CN103980845B - Pressure-sensitive-adhesive composition, contact adhesive and pressure sensitive adhesion sheet - Google Patents
Pressure-sensitive-adhesive composition, contact adhesive and pressure sensitive adhesion sheet Download PDFInfo
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- CN103980845B CN103980845B CN201410049204.4A CN201410049204A CN103980845B CN 103980845 B CN103980845 B CN 103980845B CN 201410049204 A CN201410049204 A CN 201410049204A CN 103980845 B CN103980845 B CN 103980845B
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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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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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
- C09J7/20—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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
Abstract
The present invention, which provides, has excellent antistatic property, suitable for polarizer when optical components, durability also excellent pressure-sensitive-adhesive composition, contact adhesive and pressure sensitive adhesion sheet.In order to solve the above problems, pressure-sensitive-adhesive composition is provided, is contained：(methyl) acrylate polymer (A), weight average molecular weight are 1,000,000~2,500,000, contain the monomer with hydroxyl and the monomer with aromatic rings, without monomeric unit of the monomer with carboxyl as composition polymer；Isocyanates system crosslinking agent (B)；Silane coupling agent (C), with sulfydryl as the functional group reacted with organic material；With antistatic agent (D)；The monomer with hydroxyl that (methyl) acrylate polymer (A) contains the mass % of 1 mass %~10 contains the monomer with aromatic rings of the mass % of 1 mass %~10 as the monomeric unit for forming the polymer.
Description
【Technical field】
The present invention relates to pressure-sensitive-adhesive composition, contact adhesive (making the crosslinked material of pressure-sensitive-adhesive composition) with
And pressure sensitive adhesion sheet, more particularly to it is suitable as pressure-sensitive-adhesive composition, the contact adhesive of the optical components such as polarizer
And pressure sensitive adhesion sheet.
【Background technology】
In recent years in electronic equipment of various, mostly using the touch-screen for having both display device and input equipment.The kind of touch-screen
Owner will have resistance membrane type, condenser type, optical profile type and ultrasonic type.Resistive touch panel have analogue data resistance membrane type with
And resistance matrix membrane type, capacitive touch screen have surface type and projection type.
The touch-screen of the mobile electronic equipments such as the smart mobile phone, the tablet computer terminal that attract attention recently, mostly using throwing
The capacitive touch-screen of shadow type.As the projection type capacitive touch screen of the mobile electron machine, for example, researching and proposing
Laminated liquid crystal display device (LCD), pressure sensitive adhesive layer, transparent conductive film (tin-doped indium oxide successively from below：ITO), glass
The touch-screen of the protective layers such as glass substrate, transparent conductive film (ITO) and strengthened glass.
As the optical component for forming above-mentioned liquid crystal display device, generally using Liquid crystal module.Liquid crystal module is usually will
The both alignment layers for forming the two panels transparent electrode substrate of both alignment layers are used as inside, by partition, in a manner of forming predetermined distance, into
Row configuration, by its peripheral sealing, the component of clamping liquid crystal material between two panels transparent electrode substrate.In general, in Liquid crystal module
In two panels transparent electrode substrate outside, be utilized respectively contact adhesive bonding polarizer.
As the contact adhesive used in touch-screen, for example, as it is known that there is the pressure-sensitive adhesion shown in patent document 1
Agent.The contact adhesive contains：Compared with (methyl) acrylic acid of the alkyl with carbon number 4~14 as monomeric unit
100 parts by weight of Arrcostab contain the parts by weight of 0.2 parts by weight of monomer with carboxyl~20 as copolymer composition and form (first
Base) acrylic acid series polymeric compounds and compared with 100 parts by weight of (methyl) acrylic acid series polymeric compounds, contain the mistake as crosslinking agent
The parts by weight of the parts by weight of 0.02 parts by weight of oxide~2 and 0.005 parts by weight of epoxy crosslinking agent~5.
【Prior art literature】
【Patent document】
【Patent document 1】Japanese Unexamined Patent Publication 2009-242786 publications
【The content of the invention】
【The subject that the invention solves】
With the slimming of mobile electronic device in recent years, the slimming of component parts polarizer is also promoting.Specifically
For, gradually use the polarizer as the film thickness reduction of the protective film of the polyvinyl alcohol of polarization element from both sides holding.This
Outside, the protective film as polarizer, optical functional film that gradually application deaerates the easy generation such as cyclic olefin polymer etc. (with
Under, have the situation that the one of the protective film square polarizer as cyclo-olefin-polymer films is known as to " COP polarizers ").Described
In the case of, contact adhesive requirement is than previous higher reliability (durability).In addition, contact adhesive is used as Liquid crystal module
In the case of, be noted contact adhesive it is charged make liquid crystal orientation it is chaotic the problems such as, go out from the viewpoint of the problem is prevented
Hair, also requirement are endowed the contact adhesive of antistatic property.
In this regard, the contact adhesive durability in above patent document 1 is low, due to through when or under the high temperature conditions, it is wet
Under heat condition, there is the problem of easily heaving, removing.In addition, the pressure-sensitive adhesion type optical component in above patent document 1
In, although in addition be provided with antistatic property layer structure, be not assigned in itself for contact adhesive it is antistatic
The structure of property.
It, generally, will be as the structure of (methyl) acrylic acid series polymeric compounds as the method for the durability for improving contact adhesive
The monomer with high glass-transition temperature (Tg) into ingredient carries out combined polymerization.But the polarizer of slimming is in heat-resisting item
Big shrinkage stress is generated under part, in the pressure sensitive adhesive layer for being designed to high glass-transition temperature, its shrinkage stress of relaxation
Become difficult, touch-screen can deform.The pack clearance in the end of liquid crystal display device broadens as a result, so as to display
Property brings harmful effect.
