ester；Propionic acid is modified five functional-types such as dipentaerythritol five (methyl) acrylate；Dipentaerythritol six (methyl)
Six functional-types such as acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc..These polyfunctional acrylic esters
Class monomer can be used alone a kind, and two or more also can be combined and uses.
The content of active energy ray-curable compound (B) is relative to the mass of (methyl) acrylate polymer (A) 100
Part, preferably 1~50 mass parts, particularly preferably 5~30 mass parts, more preferably 10~20 mass parts.By making work
Within the above range, the durability of the sticker obtained becomes more excellent to the content of property energy ray-curable compound (B),
And the operability of the adhering agent layer obtained becomes more excellent.In addition, can also maintain (methyl) acrylic ester polymerization well
The adherence that thing (A) is brought.
(3) crosslinking agent
In adherence composition P in present embodiment, active energy ray-curable adhesion composition contains crosslinking agent (C).
Included in adherence composition P adhesion composition：Contain the monomer containing reactive functional groups as the monomer list for constituting polymer
In the case of (methyl) acrylate polymer (A) and crosslinking agent (C) of member, if adherence composition P is heated etc., hand over
The reactive functional groups for joining monomer containing reactive functional groups of agent (C) meeting with constituting (methyl) acrylate polymer (A) are anti-
Should.Thus, by the structure of crosslinking agent (C) (methyl) acrylate polymer (A) formation crosslinking, obtained sticker is improved
Coagulability.
In addition, in adherence composition P in present embodiment, passing through above-mentioned active energy ray-curable compound
(B) it can expect that the coagulability of the sticker obtained is improved, durability is improved.In addition, by using crosslinking agent (C), can tie up simultaneously
The appropriate bonding force of sticker is held, while further improving coagulability, durability is become more excellent.
As crosslinking agent (C), as long as the reactive functional groups reaction having with (methyl) acrylate polymer (A) is i.e.
Can, it can such as enumerate：Isocyanates crosslinking agent, epoxies crosslinking agent, amine cross-linking agent, melamine class crosslinking agent, nitrogen third
Pyridine class crosslinking agent, hydrazine class crosslinking agent, aldehyde crosslinking agent, oxazoline class crosslinking agent, metal alkoxide class crosslinking agent, metallo-chelate
Class crosslinking agent, metallic salt crosslinking agent, ammonium salt class crosslinking agent etc..There is hydroxyl conduct in (methyl) acrylate polymer (A)
In the case of reactive functional groups, in above-mentioned crosslinking agent, the isocyanates crosslinking agent excellent with hydroxyl reactive is preferably used.
In addition, crosslinking agent (C) can be used alone a kind, two or more also can be combined and uses.
Isocyanates crosslinking agent comprises at least polyisocyanate compounds.As polyisocyanate compounds, it can enumerate
Go out the aromatic poly-isocyanates such as toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, eylylene diisocyanate；Six
The aliphatic polymeric isocyanates such as the aliphatic such as methylene diisocyanate；IPDI, hydrogenated methylene diphenyld two
Ester ring type PIC such as isocyanates etc., and the biuret bodies of these materials, isocyanuric acid ester body or with ethylene glycol,
Addition product of reactant of the active dydrogen compounds containing low molecule such as propane diols, neopentyl glycol, trimethylolpropane, castor oil etc..
Wherein, from the reactive angle with hydroxyl, preferably trimethylolpropane modified aromatic adoption isocyanates, particularly preferred three
Hydroxymethyl-propane modified toluene diisocyanate.
The content of crosslinking agent (C) is relative to the mass parts of (methyl) acrylate polymer (A) 100, preferably 0.01~10
Mass parts, particularly preferably 0.05~5 mass parts, more preferably 0.1~1 mass parts.
(4) various additives
Active energy ray-curable adhesion composition can contain various additives according to demand, for example：Light trigger, silane are even
Join agent, refractive index adjusters, antistatic additive, tackifier, antioxidant, ultra-violet absorber, light stabilizer, softening agent, filling
Agent etc..
In the case of using ultraviolet as the active energy ray for solidifying adherence composition P, active energy ray is solid
It is preferable that the property changed adhesion composition preferably comprises light trigger.By containing light trigger, active energy ray-curable can be allowed to adhere into
Divide and efficiently solidify, in addition, can also reduce the exposure of polymerizing curable time and active energy ray.
As light trigger, styrax, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, styrax can be included
N-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino acetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 2,2- diethyls
Epoxide -2- phenyl acetophenones, 2- hydroxy-2-methyl -1- phenylpropyl alcohol alkane -1- ketone, 1- hydroxycyclohexylphenylketones, 2- methyl isophthalic acids-[4-
(methyl mercapto) benzene] -2- morpholines-propane -1- ketone, 4- (2- hydroxyls ethoxy) phenyl -2- (hydroxyl -2- propyl group) ketone, benzophenone, to benzene
Base benzophenone, 4,4 '-lignocaine benzophenone, dichloro benzophenone, 2- first anthraquinone, 2- second anthraquinone, the tertiary fourth anthraquinones of 2-, 2-
Ammonia anthraquinone, 2- methyl mercaptos xanthone, 2- ethylmercapto groups xanthone, 2- chlorine sulfenyls xanthone, 2,4- dimethyl sulphur-baseds xanthone, 2,4- bis-
Ethylmercapto group xanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, to dimethylamino benzoin ester, widow [2- hydroxyls -2-
Methyl isophthalic acid [4- (1- methyl ethylenes) benzene] acetone], 2,4,6- trimethylbenzoy-diphenies-phosphine oxide etc..These light
Initiator can be used alone a kind, and two or more also can be combined and uses.
Relative to the mass parts of active energy ray-curable compound (B) 100 in active energy ray-curable adhesion composition,
It is preferred that using light trigger with the amount of the scope of 0.1~20 mass parts, particularly preferably used with the amount of the scope of 1~12 mass parts
Light trigger.