The present invention be in view of such present situation and make, and it is an object of the present invention to provide suitable for having excellent antistatic property,
And pressure-sensitive-adhesive composition that be suitable as the optical components such as polarizer, excellent in te pins of durability, contact adhesive and pressure
Quick bonding sheet.
【Means for solving the problems】
In order to achieve the above objectives, first, the present invention provides pressure-sensitive-adhesive composition, contains：(methyl) acrylic acid
Ester polymer (A), weight average molecular weight are 1,000,000~2,500,000, containing the monomer with hydroxyl and the monomer with aromatic rings,
Without the monomer with carboxyl as the monomeric unit for forming polymer；Isocyanates system crosslinking agent (B)；Silane coupling agent (C),
It is with sulfydryl as the functional group reacted with organic material；With antistatic agent (D)；(methyl) acrylate polymer
(A) containing 1 mass %~the mass % of 10 monomer with hydroxyl described in mass %, containing 1 mass %~10 described in fragrance
The monomer of ring is as the monomeric unit (invention 1) for forming the polymer.
In foregoing invention (invention 1), monomer with hydroxyl of (methyl) acrylate polymer (A) containing specified amount
And the monomer with aromatic rings, meanwhile, pressure-sensitive-adhesive composition is obtained pressure-sensitive by containing silane coupling agent (C)
The durability of adhesive is high.In addition, the pressure-sensitive-adhesive composition is by containing antistatic agent (D), it is obtained pressure-sensitive viscous
Not only durability is high for mixture, and antistatic property is also excellent.
In foregoing invention (invention 1), isocyanates system crosslinking agent (B) in the pressure-sensitive-adhesive composition
Content is preferably the mass parts (invention of 0.1 mass parts~1 compared with 100 mass parts of (methyl) acrylate polymer (A)
2)。
Foregoing invention (invention 1, in invention 2), the silane coupling agent (C) in the pressure-sensitive-adhesive composition
Content is preferably the mass parts (hair of 0.01 mass parts~1 compared with 100 mass parts of (methyl) acrylate polymer (A)
It is bright 3).
Second, present invention offer is pressure-sensitive viscous obtained from pressure-sensitive-adhesive composition (invention 1~invention 3) is crosslinked
Mixture (invention 4).
In foregoing invention (invention 4), from pressure sensitive adhesive layer formation, in the environment of 23 DEG C, 50%RH, preserve 7 days
Afterwards, preferably gel fraction is 75%~90% (invention 5).
Foregoing invention (invention 4, invention 5) in, preferably 23 DEG C storage modulus (G ') for 0.05MPa~
0.20MPa is 0.05MPa~0.15MPa (invention 6) in 80 DEG C of storage modulus (G ').
3rd, the present invention provides pressure sensitive adhesion sheet, it is characterised in that：To be glued with base material and the pressure-sensitive of pressure sensitive adhesive layer
Piece is closed, the pressure sensitive adhesive layer includes the contact adhesive (invention 4~invention 6) (invention 7).
In foregoing invention (invention 7), the base material is preferably optical component (invention 8).
In foregoing invention (invention 8), the optical component is preferably polarizer (invention 9).
4th, the present invention provides pressure sensitive adhesion sheet, it is characterised in that：It is removed with two panels stripping film and with the two panels
The mode that the release surface of piece connects clamps the pressure sensitive adhesive layer of the stripping film, and the pressure sensitive adhesive layer includes described pressure-sensitive
Adhesive (invention 4~invention 6) (invention 10).
【The effect of invention】
(methyl) acrylate polymer of pressure-sensitive-adhesive composition of the present invention contain specified amount have hydroxyl
The monomer of base and the monomer with aromatic rings, obtained contact adhesive is not only with excellent cohesive force, stress as a result,
Slackness is also enriched, and durability is high as a result,.In addition, pressure-sensitive-adhesive composition of the present invention contains sulfydryl as with having
The silane coupling agent of the functional group of machine material reaction, obtained contact adhesive adhesiveness is excellent as a result, durability higher.
In addition, heretofore described pressure-sensitive-adhesive composition contains antistatic agent, obtained contact adhesive not only has as a result,
There is high-durability, antistatic property is also excellent.
【Description of the drawings】
Fig. 1 is the sectional view of the pressure sensitive adhesion sheet involved by first embodiment of the present invention.
Fig. 2 is the sectional view of the pressure sensitive adhesion sheet involved by second embodiment of the present invention.
【Reference sign】
1A, 1B ... pressure sensitive adhesion sheet
11 ... pressure sensitive adhesive layers
12,12a, 12b ... stripping film
13 ... base materials
【The embodiment of invention】
Hereinafter, illustrated on embodiments of the present invention.
(pressure-sensitive-adhesive composition)
Pressure-sensitive-adhesive composition (hereinafter referred to as " pressure-sensitive-adhesive composition P ") involved by present embodiment, contains：
(methyl) acrylate polymer (A), isocyanates system crosslinking agent (B) have sulfydryl as the function reacted with organic material
Silane coupling agent (C), the antistatic agent (D) of group, the weight average molecular weight of (methyl) acrylate polymer (A) is 1,000,000
~250 ten thousand, containing the monomer (hydroxyl monomer) with hydroxyl and the monomer (monomer containing aromatic rings) with aromatic rings, without tool
There is the monomer (carboxyl group-containing monomer) of carboxyl as the monomeric unit for forming polymer.In addition, (methyl) acrylate polymer
(A), containing 1 mass %~10 mass % hydroxyl monomer and the mass % of 1 mass %~10 monomer containing aromatic rings as form should
The monomeric unit of polymer.In addition, in the present specification, so-called (methyl) acrylate refers to acrylate and methyl-prop
Two sides of olefin(e) acid ester.Other similar terms are also the same.In addition, " polymer " also includes the concept of " copolymer ".