In addition, from angle of the obtained sticker for the bonding force of glass surface etc. is improved, active energy ray is solid
The property changed adhesion composition preferably comprises silane coupler.As silane coupler, it is that intramolecular has at least one alcoxyl silicon substrate
Organo-silicon compound, preferably with adhere composition intermiscibility it is good and have excellent translucency silane coupler.
As this silane coupler, vinyltrimethoxy silane, VTES, methyl can be included
The silicon compound containing polymerism unsaturated group such as acryloxypropyl trimethoxy silane；3- glycidoxypropyl group front threes
The silicon compounds containing epoxy construction such as TMOS, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane；3- sulfydryls third
Base trimethoxy silane, 3- Mercaptopropyltriethoxysilanes, 3- mercaptopropyi dimethoxymethylsilanes etc. contain sulfydryl
Silicon compound；3- TSL 8330s, N- (2- amino-ethyls) -3- TSL 8330s, N- (2- ammonia
Base ethyl) silicon compound containing amino such as -3- amino propyl methyl dimethoxysilanes；3- r-chloropropyl trimethoxyl silanes,
3- isocyanates propyl-triethoxysilicanes, or it is at least one of above-mentioned with MTES, ethyl triethoxy silicane
Condensation product of the silicon compounds containing alkyl such as alkane, MTMS, ethyl trimethoxy silane etc..These silane couplers
It can be used alone a kind, two or more also can be combined and uses.
The content of silane coupler is relative to the mass parts of (methyl) acrylate polymer (A) 100, preferably 0.01~10
Mass parts, particularly preferably 0.05~5 mass parts, more preferably 0.1~1 mass parts.
2. organic fine particles
The refractive index of organic fine particles contained by the adherence composition P of present embodiment is 1.50~2.00, is preferably
1.52~1.80, particularly preferably 1.54~1.65.By making above-mentioned refractive index be more than 1.50, even if being film sticker,
Also sufficient light diffusivity can be assigned in the case where not damaging durability.On the other hand, in above-mentioned refractive index more than 2.00
In the case of, because the reflection of particle interface can become too much, there is the possibility for making optical characteristics be deteriorated.
As the organic fine particles for meeting above-mentioned refractive index, acrylic resin, polystyrene resin, polyethylene tree can be included
Organic translucency particulate such as fat, epoxy resin etc.；As acrylic resin particulate, the equal of methyl methacrylate can be included
Polymers or the monomer such as methyl methacrylate and vinyl acetate, styrene, methacrylate, (methyl) ethyl acrylate
The particulate that copolymer etc. is formed.Wherein, as organic fine particles, preferably acrylic resin particulate, particularly preferably by including first
The particulate that base methyl acrylate is formed as the polymer of structures alone unit, further preferably by methyl methacrylate and benzene
The particulate of the copolymer formation of ethene.Because this particulate readily satisfies above-mentioned refractive index, therefore suitably.Above organic fine particles can
1 kind is used alone, two or more also can be combined and uses.
It is used as the shape of organic fine particles, the preferably uniform spheroidal particle of light diffusion.Organic fine particles pass through centrifugal sedimentation light
The average grain diameter that saturating method is obtained is preferably 0.5~10 μm, particularly preferably 1.0~4.0 μm, more preferably 1.2~2.5 μ
m.It is less than 10 μm by making the average grain diameter of organic fine particles, is being applicable the light with adhering agent layer of the sticker obtained
Learn in component, fineness becomes more excellent.On the other hand, it is more than 0.5 μm by the average grain diameter for making organic fine particles, can obtains
Obtain sufficient light diffusivity.
In addition, for the average grain diameter obtained above by centrifugal sedimentation light transmission method, it is by 1.2g particulates and 98.8g isopropyls
Alcohol be sufficiently stirred for after material as test sample, using telecentricity decanter type particle size analyzer (Horiba, Ltd. are manufactured,
CAPA-700) it is measured.
Organic fine particles content in adherence composition P is relative to the above-mentioned active energy ray-curable adhesion matter of composition 100
Measure part, more preferably preferably 1~30 mass parts, particularly preferably 2~15 mass parts, 4~9 mass parts.This embodiment party
In the adherence composition P of formula, active energy ray-curable adhesion composition refractive index and organic fine particles refractive index it is poor
Absolute value is larger.Therefore, even if the content of organic fine particles is few, sufficient light diffusivity can also be realized.Further, since can reduce
Content, therefore can suppress the problem of the durability caused by adding organic fine particles is reduced, and then realize excellent durability.
3. refringence
The poor absolute value of the refractive index of active energy ray-curable adhesion composition and the refractive index of organic fine particles is 0.02
~0.50, preferably 0.04~0.20, particularly preferably 0.06~0.10.Adhered into by active energy ray-curable like this
Point and organic fine particles refringence absolute value it is larger, high light diffusivity can be realized with a small amount of addition.Particularly
In the case of adhering agent layer of the use adherence composition p-shaped into thickness of thin, sufficient high light diffusivity can be also realized.
Further, since the amount of the required organic fine particles for light diffusivity needed for realizing can be reduced, therefore it can suppress because being added with
Durability reduction caused by machine particulate, and then realize excellent durability.
In addition, the refractive index of active energy ray-curable adhesion composition is preferably 1.40~1.55, particularly preferably 1.42
~1.50, more preferably 1.44~1.49.
Here, the refractive index of active energy ray-curable adhesion composition is uses Abbe refractometer, using JIS K0062 as base
The numerical value that standard is determined.Further, since the refractive index of active energy ray-curable adhesion composition is constant before and after its solidification, because
This, can use the numerical value determined before its solidification, also can use the numerical value determined after its solidification.On the other hand, the folding of organic fine particles
Penetrate shown in the test example of rate as be described hereinafter, for the numerical value determined using refractive index titer.