In the pressure-sensitive-adhesive composition P, (methyl) acrylate polymer (A) passes through having containing specified amount
Pressure-sensitive-adhesive composition P, is crosslinked by the monomer of hydroxyl and the monomer with aromatic rings as a result, obtained pressure-sensitive viscous
Mixture has both cohesive force and stress relaxation, and durability is high.
In addition, if above-mentioned pressure-sensitive-adhesive composition P is crosslinked, the sulfydryl and isocyanic acid of silane coupling agent (C)
The isocyanate group of ester system crosslinking agent (B) easily forms thiocarbamate key, the isocyanates system crosslinking agent (B) other
The hydroxyl reaction of isocyanate group and (methyl) acrylate polymer (A) and will (methyl) acrylate polymer (A) crosslinking,
Form three-dimensional net structure.Moreover, the alkoxysilyl of silane coupling agent (C) by inference, gathers with (methyl) acrylate
The distance that object (A) keeps suitable is closed, becomes the form for hanging on (methyl) acrylate polymer (A).It plays as a result, excellent
Coupling effect, obtained contact adhesive, even if under the high temperature conditions or under wet heat condition, adhesion durability is also more excellent.
In addition, in the pressure-sensitive-adhesive composition P, (methyl) acrylate polymer (A) is not due to containing conduct
The monomer with carboxyl of sour ingredient can inhibit the pasted objects of obtained contact adhesive due to bad caused by acid
Phenomenon, such as when transparent conductive film or metal film, can inhibit due to these bad phenomenons caused by acid.Especially
It is that, when pasted objects are the situation of transparent conductive film, the transparent conductive film can be inhibited and be corroded or the transparent conductive film
Resistance value changes.Moreover, the silane coupling agent (C) with sulfydryl, also effectively plays in such no acid system
Effect.
(1) (methyl) acrylate polymer (A)
(methyl) acrylate polymer (A), in addition to containing above-mentioned hydroxyl monomer and monomer containing aromatic rings, preferably
Monomeric unit of (methyl) alkyl acrylate that the carbon number for containing alkyl is 1~20 as the composition polymer, especially
It is to contain preferably as principal component.In addition, it can also contain other monomers as needed (in addition to the monomer containing carboxyl).
The carbon number of (methyl) acrylate polymer (A) containing alkyl is 1~20 (methyl) alkyl acrylate
As the monomeric unit for forming the polymer, thus, it is possible to show excellent adhesiveness.Carbon number as alkyl for 1~
20 (methyl) alkyl acrylate, for example, can include (methyl) methyl acrylate, (methyl) ethyl acrylate,
(methyl) propyl acrylate, (methyl) n-butylacrylate, (methyl) acrylic acid n-pentyl ester, (methyl) acrylic acid just oneself
Base ester, (methyl) 2-ethylhexyl acrylate, (methyl) iso-octyl acrylate, (methyl) acrylic acid positive decyl ester, (first
Base) acrylic acid n-dodecane base ester, (methyl) myristyl base ester, (methyl) acrylic acid palm base ester, (methyl) propylene
Sour stearyl etc..Wherein, from the viewpoint of adhesiveness is improved, the carbon number of optimizing alkyl is 1~4 (methyl) propylene
Acid esters, particularly preferably (methyl) methyl acrylate and (methyl) n-butylacrylate.Moreover, these can individually make
With can also be used in combination of two or more.
(methyl) acrylate polymer (A) preferably comprises the mass % of 50 mass %~98, particularly preferably contains 70 mass %
The carbon number of the alkyl of the mass % of~96 mass %, further preferably 80 mass %~94 is 1~20 (methyl) acrylic acid
Arrcostab is as the monomeric unit for forming the polymer.
(methyl) acrylate polymer (A) contains monomeric unit of the monomer with hydroxyl as the composition polymer,
The isocyanate group reactivity of the hydroxyl and isocyanates system crosslinking agent (B) is high, and due to these reactions, (methyl) acrylate gathers
Object (A) is closed to be crosslinked by isocyanates system crosslinking agent (B).By this cross-linked structure, obtained contact adhesive durability is excellent
It is different.
As hydroxyl monomer, for example, (methyl) acrylic acid 2- hydroxyethyls ester, (methyl) acrylic acid 2- hydroxyls can be enumerated
Propyl diester, (methyl) acrylic acid 3- hydroxy-propyl esters, (methyl) acrylic acid 2- hydroxybutyls ester, (methyl) acrylic acid 3- hydroxyl fourths
(methyl) hydroxyalkyl acrylates such as base ester, (methyl) acrylic acid 4- hydroxybutyl esters etc., wherein, it is handed over from isocyanates system
From the aspect of joining agent (B) reactivity, preferably (methyl) acrylic acid 2- hydroxyethyls ester or (methyl) acrylic acid 4- hydroxybutyls
Ester.These both may be used singly or in combination of two or more use.