4. the preparation method of adherence composition
Adherence composition P can be by by (methyl) acrylate polymer (A), active energy ray-curable compound
(B), crosslinking agent (C) and organic fine particles are mixed and prepared.For example, (methyl) acrylate polymer (A) can be first prepared, then
Blended by active energy ray-curable compound (B), crosslinking agent (C) and organic fine particles and according to required additive,
Prepare adherence composition P.
(methyl) acrylate polymer (A) can pass through：Using common radical polymerization, the list to constituting polymer
The mixture of body unit is polymerize and prepared.The polymerization of (methyl) acrylate polymer (A), can be according to demand using polymerization
Initiator, is acted on etc. by polymerisation in solution and carried out.As polymer solvent, ethyl acetate, n-butyl acetate, acetic acid can be included different
Butyl ester, toluene, acetone, hexane, MEK etc., two or more can be also used simultaneously.
As polymerization initiator, azo compound, organic peroxide etc. can be included, also can simultaneously using 2 kinds with
On.Azo compound, can include 2,2'- azobis isobutyronitriles, 2,2'- azos double (2- methylbutyronitriles), 1,1'- azos double
(hexamethylene 1- formonitrile HCNs), 2,2'- azos double (2,4- methyl pentane nitriles), the double (2,4- dimethyl -4- methoxyl groups penta of 2,2'- azos
Nitrile), dimethyl 2,2'- azos double (2- methyl propionates), 4,4'- azos double (the positive valeric acids of 4- cyano group), double (the 2- hydroxyls of 2,2'- azos
Ylmethyl propionitrile), 2,2'- azos double [2- (2- imidazoline -2- bases) propane] etc..
As organic peroxide, benzoyl peroxide, peroxidized t-butyl perbenzoate, hydrogen peroxide isopropyl can be included
Benzene, di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, peroxide two carbonic acid two (2- ethoxyethyl groups) ester, mistake
Aoxidize the neodecanoic acid tert-butyl ester, tert-Butyl peroxypivalate, peroxidating (3,5,5- front threes hexanoyl), dipropyonyl peroxide, peroxide
Change diacetyl etc..
In addition, in above-mentioned polymerization process, obtained polymer can be adjusted by blending the chain-transferring agents such as 2- mercaptoethanols
Weight average molecular weight.
Obtain after (methyl) acrylate polymer (A), by being added to the solution of (methyl) acrylate polymer (A)
Active energy ray-curable compound (B), crosslinking agent (C) and organic fine particles and according to required addition additive, it is fully mixed
Close, be derived from forming adherence composition P (coating solution) through solvent dilution.
As the retarder thinner that coating solution is prepared for diluting adherence composition P, hexane, heptane, ring can be included
The aliphatic hydrocarbons such as hexane；The aromatic hydrocarbons such as toluene, dimethylbenzene；The halogenated hydrocarbons such as dichloromethane, dichloroethanes；Methanol, ethanol, third
The alcohol such as alcohol, butanol, 1- methoxy-2-propanols；The ketone such as acetone, MEK, 2 pentanone, isophorone, cyclohexanone；Ethyl acetate,
The esters such as butyl acetate；Cellosolve type solvents such as ethyl cellosolve etc..
As the concentration and viscosity according to the above-mentioned coating solution being prepared from, as long as in the scope that can be coated
There is no particular restriction, according to circumstances can suitably select.For example, using adherence composition P concentration as 10~40 mass %'s
Mode is diluted.In addition, when obtaining coating solution, retarder thinner not necessarily condition is added, if adherence composition P is can
The viscosity being coated, also can be without retarder thinner etc..
[sticker]
The sticker of present embodiment is formed by solidifying adherence composition P, needed for adherence composition P is coated on
Object and make its dry after, by the irradiation of active energy ray make adherence composition P solidify, preferable adhesion can be obtained
Agent.
Though adherence composition P drying can be by air-drying progress, generally by heating (preferably heated-air drying)
Carry out.In the case where being heated, heating-up temperature is preferably 50~150 DEG C, particularly preferably 70~120 DEG C.In addition,
Heat time is preferably 10 seconds~10 minutes, particularly preferably 50 seconds~2 minutes.
As active energy ray, generally using ultraviolet, electron beam etc..Though the exposure of active energy ray is according to energy
The species of line and it is different, but for example using in the case of ultraviolet, light quantity is preferably 50~1000mJ/cm2, particularly preferably
100~500mJ/cm2.In addition, in the case of using electron beam, preferably 10~1000krad or so.
In adherence composition P active energy ray-curable adhesion composition, by adherence composition P drying (plus
Heat treatment), (methyl) acrylate polymer (A) is crosslinked by crosslinking agent (C) and is formed cross-linked structure.In addition, by right
Adherence composition P irradiates active energy ray, and the formation connected to each other of multiple active energy ray-curable compounds (B) is solid netted
Structure, thus it is speculated that (methyl) acrylate polymer that capture is crosslinked by crosslinking agent (C) in the space network
(A)。
[adhesive sheet]
As shown in figure 1, the adhesive sheet 1A of first embodiment since lower successively by stripping film 12, be laminated in stripping film 12
Release surface adhering agent layer 11 and be laminated in the base material 13 of adhering agent layer 11 and constitute.
In addition, as shown in Fig. 2 the adhesive sheet 1B of second embodiment is by 2 stripping film 12a, 12b and adhering agent layer
11 are constituted, and the adhering agent layer 11 is held in the way of the release surface with this 2 stripping film 12a, 12b is contacted this 2
Between stripping film 12a, 12b.In addition, the release surface of the stripping film in this specification refers to, the face in stripping film with fissility,
Even if including implementing the face of lift-off processing and lift-off processing is not carried out but showing any of the face of fissility.
In any adhesive sheet 1A, 1B, adhering agent layer 11 is by above-mentioned by the way that adherence composition P solidified
Sticker is formed.