(methyl) acrylate polymer (A) preferably comprises the mass % of 2 mass %~8 containing the mass % of 1 mass %~10, special
The hydroxyl monomer of the mass % of 2.5 mass %~5 You Xuanwei not contained as the monomeric unit for forming the polymer.Pass through hydroxyl
For the content of monomer in above range, the cross-linked structure formed is good, and obtained contact adhesive has superior durable
Property.The content of hydroxyl monomer is if less than 1 mass %, then crosslinking points are very few, and cohesive force reduces, obtained contact adhesive
Excellent durability is not played.On the other hand, the content of hydroxyl monomer is if it exceeds 10 mass %, then crosslinking points are excessive, gained
To contact adhesive become not soft, stress relaxation reduces, therefore can not tackle the contraction of base material, and durability is caused to drop
It is low.
(methyl) acrylate polymer (A) preferably comprises the monomer with aromatic rings as the list for forming the polymer
Body unit, as a result, (methyl) acrylate polymer (A) there is appropriate hardness, obtained contact adhesive has cohesion concurrently
Force and stress slackness has more excellent durability.
As monomer containing aromatic rings, for example, (methyl) phenyl acrylate, (methyl) acrylic acid 2- phenyl second can be enumerated
Base ester, (methyl) benzyl acrylate, (methyl) acrylic acid naphthalene ester, (methyl) phenoxyethyl acrylate, (methyl) propylene
Sour phenoxy group butyl ester, ethoxylation o-phenyl phenol acrylate, phenoxy group diethylene glycol (DEG) (methyl) acrylate, ethylene oxide change
Property cresols (methyl) acrylate, modified nonyl phenol (methyl) acrylate of ethylene oxide (EO) etc., wherein, from polymerism
Viewpoint consideration, preferably (methyl) acrylic acid 2- phenylethylesters.These both may be used singly or in combination of two or more
It uses.
(methyl) acrylate polymer (A), containing 1 mass %~10 mass %, preferably containing 2 mass %~8 mass %,
The monomer with aromatic rings of the mass % of particularly preferably 3 mass %~5 is as the monomeric unit for forming the polymer.By containing virtue
The content of fragrant ring monomer has excellent stress relaxation and durability in above range, obtained contact adhesive.Contain
There is the content of the monomer of aromatic rings if less than 1 mass %, obtained contact adhesive is especially when for COP polarizers, meeting
Generate the bad phenomenon of light leak.On the other hand, the content of the monomer containing aromatic rings is if it exceeds 10 mass %, obtained pressure-sensitive viscous
The durability deterioration of mixture.
As the other monomers, in order not to interfere the hydroxyl of the hydroxyl monomer and isocyanates system crosslinking agent (B)
Reaction does not preferably include the monomer for the functional group for having reactivity with isocyanates system crosslinking agent (B).As such monomer, example
Such as, ((methyl) alkyl acrylate such as (methyl) methoxyethyl ethyl ester, (methyl) ethioxy ethyl ester can be included
Base alkoxy ester, (methyl) cyclohexyl acrylate etc. have (methyl) acrylate of alicyclic ring, acrylamide, methacryl
Acrylamide, (methyl) acrylic acid N, N- dimethyl aminoethyl ester, (methyl) the acrylic acid N, N- bis- of the non-crosslinked property such as amine
(methyl) acrylate with tertiary amino of the non-crosslinked property such as dimethylaminopropyl ester, vinyl acetate, styrene etc..These
Both use had been may be used singly or in combination of two or more.
The polymeric species of (methyl) acrylate polymer (A) can be random copolymer, or block copolymerization
Object.
The weight average molecular weight of (methyl) acrylate polymer (A) is 1,000,000~2,500,000, is preferably 1,500,000~2,200,000,
Particularly preferably 1,800,000~2,000,000.In addition, the weight average molecular weight in this specification, is according to gel permeation chromatography (GPC)
The value that the Ju Ben Yi Xi Change that method is measured are calculated.
The weight average molecular weight of (methyl) acrylate polymer (A) is if less than 1,000,000, then obtained contact adhesive
Durability it is poor.Moreover, the weight average molecular weight of (methyl) acrylate polymer (A) is if it exceeds 2,500,000, then obtained pressure
The stress relaxation deterioration of sensitive adhesive.
In addition, in pressure-sensitive-adhesive composition P, (methyl) acrylate polymer (A) can be used alone,
It can be used in combination of two or more.It is not contained wherein containing hydroxyl moreover, pressure-sensitive-adhesive composition P can further contain
Monomer and/or contain the monomer of aromatic rings as (methyl) acrylate polymer for forming monomeric unit.
(2) isocyanates system crosslinking agent (B)
Isocyanates system crosslinking agent (B) have contain with (methyl) acrylate polymer (A) hydroxyl reactivity with
And the sulfydryl contained with silane coupling agent (C) reactivity it is excellent the advantages of.
Isocyanates system crosslinking agent (B) is the crosslinking agent including at least polyisocyanate compound.As polyisocyanates
Compound, for example, toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, benzene dimethylene diisocyanate etc. can be enumerated
The aliphatic polyisocyantes such as aromatic polyisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenation
Ester ring types polyisocyanates such as '-diphenylmethane diisocyanate etc. and their biuret body, isocyanuric acid ester body, further
Can enumerate ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil etc. as with low molecule chemical combination containing reactive hydrogen
Addition product of the reactant of object etc., wherein, durability viewpoint during from for COP polarizer situations considers, preferably trihydroxy methyl
The aromatic polyisocyanate that propane is modified, particularly preferred trimethylolpropane are modified benzene dimethylene diisocyanate.It is described
Isocyanates system crosslinking agent (B) a kind of can both be used alone, and can also be used in combination of two or more.