The thickness of adhering agent layer 11 can suitably determine according to adhesive sheet 1A, 1B application target, but from realizing adhesive sheet
The angle of 1A, 1B filming and excellent durability and light diffusivity is set out, preferably 1~50 μm, more preferably 3~20
μm, in addition, along with the angle from fineness, particularly preferably 5~15 μm.As described earlier, present embodiment
By the way that the adherence composition P stickers solidified are contained into organic fine particles, while showing high coagulability.Therefore, adhere
Even if the thickness of oxidant layer 11 is thin, excellent durability can be also realized.That is, by the adherence composition P of present embodiment, it can obtain
There must be the adhering agent layer of the film of excellent light diffusivity and durability.
As base material 13, there is no particular restriction, and the base material used generally as the substrate sheets of adhesive sheet can be used.Example
Such as, in addition to required optical module, the spinning cloth or non-woven fabrics of the fibers such as artificial silk, acrylic acid, polyester are used；Glazed printing paper,
The stationeries such as glassine paper, dipping paper, coating paper；The metal foils such as aluminium, copper；The foaming bodies such as polyurethane foaming body, foam polyethylene；It is poly-
The polyester films such as PETP film, polybutylene terephthalate film, PEN film；Polyethylene film,
The polyolefin films such as polypropylene screen；The cellulose membranes such as cellulose triacetate；Polychloroethylene film, polyvinylidene chloride film, polyvinyl alcohol
Film, vinyl-vinyl acetate copolymer film, polyurethane film, polystyrene film, polycarbonate membrane, acrylic resin film, norborneol
The plastic foils such as vinyl resin film, cycloolefin resin film, layered product of two or more these film etc..Plastic foil can pass through uniaxial tension,
It may also pass through biaxial stretch-formed.
As optical module, polarizer (polarizing coating), polarizer, polarizer (phase retardation film), visual angle benefit can be included
Repay film, brightness and improve film, contrast raising film, liquid crystalline polymer film, diffusion barrier, Transflective film etc..Wherein, due to polarizer
(polarizing coating) shrinks easily and change in size is big, from the angle of durability, is suitable as being formed the adhesion of present embodiment
The object of agent (above-mentioned adhering agent layer 11).
Although the thickness of base material 13 is different according to species, such as in the case of optical module, usually 10~500 μ
M, particularly preferably preferably 50~300 μm, 80~150 μm.
As stripping film 12,12a, 12b, polyethylene film can be included, polypropylene screen, polybutene film, polybutadiene film, poly-
Methylpentene film, polychloroethylene film, vinyl chloride copolymer film, polyethylene terephthalate film, PEN film,
Polybutylene terephthalate film, polyurethane film, ethane-acetic acid ethyenyl ester film, ionomer resin film, ethene-(methyl) propylene
Acid copolymer film, ethene-(methyl) acrylate copolymer film, polystyrene film, polycarbonate membrane, polyimide film, fluorine tree
Adipose membrane etc..In addition, it is also possible to use the cross linking membrane of these films.The stacked film of further or these films.
It is preferred that implementing lift-off processing in the release surface (face particularly contacted with adhering agent layer 11) of above-mentioned stripping film.Make
For the remover used in lift-off processing, can include alcohol acids, silicone, fluorine class, unsaturated polyester (UP) class, TPO,
The remover of wax class.Peeled off furthermore it is preferred that a stripping film in stripping film 12a, 12b is set into the big re-release type of peeling force
Piece, another stripping film is set to the small light exfoliated stripping film of peeling force.
Though it is not particularly limited for stripping film 12,12a, 12b thickness, usually 20~150 μm or so.
It is coated and dried molten comprising adherence composition P in the release surface of stripping film 12 when manufacturing above-mentioned adhesive sheet 1A
After liquid (coating solution), the film layer for forming adhesion agent composition P, the laminated substrate 13 on the film layer.Also, by across
Stripping film 12 solidifies it above-mentioned film layer irradiation active energy ray, is consequently formed adhering agent layer 11.In addition, active energy ray
Irradiation condition is as hereinbefore.
In addition, when manufacturing above-mentioned adhesive sheet 1B, it is coated and dried in the stripping film 12a (or 12b) of side release surface
Above-mentioned adherence composition P coating solution is included, after the film layer for forming adherence composition P, is laminated on the film layer
The stripping film 12b (or 12a) of the opposing party.Also, by irradiating active energy to above-mentioned film layer across stripping film 12a (or 12b)
Amount line solidifies it, is consequently formed adhering agent layer 11.
In addition, can be substituted with following methods as described above across stripping film irradiation active energy ray formation adhering agent layer
11：Adherence composition P film layer is formed on stripping film, in the film layer to irradiate active-energy in the state of exposed
Line, is formed after adhering agent layer 11, laminated substrate or stripping film on the adhering agent layer 11.Further, can also be straight on base material
The film layer to form adherence composition P is connect, active energy ray is irradiated to the film layer, adhering agent layer 11 is formed.
As the method for being coated with above-mentioned coating solution, it can include using scraper rubbing method, scraper for coating method (knife
Coating method), rolling method, scraping blade rubbing method (blade coating method), die coating methods (die
Coating method), gravure coating process etc..
The bonding force of the adhesive sheet of present embodiment, the bonding force preferably for alkali-free glass is 0.5~20N/25mm, special
You Xuanwei not 1~15N/25mm, more preferably 3~more than 10N/25mm.In addition, herein so-called bonding force refer to
JIS Z0237:180 ° of peel adhesions (peeling rate 300mm/min) on the basis of 2009, are pasted on adherend,
0.5MPa, at 50 DEG C after pressurization 20 minutes, it is measured after standing 24 hours under conditions of 23 DEG C, 50%RH.By making bonding
Power within the above range, can be prevented from floating or peeled off when suitable for optical modules such as polarizers.