The content of isocyanates system crosslinking agent (B) in pressure-sensitive-adhesive composition P, compared with (methyl) acrylic ester polymerization
100 mass parts of object (A) are preferably the mass parts of 0.1 mass parts~1, the mass parts of particularly preferably 0.2 mass parts~0.5, further
The mass parts of preferably 0.3 mass parts~0.4.It is obtained by the content of isocyanates system crosslinking agent (B) in the scope
Contact adhesive forms durability and the excellent cross-linked structure of stress relaxation.
(3) silane coupling agent (C)
In the present embodiment, silane coupling agent (C) has the functional group's sulfydryl that can be reacted with organic material, but due to this
Sulfydryl is easily reacted with the isocyanate group of isocyanates system crosslinking agent (B), even if the crosslinking of (methyl) acrylate polymer (A)
Property functional group be only the hydroxyl to work is difficult in general silane coupling agent, ((methyl) acrylate polymer (A) conduct
Cross-linking functional group, even if not comprising carboxyl), it can also obtain the coupling effect that silane coupling agent (C) is brought.
As described above, for the contact adhesive for being crosslinked pressure-sensitive-adhesive composition P, it is assumed that silane is even
The alkoxysilyl and (methyl) acrylate polymer (A) for joining agent (C) keep suitable distance, i.e. in isocyanates system
In crosslinking agent (B), multiple isocyanate group are kept at a distance between each other, and formation is suspended on (methyl) acrylate polymer (A)
On form.Suitable distance is kept by alkoxysilyl and (crosslinked) (methyl) acrylate polymer (A) as a result,
And exist, excellent coupling effect is played, the adhesiveness of the contact adhesive obtained as a result, is excellent, under the high temperature conditions, damp and hot
Under the conditions of adhesion durability it is also excellent.The effect the pasted objects of contact adhesive be glass or metal when inorganic material when send out
Wave particularly significant.
As silane coupling agent (C), there is at least one sulfydryl for intramolecular, there is at least one alkoxysilyl
Organo-silicon compound, it is preferably good with the compatibility of contact adhesive ingredient, and with photopermeability organo-silicon compound,
Such as it is substantially transparent organo-silicon compound.
As the concrete example of the silane coupling agent (C), 3-mercaptopropyi trimethoxy silane, 3- mercaptos can be enumerated
The low molecule type silane coupling agent containing sulfydryl such as base propyl-triethoxysilicane, 3- mercaptopropyi dimethoxymethylsilanes；
3-mercaptopropyi trimethoxy silane, 3- Mercaptopropyltriethoxysilanes, 3- mercaptopropyi dimethoxymethylsilanes etc. contain
There are the silane compound of sulfydryl and methyltriethoxysilane, ethyl triethoxysilane, methyltrimethoxysilane, ethyl three
Oligomeric silane coupling agents containing sulfydryl such as the cocondensation of the silane compound containing alkyl such as methoxy silane etc..Its
In, from the viewpoint of durability is improved, the oligomeric silane coupling agent of sulfydryl is preferably comprised, particularly preferably containing sulfydryl
Silane compound and the cocondensation containing alkyl silane cpd, further preferred 3-mercaptopropyi trimethoxy silane with
The cocondensation of methyltriethoxysilane.These can be used alone, and can also be used in combination of two or more.
The content of silane coupling agent (C) in pressure-sensitive-adhesive composition P, compared with (methyl) acrylate polymer
(A) 100 mass parts are preferably the mass parts of 0.01 mass parts~1, the mass parts of particularly preferably 0.05 mass parts~0.8, further
The mass parts of preferably 0.1 mass parts~0.5.The content of silane coupling agent (C) if less than 0.01 mass parts, then is difficult to obtain
The effect as caused by the silane coupling agent (C).On the other hand, the content of silane coupling agent (C) is if it exceeds 1 mass parts, then
There are obstruction and the possibility of isocyanates system crosslinking agent (B) and (methyl) acrylate polymer (A) reaction.
(4) antistatic agent (D)
Antistatic agent (D) is contained by pressure-sensitive adhesive composition P, obtained contact adhesive plays excellent anti-quiet
Electrically.In addition, (A)~(C) ingredients (crosslinked for including them) in pressure-sensitive adhesive composition P, due to antistatic agent
(D) excellent in compatibility, obtained contact adhesive also plays excellent effect on durability and optical characteristics.
As antistatic agent (D), for example, ionic compound, surfactant etc., wherein preferably ion
Property compound.Ionic compound can be liquid or solid.Ionic compound in this specification refers to, sun from
Son and anion mainly combine formed compound by electrostatic attraction.
As ionic compound, preferably containing nitrogen salt, containing sulfosalt, phosphorous salts, alkali metal salt and alkaline earth gold
Belong to salt.It is preferably lithium salts, sylvite in addition, as alkali metal salt.
As the concrete example of the antistatic agent (D), N- butyl -4- picolines hexafluorophosphate, N- can be lifted
Hexyl -4- picolines hexafluorophosphate, N- butyl -2- hexyl pyridines perchlorate, double (fluorine sulfimide) potassium (KFSI),
Double (trifluoromethanesulfonimide) potassium (KTFSI), double (fluorine sulfimide) lithiums (LiFSI), double (trifluoromethanesulfonimide) lithiums
(LiTFSI,（ビス（トリフルオロメタンスルホニウムイミド）リ チ ウ system, bis
(trifluoromethanesulfoniumimide)lithium）), N- butyl -2- hexyls pyridines it is double (fluoroform sulphonyl)
Imines etc..Above-mentioned antistatic agent (D) can be used alone, and can also be used in combination of two or more.
The mass % of the content of antistatic agent in pressure-sensitive-adhesive composition P, preferably 0.5 mass %~5, particularly preferably 1
The mass % of quality %~2.5.By the content of antistatic agent within the above range, then antistatic property and contact adhesive is durable
The balance of property becomes good.
(5) various additives
In pressure-sensitive-adhesive composition P, as needed, it can add usually used in acrylic pressure-sensitive adhesive
Various additives, such as adhesiveness imparting agent, antioxidant, ultra-violet absorber, light stabilizer, softening agent, filler, refraction
Rate regulator etc..
(manufacturing method of pressure-sensitive-adhesive composition)
Pressure-sensitive-adhesive composition P can be by manufacturing (methyl) acrylate polymer (A), by (methyl) third of gained
Olefine acid ester polymer (A), isocyanates system crosslinking agent (B), silane coupling agent (C) and antistatic agent (D) are mixed, meanwhile,
As needed, additive is added in manufacture.
(methyl) acrylate polymer (A) can polymerize by using common radical polymerization and form polymer
The mixture of monomeric unit manufactures.The polymerization of (methyl) acrylate polymer (A), can be as needed, is drawn using polymerization
Agent is sent out, by the progress such as solution polymerization process.As polymer solvent, for example, ethyl acetate, acetic acid normal-butyl, Sucrose Acetate
Base ester, toluene, acetone, hexane, methyl ethyl ketone etc. can be used together two or more.
As polymerization initiator, azo compound, organic peroxide etc. can be enumerated, can simultaneously using two kinds with
On.As azo compound, 2 can be enumerated, 2 '-azodiisobutyronitrile, 2,2 '-azo two (2- methylbutyronitriles), 1,1 '-even
Nitrogen two (hexamethylene 1- nitriles), 2,2 '-azo two (2,4- methyl pentane nitrile), 2, (2, the 4- dimethyl -4- methoxyl groups of 2 '-azo two
Valeronitrile), dimethyl 2,2 '-azo two (2 Methylpropionic acid ester), 4,4 '-azo two (4- cyanopentanoic acids), 2,2 '-azo, two (2-
Hydroxymethyl propionitrile), 2,2 '-azo two (2- (2- imidazoline -2- bases) propane) etc..
As organic peroxide, such as benzoyl peroxide, t-butyl-oxybenzoate, cumenyl hydrogen can be enumerated
Peroxide, diisopropyl peroxydicarbonate, diη-propyl peroxy dicarbonate, two (2- ethoxyethyl groups) peroxidating
Two carbonic esters, peroxidating neodecanoic acid tertiary butyl ester, peroxypivalic acid tertiary butyl ester, (3,5,5- trimethyl acetyl base) peroxidating
Object, dipropionyl peroxide, diacetyl peroxide etc..
It, can be to obtained polymer by being compounded the chain-transferring agents such as 2 mercapto ethanol in addition, in above-mentioned polymerization procedure
Weight average molecular weight be adjusted.
After obtaining (methyl) acrylate polymer (A), in the solution of (methyl) acrylate polymer (A), addition
Isocyanates system crosslinking agent (B), silane coupling agent (C), antistatic agent (D), retarder thinner and addition addition as needed
Agent is sufficiently mixed, and obtains the pressure-sensitive-adhesive composition P (coating solution) diluted with solvent.
As for by the retarder thinner of the diluted coating solutions of pressure-sensitive-adhesive composition P, such as hexane, heptan can be used
The aliphatic hydrocarbons such as alkane, hexamethylene；The aromatic hydrocarbons such as toluene and dimethylbenzene；The halogenated hydrocarbons such as dichloromethane and dichloroethanes；First
The alcohol such as alcohol, ethyl alcohol, propyl alcohol, butanol, 1- methoxy-2-propanols；Acetone, methyl ethyl ketone, 2 pentanone, isophorone, cyclohexanone
Wait ketone；Cellosolves series solvents such as the esters such as ethyl acetate and acetic acid butyl ester, ethyl cellosolve etc..
Concentration, viscosity as the coating solution so modulated, as long as being in the range of it can be coated with, without spy
Other limitation according to circumstances can be selected suitably.For example, the concentration of pressure-sensitive-adhesive composition P can be diluted to 10 matter
Measure the mass % of %~40.In addition, when obtaining coating solution, the addition of retarder thinner etc. is not necessary condition, and pressure-sensitive-adhesive combines
As long as the viscosity that object P can be coated with can not also add retarder thinner.In this case, pressure-sensitive-adhesive composition P can be straight
It connects as coating solution.
(contact adhesive)
Pressure-sensitive-adhesive composition P is crosslinked to obtain by the contact adhesive described in present embodiment.Pressure-sensitive-adhesive
The crosslinking of composition P can be carried out by heating.In addition, this heating can also be also used as to pressure-sensitive-adhesive composition P
Drying process of the retarder thinner when being volatilized.
In situation about being heated, heating temperature is preferably 50 DEG C~150 DEG C, and particularly preferably 70 DEG C~120
℃.In addition, heating time is preferably 30 seconds~10 minutes, particularly preferably 50 seconds~2 minutes.Further preferably heat
Afterwards, the maturation time of 1~2 week or so is placed under room temperature (such as 23 DEG C, 50%RH).
By above-mentioned heating (and maturation), (methyl) acrylate polymer (A) passes through isocyanates system crosslinking agent
(B) it is crosslinked, forms three-dimensional net structure.In addition it is assumed that the sulfydryl of silane coupling agent (C) is easily crosslinked with isocyanates system
The isocyanate group reaction of agent (B), the alkoxysilyl of above-mentioned silane coupling agent (C) utilize isocyanates system crosslinking agent
(B), keep suitable distance with (methyl) acrylate polymer (A) or even the three-dimensional net structure and exist, play excellent
Different coupling effect.In addition, there is the hydroxyl of appropriate amount remaining in above-mentioned three-dimensional net structure, simultaneously as cross-linked structure ratio
Loosely, the three-dimensional net structure with it is also excellent in the compatibility of antistatic agent (D).