The transmission definition (image definition) of adhering agent layer in the adhesive sheet of present embodiment, by 0.125mm,
In the case that the transmission definition total value of the light comb of 0.25mm, 0.5mm, 1.0mm and 2.0mm comb width is represented, preferably 200
~500%, particularly preferably 290~490%, more preferably 400~480%.Adhering agent layer thickness now, be, for example,
5~15 μm.In addition, transmission definition herein refers to JIS K7374:Measured transmission is clear on the basis of 2007 transmission beam method
Degree.
The haze value of adhering agent layer in the adhesive sheet of present embodiment is (with JIS K7136:Determined on the basis of 2000
Numerical value) it is preferably 20~95%, particularly preferably 40~90%, more preferably 50~85%.By making haze value upper
In the range of stating, the sticker of present embodiment can take into account light diffusivity and fineness.Adhering agent layer thickness now, be, for example,
5~15 μm.
Herein, for example, manufacture be made up of liquid crystal cells and polarizer liquid crystal display device when, using polarizer as viscous
Piece 1A base material 13, adhesive sheet 1A stripping film 12 is peeled off, exposed adhering agent layer 11 and liquid crystal cells of fitting.
In addition, for example, being used as the liquid crystal display device for manufacturing the poor plate of the configuration phase between liquid crystal cells and polarizer
One example, first, the stripping film 12a (or 12b) of an adhesive sheet 1B side is peeled off, by adhesive sheet 1B exposed sticker
Layer 11 is fitted with polarizer.Then, the stripping film 12 for having used polarizer as the adhesive sheet 1A of base material 13 is peeled off, will be viscous
The exposed adhering agent layer 11 for piece 1A is fitted with above-mentioned polarizer.Further, from above-mentioned adhesive sheet B adhering agent layer 11
The stripping film 12b (or 12a) of the opposing party is peeled off, adhesive sheet B exposed adhering agent layer 11 is fitted with liquid crystal cells.
Adhesive sheet 1A, 1B more than, can obtain can play the optics group of excellent light diffusivity by adhering agent layer 11
Part.Further, since the morphological stability of adhering agent layer 11 is very excellent, such as, thus it is speculated that even in the bonding suitable for polarizer
In the case of, the deformation that adhering agent layer 11 suppresses polarizer can also be used, and then play high-durability.Thus, even in by
Under the environment for accumulating heat, the excellent light diffusivity of optical module and excellent ageing stability can be also assigned.
Embodiments described above, is to be recorded for the ease of understanding the present invention, is not intended to limit implementation of the present invention
Scope.Therefore, all design alterations or equivalent belonged in the technical scope of each element described in above-mentioned embodiment
Thing, is belonged in the range of patent of the present invention covers.
For example, adhesive sheet 1A stripping film 12 can be omitted, appointing in stripping film 12a, 12b in adhesive sheet 1B can be also omitted
One.
Embodiment
Hereinafter, further the present invention is specifically described by embodiment etc., but the scope of the present invention is not by these
Embodiment etc. is limited.
[embodiment 1]
The preparation of (1. methyl) acrylate polymer
Make the mass parts of n-butyl acrylate 94.5, the mass parts of acrylic acid 5 and the mass parts of acrylic acid 2- hydroxyl ethyl esters 0.5 common
It is poly-, (methyl) acrylate polymer (A) is prepared, the molecule for being somebody's turn to do (methyl) acrylate polymer (A) is determined in aftermentioned method
Amount, its weight average molecular weight is 1,800,000.
2. the preparation of adherence composition
By mass parts (the solid constituent scaled value of (methyl) acrylate polymer (A) 100 obtained in above-mentioned operation；
It is same as below), be used as three (acryloyl-oxyethyl) isocyanuric acid esters of active energy ray-curable compound (B)
(Toagosei Co., Ltd.s manufacture, ProductName " Aronix M-315 "；Molecular weight 423) 15 mass parts, and it is used as crosslinking agent
(C) trimethylolpropane modified toluene diisocyanate (Nippon Polyurethane Industry Co., Ltd. systems
Make, ProductName " Coronate L ") after the mixing of 0.3 mass parts, using as light trigger by benzophenone and 1- hydroxyl rings
Hexyl phenyl ketone is with 1:(Chiba Speciality Chemicals companies manufacture the mixture that 1 mass ratio is mixed, production
The name of an article " Iragacure 500 ") 1.5 mass parts, the 3- glycidoxypropyltrime,hoxysilanes as silane coupler
(Shin-Etsu Chemical Co., Ltd.s manufacture, ProductName " KBM-403 ") 0.2 mass parts are (solid for active energy ray above
The property changed adhesion composition) and being total to by styrene and methyl methacrylate as organic fine particles (acrylic resin particulate)
(Sekisui Plastics Co., Ltd.s manufacture the resin bead of polymers formation, ProductName " XX-16LA ", average grain diameter：2.5μ
M, refractive index 1.555) it is sufficiently stirred for after the addition of 5 mass parts, diluted using ethyl acetate and obtain the coating of adherence composition
Solution.
The blending of the adherence composition is shown in Table 1 herein.In addition, the detailed content such as code name described in table 1 is such as
Under：
[styrene/PMMA copolymer particles]
XX-16LA：Resin bead (the Sekisui Plastics formed by the copolymer of styrene and methyl methacrylate
Co., Ltd. manufactures, ProductName " XX-16LA ", average grain diameter：2.5 μm, refractive index：1.555)
XX-11LA：Resin bead (the Sekisui Plastics formed by the copolymer of styrene and methyl methacrylate
Co., Ltd. manufactures, ProductName " XX-11LA ", average grain diameter：3.5 μm, refractive index：1.555)
XX-06LA：Resin bead (the Sekisui Plastics formed by the copolymer of styrene and methyl methacrylate
Co., Ltd. manufactures, ProductName " XX-06LA ", average grain diameter：6 μm, refractive index：1.555)
[PMMA particulates]
XX-28LA：Formed by the methacrylate polymers being crosslinked resin bead (Sekisui Plastics Co.,
Ltd. manufacture, ProductName " XX-28LA ", average grain diameter：1.5 μm, refractive index：1.525)
SSX-103：Formed by the methacrylate polymers being crosslinked resin bead (Sekisui Plastics Co.,
Ltd. manufacture, ProductName " SSX-103 ", average grain diameter：3.0 μm, refractive index：1.490)
[silicone particulate]
tospearl 120：By with the inorganic particulate formed with organic intermediate structure silicon-containing compound
(Momentive Performance Materials Japan Inc. are manufactured, ProductName " tospearl120 ", average grain diameter：
2.0 μm, refractive index：1.430)
tospearl 145：By with the inorganic silicon-containing compound with organic intermediate structure formed it is micro-
(Momentive Performance Materials Japan Inc. are manufactured grain, ProductName
" tospearl145 ", average grain diameter：4.5 μm, refractive index：1.430)
3. the manufacture of the polarizer with adhering agent layer
Using knife type coater, by the coating solution of the adherence composition obtained in above-mentioned operation, utilization is coated on
Silicone remover has carried out the stripping film (Lintec of lift-off processing to the one side of polyethylene terephthalate film
Corporation. manufacture, SP-PET3811, thickness：38 μm) lift-off processing face on, afterwards with 90 DEG C heat 1 minute,
Form the film layer of adherence composition.
Then, be made up of the polarizing coating with discotic liquid crystal layer, polarizing coating and visual angle are expanded into the integrated polarization of film
Piece, fits in the exposed face of above-mentioned film layer.Then, across stripping film with following condition irradiation ultraviolet radiation, by making above-mentioned painting
Film layer is located at adhering agent layer, obtains the polarizer with adhering agent layer.In addition, the adhering agent layer thickness formed is 15 μm.
<Ultraviolet irradiates condition>
The electrodeless lamp H bulbs manufactured using Fusion companies
Illumination 600mW/cm2, light quantity 150mJ/cm2
UV illumination-quantometer uses Eye Graphics Co., " UVPF-36 " of Ltd. manufactures
[embodiment 2~12, comparative example 1~6]
Except organic fine particles species and blended amount are changed to it is as shown in table 1 in addition to, with side same as Example 1
Polarizer of the formula manufacture with adhering agent layer.
Herein, foresaid weight average molecular weight (Mw) is using gel permeation chromatography (GPC), and (GPC surveys are determined in following condition
Polystyrene conversion weight average molecular weight calmly).
<Condition determination>
GPC determining instruments：Tosoh Corporation are manufactured, HLC-8020
GPC tubing strings (pass through) in the following order：Tosoh Corporation are manufactured
TSK guard column HXL-H
TSK gel GMHXL(×2)
TSK gel G2000HXL
Determine solvent：Tetrahydrofuran
Determine temperature：40℃
[test example 1] (calculating of the measure and refringence of refractive index)
The refractive index of organic fine particles used in embodiment and comparative example is determined by the following method.Particulate is placed in
On slide, refractive index titer is dripped on particulate, covered makes sample., will using the micro- sem observation sample
Be most difficult to see particulate profile refractive index titer refractive index as particulate refractive index.
On the other hand, the adhesion composition refractive index used in embodiment and comparative example is determined by the following method.It is real
Apply in example and the respective adherence composition of comparative example without organic fine particles, and, carry sticker without using for making
The polarizer of the polarizer of layer, is used instead and the one side of polyethylene terephthalate film is peeled off using silicone remover
(Lintec Corporation. are manufactured the stripping film of processing, SP-PET3801, thickness：38 μm), it is 25 to make adhering agent layer thickness
μm, other parts are as described above, manufacture is by stripping film (SP-PET3801)/adhering agent layer (thickness：25 μm)/stripping film (SP-
PET3811 the adhesive sheet that composition) is constituted.
It regard the adhering agent layer that the individual layer that 2 stripping films are obtained is peeled off from above-mentioned adhesive sheet as determination sample.For
The determination sample, determines refractive index, in this, as active energy ray using Abbe refractometer on the basis of JIS K0062-1992
The refractive index of curability adhesion composition.
The refringence of active energy ray-curable adhesion composition and organic fine particles is calculated from above measurement result.
The refractive index of the organic fine particles that measure through the above way and composition of adhering and the refractive index that calculates it is poor
Absolute value is as shown in table 2.
[test example 2] (measure of haze value)
In embodiment and comparative example, without using the polarizer used when making the polarizer with adhering agent layer, use instead
Stripping film (the Lintec of lift-off processing has been carried out to the one side of polyethylene terephthalate film using silicone remover
Corporation. manufacture, SP-PET3801, thickness：38 μm), manufacture with stripping film (SP-PET3801)/adhering agent layer/stripping
The adhesive sheet that the composition of piece (SP-PET3811) is constituted.
For the adhering agent layer of the adhesive sheet obtained, haze meter (Nippon Denshoku Industries are utilized
Co., Ltd. manufactures, NDH2000), with JIS K7136:Haze value (%) is determined on the basis of 2000, as a result as shown in table 2.
[test example 3] (measure of transmission definition)
In embodiment and comparative example, without using the polarizer used when making the polarizer with adhering agent layer, use instead
Stripping film (the Lintec of lift-off processing has been carried out to the one side of polyethylene terephthalate film using silicone remover
Corporation. manufacture, SP-PET3801, thickness：38 μm), manufacture by stripping film (SP-PET3801)/adhering agent layer/stripping
The adhesive sheet that the composition of piece (SP-PET3811) is constituted.