In addition, pressure-sensitive-adhesive composition P is crosslinked obtained contact adhesive, although above-mentioned three-dimensional net structure is in
More open state still by containing aromatic rings, has appropriate cohesive force.Not reducing cohesive force as a result, can improve
Stress relaxation, thus the durability of contact adhesive is high.In addition, pass through coupling excellent caused by silane coupling agent (C)
Effect, adhesiveness is excellent, even if under the high temperature conditions or under wet heat condition, also playing excellent adhesion durability.For example, 85
DEG C hot conditions under or 60 DEG C, under the wet heat condition of 90%RH, place 250 it is small when be also possible to prevent to inhibit to heave, remove, gas
The generation of bubble etc..
The gel fraction of contact adhesive described in present embodiment is preferably 75%~95%, particularly preferably 80%~
93%, further preferably 85%~90%.If gel fraction is less than 75%, the cohesive force deficiency of contact adhesive has durable
Property and re-workability reduce situation.When being particularly used for the situation of COP polarizers, have fully to be glued at high temperature
Close the situation of durability.On the other hand, if gel fraction is more than 95%, have stress relaxation is too low, durability reduces can
It can property.In addition, above-mentioned gel fraction be from pressure sensitive adhesive layer formation, in the environment of 23 DEG C, 50%RH, preserve 7 days it is (ripe
Into the time after) after value.When whether do not know is the situation of maturation time, as long as again in 23 DEG C, the environment of 50%RH
After lower preservation 7 days, if gel fraction is within the above range.
Contact adhesive described in present embodiment, 23 DEG C of storage modulus (G ') be preferably 0.05MPa~
0.20MPa, particularly preferably 0.08MPa~0.18MPa, further preferably 0.1MPa~0.15MPa.In addition, this embodiment party
Contact adhesive involved by formula is preferably 0.05MPa~0.15MPa in 80 DEG C of storage modulus (G '), particularly preferably
0.07MPa~0.15MPa, further preferably 0.08MPa~0.13MPa.By the storage modulus (G ') for making 23 DEG C and 80 DEG C
Within the above range, required substrate adherence and cohesive force are obtained, suitable for polarizer when optical component when, (for example, 80
At a high temperature of DEG C), can effectively prevent under durable environment with the interface of optical component or with the heaving of the interface of glass substrate, shell
From etc..In addition, above-mentioned storage modulus is using JIS K7244-6 as foundation, torsional shear method institute is utilized under 1Hz measurinng frequencies
The value of measure.
(pressure sensitive adhesion sheet)
As shown in Figure 1, the pressure sensitive adhesion sheet 1A described in the 1st embodiment, under sequentially, by stripping film 12, is laminated in stripping
The pressure sensitive adhesive layer 11 of release surface from piece 12 and the base material 13 being laminated on pressure sensitive adhesive layer 11 are formed.
In addition, as shown in Fig. 2, pressure sensitive adhesion sheet 1B described in the 2nd embodiment, by two panels stripping film 12a, 12b and
By pressure-sensitive viscous clamped by this two panels stripping film 12a, 12b in a manner that the release surface with this two panels stripping film 12a, 12b connects
Mixture layer 11 is formed.Furthermore the release surface of so-called stripping film in this specification refers to there is fissility in stripping film
Face also includes the face for implementing lift-off processing and even if lift-off processing, which is not carried out, also shows that any in the face of fissility
Kind.
In any one of pressure sensitive adhesion sheet 1A, 1B, pressure sensitive adhesive layer 11 is included by curing above-mentioned pressure-sensitive adhesion
Contact adhesive formed by property composition P.
The thickness of pressure sensitive adhesive layer 11, according to the purpose of usage of pressure sensitive adhesion sheet 1A, 1B suitable for determining, but usually
It is preferably 10 μm~60 μm of scope for 5 μm~100 μm.For example, it using as optical component, used especially as polarizer
Pressure sensitive adhesive layer use situation when, be preferably 10 μm~50 μm, particularly preferably 15 μm~30 μm.
It as base material 13, is not particularly limited, as base material used in the substrate sheets of common pressure sensitive adhesion sheet all
It can use.For example, in addition to desirable optical component, it can enumerate and use the fibres such as artificial silk, acrylonitrile and polyester
The woven cloths or non-woven cloth of dimension；Synthetic paper；Upper matter paper, glassine paper, containing the paper such as impregnated paper, art paper system；The metal of aluminium, copper etc.
Paper tinsel；The foaming bodies such as polyurethane foaming body, foam polyethylene；Polyethylene terephthalate, polybutylene terephthalate
The polyester films such as ester, polyethylene naphthalate；The fibers such as polyurethane film, polyethylene film, polypropylene screen, tri acetyl cellulose
Plain film；Polychloroethylene film, polyvinylidene chlorida film, polyvinyl alcohol film, ethylene vinyl acetate film, polystyrene
The plastic foils such as film, polycarbonate membrane, acrylic resin film, norbornene resin film, cycloolefin resin film；They two kinds with
On lamilate etc..Plastic foil can be uniaxial stretching or biaxial stretch-formed film.