The bonding plane of the adhering agent layer within 1 minute for peeling off stripping film from the adhesive sheet obtained, with JIS
K7374:On the basis of 2007 transmission beam method, using write as property analyzer (Suga Test Instruments Co., Ltd.s manufacture,
ICM-1DP transmission definition (image definition)) is determined.It is used to write as the comb width of the light comb in property analyzer is
0.125mm, 0.25mm, 0.5mm, 1.0mm, and 2.0mm, for transmission definition total value (%) such as table measured by each light comb
Shown in 2.
[test example 4] (durability evaluation)
For carrying adhering agent layer polarizer obtained in embodiment and comparative example, using cutting instrument (Ogino
Seisakusho Co., Ltd.s manufacture, Super Cutter, PN1-600) it is cut into 233mm × 309mm size.From above-mentioned band
Have and stripping film is peeled off on the polarizer of adhering agent layer, exposed adhering agent layer is pasted on alkali-free glass (Corning
Incorporated. manufacture, Eagle XG) after, with Kurihara Seisakusho manufacture autoclave 0.5MPa, 50 DEG C
Middle pressurization 20 minutes, regard this as evaluation sample.
After above-mentioned evaluation sample is placed 500 hours in the environment of 80 DEG C, drying regime (relative humidity is less than 35%),
It is confirmed whether to have using 10 times of magnifying glasses and floats or peel off, and durability is evaluated with following evaluation criterion, as a result as shown in table 2.
◎：It is unconfirmed to floating or peel off.
○：Confirm floating or peeling off for below 0.5mm sizes.
×：Confirm floating or peel off more than 0.5mm sizes.
[test example 5] (evaluation of fineness)
Metal vapor deposition layer is set on a glass, by carrying out at protective layer process (Resist process) and etching
Reason, forms the lattice-shaped pattern with the transmittance section that size is 60ppi (pixel/cun) size.By provided with this lattice-shaped pattern
Glass plate is carried on backlight (King.com Ltd. are manufactured, Bright Box 5000).
Then, the stripping film of the polarizer with adhering agent layer obtained in embodiment and comparative example is peeled off, so that
The unilateral side of polarization of polarizer with adhering agent layer is following mode, is carried on above-mentioned lattice-shaped pattern, really
Recognize the part that flash of light occurs.Then, the above-mentioned polarizer with adhering agent layer is made on lattice-shaped pattern, with parallel with glass plate
Direction movement, the flash of light confirmed in advance occur part and the above-mentioned polarizer with adhering agent layer it is mobile together in the case of,
Can determine whether the flash of light is due to caused by the above-mentioned polarizer with adhering agent layer.
In addition, the hair that glistened caused by the polarizer with adhering agent layer can not be confirmed in 60ppi lattice-shaped pattern
In the case of life, then using 70ppi lattice-shaped pattern, still it can not confirm because the above-mentioned polarizer with adhering agent layer causes
Flash of light occur when, further using 80ppi lattice-shaped pattern, like this in order, use every time be incremented by 10ppi grid
Shape pattern confirms that the flash of light caused by the polarizer with adhering agent layer occurs, and repeatedly same steps are dodged until that can confirm always
Untill light occurs.The flash of light unconfirmed arrived caused by the polarizer with adhering agent layer occurs, ppi is shown in table 2 most
Big lattice-shaped pattern (ppi).
Herein, the ppi in the flash of light caused by the polarizer with adhering agent layer, lattice-shaped pattern is bigger, in other words
The image quality of display is higher, then easier to occur.Therefore, ppi numerical value shown in table 2 is bigger, more can efficiently suppress
Flash of light occurs.In addition, can be described as high image quality polarizer more than 100ppi.
[test example 6] (measure of bonding force)
After the polarizer with adhering agent layer resulting in embodiment or comparative example is cut, breadth 25mm, length are made
Spend 100mm sample.Stripping film is peeled off from this sample, via exposed adhering agent layer in alkali-free glass (Corning
Incorporated manufacture, Eagle XG) on paste after the sample, utilize Kurihara Seisakusho companies manufacture height
Kettle is pressed in pressurization 20 minutes at 0.5MPa, 50 DEG C.Afterwards, after standing 24 hours under conditions of 23 DEG C, 50%RH, stretching is utilized
Testing machine (Orientec Co., Ltd.s manufacture, Tensilon), in peeling rate 300mm/min, the condition of 180 ° of peel angle
It is lower to determine the bonding force (bonding force after pasting 1 day；N/25mm), as a result as shown in table 2.
[table 1]
[table 2]
As known from Table 2, the polarizer with adhering agent layer of embodiment has excellent light diffusivity and excellent durability.
In addition, the polarizer with adhering agent layer of embodiment has sufficient fineness and bonding force.
Industrial applicibility
Adherence composition, sticker and the adhesive sheet of the present invention, which is suitable as the optical module with light diffusivity, to be made
With, especially can as in order that in liquid crystal display device the light from backlight uniformly diffusion used in optical module
With.
Description of reference numerals
1A、1B：Adhesive sheet；11：Adhering agent layer；12、12a、12b：Stripping film；13：Base material.
Claims (7)
1. a kind of adherence composition, it contains active energy ray-curable adhesion composition and organic fine particles, it is characterised in that
The active energy ray-curable adhesion composition contains (methyl) acrylate polymer, active energy ray-curable chemical combination
Thing and crosslinking agent,
The refractive index of the organic fine particles is 1.50~2.00,
The poor absolute value of the refractive index of active energy ray-curable adhesion composition and the refractive index of the organic fine particles is
0.02~0.50.
2. adherence composition according to claim 1, it is characterised in that the organic fine particles are saturating by centrifugal sedimentation light
The average grain diameter that method is obtained is 0.5~10 μm.
3. adherence composition according to claim 1 or 2, it is characterised in that the organic fine particles are by including methyl
The particulate that methyl acrylate is formed as the polymer of structures alone unit.
4. a kind of sticker, it is by the way that adherence composition according to any one of claims 1 to 3 solidification is formed.
5. sticker according to claim 4, it is characterised in that haze value is 20~95%.
6. a kind of adhesive sheet, it has base material and adhering agent layer, it is characterised in that the adhering agent layer is by the institute of claim 4 or 5
The sticker stated is formed.
7. a kind of adhesive sheet, it is characterised in that it is had 2 stripping films and contacted with the release surface with 2 stripping films
The adhering agent layer that mode is clamped by the stripping film, the adhering agent layer is formed as the sticker described in claim 4 or 5.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010077628.7A CN111171730B (en) | 2015-01-27 | 2015-01-27 | Adhesive composition, adhesive and adhesive sheet |
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/JP2015/052202 WO2016121001A1 (en) | 2015-01-27 | 2015-01-27 | Adhesive composition, adhesive and adhesive sheet |
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| CN202010077628.7A Division CN111171730B (en) | 2015-01-27 | 2015-01-27 | Adhesive composition, adhesive and adhesive sheet |
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| CN107001890A true CN107001890A (en) | 2017-08-01 |
| CN107001890B CN107001890B (en) | 2020-06-12 |
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| CN201580064801.7A Active CN107001890B (en) | 2015-01-27 | 2015-01-27 | Adhesive composition, adhesive and adhesive sheet |
| CN202010077628.7A Active CN111171730B (en) | 2015-01-27 | 2015-01-27 | Adhesive composition, adhesive and adhesive sheet |
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|---|---|
| JP (1) | JP6214797B2 (en) |
| KR (1) | KR102298392B1 (en) |
| CN (2) | CN107001890B (en) |
| TW (1) | TWI683874B (en) |
| WO (1) | WO2016121001A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110643287A (en) * | 2018-06-27 | 2020-01-03 | 琳得科株式会社 | Adhesive sheet and optical laminate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018090727A (en) * | 2016-12-06 | 2018-06-14 | Dic株式会社 | Optical film and information display device prepared therewith |
| TW202128921A (en) * | 2019-10-15 | 2021-08-01 | 日商積水化學工業股份有限公司 | Gap material, adhesive, and display device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074349A (en) * | 2006-05-19 | 2007-11-21 | 琳得科株式会社 | Pressure-sensitive adhesive for applying optically functional film, optically functional film and production process for the same |
| CN102171300A (en) * | 2008-09-17 | 2011-08-31 | 3M创新有限公司 | Light diffusive pressure sensitive adhesive |
| CN103298898A (en) * | 2010-11-08 | 2013-09-11 | Lg化学株式会社 | Adhesive composition |
| CN106133079A (en) * | 2014-03-26 | 2016-11-16 | 琳得科株式会社 | Cohesiveness compositions, sticker and adhesive sheet |
| CN106164194A (en) * | 2014-03-26 | 2016-11-23 | 琳得科株式会社 | Adhesive phase and the anti-bonding sheet that disperses |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5258332B2 (en) * | 2008-03-06 | 2013-08-07 | 日東電工株式会社 | Light scattering adhesive composition, light scattering adhesive layer, light scattering adhesive sheet, and backlight system using them |
| JP5590582B2 (en) * | 2009-11-05 | 2014-09-17 | エルジー・ケム・リミテッド | Backlight unit |
| JP5645487B2 (en) * | 2010-02-01 | 2014-12-24 | 日本カーバイド工業株式会社 | Light diffusion sheet, lighting device using light diffusion sheet, and display device |
| JP5592671B2 (en) * | 2010-03-02 | 2014-09-17 | リンテック株式会社 | Anti-glare hard coat film and polarizing plate using the same |
| JP5008734B2 (en) * | 2010-03-18 | 2012-08-22 | 大日本印刷株式会社 | Antiglare film, method for producing antiglare film, polarizing plate and image display device |
| JP5821309B2 (en) * | 2011-06-14 | 2015-11-24 | 住友化学株式会社 | Light diffusing adhesive sheet, polarizing plate and liquid crystal display panel |
| JP5613109B2 (en) * | 2011-06-28 | 2014-10-22 | リンテック株式会社 | Adhesive and adhesive sheet |
| KR101630012B1 (en) * | 2013-06-19 | 2016-06-13 | 주식회사 엘지화학 | Adhesive film and preparation method of adhesive film using electric field |
-
2015
- 2015-01-27 KR KR1020177017821A patent/KR102298392B1/en active IP Right Grant
- 2015-01-27 JP JP2016571551A patent/JP6214797B2/en active Active
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074349A (en) * | 2006-05-19 | 2007-11-21 | 琳得科株式会社 | Pressure-sensitive adhesive for applying optically functional film, optically functional film and production process for the same |
| CN102171300A (en) * | 2008-09-17 | 2011-08-31 | 3M创新有限公司 | Light diffusive pressure sensitive adhesive |
| CN103298898A (en) * | 2010-11-08 | 2013-09-11 | Lg化学株式会社 | Adhesive composition |
| CN106133079A (en) * | 2014-03-26 | 2016-11-16 | 琳得科株式会社 | Cohesiveness compositions, sticker and adhesive sheet |
| CN106164194A (en) * | 2014-03-26 | 2016-11-23 | 琳得科株式会社 | Adhesive phase and the anti-bonding sheet that disperses |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110643287A (en) * | 2018-06-27 | 2020-01-03 | 琳得科株式会社 | Adhesive sheet and optical laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016121001A1 (en) | 2016-08-04 |
| CN107001890B (en) | 2020-06-12 |
| JP6214797B2 (en) | 2017-10-18 |
| CN111171730B (en) | 2022-03-18 |
| KR20170107980A (en) | 2017-09-26 |
| CN111171730A (en) | 2020-05-19 |
| TW201634643A (en) | 2016-10-01 |
| TWI683874B (en) | 2020-02-01 |
| JPWO2016121001A1 (en) | 2017-10-05 |
| KR102298392B1 (en) | 2021-09-07 |
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