As optical component, such as polarizer (light polarizing film), polarization element can be enumerated, polarizer (phase difference film), regarded
Wild angle compensation film, briliancy improve film, contrast improves film, liquid crystalline polymer film, diffusion barrier, semipermeable reflection film etc..Wherein, partially
Tabula rasa (light polarizing film) is due to easily shrinking, change in size is big, from the viewpoint of durability is required, as formation present embodiment
The base material of the contact adhesive (above-mentioned pressure sensitive adhesive layer 11) is preferred.In addition, particularly polycyclic olefin mesentery or tool
Have the polarizer (COP polarizers) of the film, not only easily shrink, change in size it is big, go back that contact angle is big, stickup property is low, therefore, from
It is required that from the viewpoint of adhesiveness adhesion durability, the contact adhesive for being suitable as being formed described in present embodiment is (above-mentioned
Pressure sensitive adhesive layer 11) base material.
The thickness of base material 13, it is different according to its species, still, in the situation of for example, optical component, usually
For 10 μm~500 μm, it is preferably 50 μm~300 μm, is particularly preferably 80 μm~150 μm.
As stripping film 12,12a, 12b, such as polyethylene film, polypropylene screen, polybutene film, polybutadiene can be used
Film, polymethylpentene film, polychloroethylene film, vinyl chloride copolymer film, polyethylene terephthalate film, poly- naphthalenedicarboxylic acid second
Diol ester film, polybutylene terephthalate (PBT) film, polyurethane film, vinyl-vinyl-acetic ester film, ionomer resin film, second
It is alkene-(methyl) acrylic copolymer film, ethylene-(methyl) acrylate copolymer film, polystyrene film, polycarbonate membrane, poly-
Acid imide film, fluororesin film etc..Alternatively, it is also possible to use their cross linking membrane.Further, or their laminate film.
The release surface (face particularly to connect with pressure sensitive adhesive layer 11) of above-mentioned stripping film, is preferably implemented at stripping
Reason.As the remover used in lift-off processing, such as alkyd system, silicon-type, fluorine system, unsaturated polyester (UP) can be included
The remover of system, polyolefin and wax system.
On stripping film 12,12a, the thickness of 12b is not particularly limited, and is usually 20 μm~150 μm or so.
In above-mentioned pressure sensitive adhesion sheet 1A is manufactured, in the release surface of stripping film 12, pressure-sensitive-adhesive composition will be contained
Solution (coating solution) is coated, heats, will on the pressure sensitive adhesive layer 11 after pressure sensitive adhesive layer 11 is formed
Base material 13 is stacked.Then, the maturation time is preferably set.In addition, the condition on heating and maturation is as described above.
In addition, in above-mentioned pressure sensitive adhesion sheet 1B is manufactured, in the release surface of a stripping film 12a (or 12b), will contain
The coating solution for having above-mentioned pressure-sensitive-adhesive composition is coated, heats, will be another after pressure sensitive adhesive layer 11 is formed
The release surface of one stripping film 12b (or 12a) coincides with the pressure sensitive adhesive layer 11.
As the method for being coated with above-mentioned coating solution, for example, can utilize rod coating method, scraper for coating method, roller coating method,
Scraper plate rubbing method, die coating methods, gravure roller coating method etc..
Pressure sensitive adhesive layer 11 in pressure sensitive adhesion sheet 1A, 1B, haze value is (according to JISK7136：2000 measure obtain
Value) be preferably less than 1.0%, be particularly preferably less than 0.9%, further preferably less than 0.8%.If haze value is
Less than 1.0%, then it is transparent very high, become the pressure sensitive adhesive layer suitable as optical applications.
Here, for example, in the liquid crystal display device that is made of Liquid crystal module and polarizer of manufacture, as pressure-sensitive adhesion
Using polarizer, the stripping film 12 of pressure sensitive adhesion sheet 1A is removed for the base material 13 of piece 1A, by the pressure sensitive adhesive layer 11 of exposing
It is bonded with Liquid crystal module.
In addition, being configured with for example, manufacturing between Liquid crystal module and polarizer in the liquid crystal display device of polarizer, make
As an example of, first, a stripping film 12a (or 12b) of pressure sensitive adhesion sheet 1B is removed, by the exposing of pressure sensitive adhesion sheet 1B
Pressure sensitive adhesive layer 11 and polarizer are bonded.Then, polarizer will be used as the pressure sensitive adhesion sheet 1A's of base material 13
Stripping film 12 is removed, and pressure sensitive adhesive layer 11 that pressure sensitive adhesion sheet 1A exposes and above-mentioned polarizer are bonded.Further,
From the pressure sensitive adhesive layer 11 of above-mentioned pressure sensitive adhesion sheet B, another stripping film 12b (or 12a) is removed, by pressure sensitive adhesion sheet
Pressure sensitive adhesive layer 11 and the Liquid crystal module fitting of the exposing of B.
According to above pressure sensitive adhesion sheet 1A, 1B, the excellent in te pins of durability of pressure sensitive adhesive layer 11, therefore even if in high temperature item
Under part or under wet heat condition, it is also possible to prevent to inhibit in base material 13 or is generated between adherend and heave, remove, foam
Deng.Particularly, using base material 13 as during the situation of COP polarizers, the issuable stress of the deformation of COP polarizers can pressed
Sensitive adhesive layer 11 is absorbed and relaxed, and thus plays excellent durability.In addition, according to pressure sensitive adhesion sheet 1A, 1B, resist quiet
It is electrically excellent.
Pressure sensitive adhesion sheet 1A, 1B of the present embodiment, preferably using transparent conductive film as adherend.Pressure-sensitive-adhesive
(methyl) acrylate polymer (A) in composition P, without the monomer with carboxyl as the monomer list for forming the polymer
Member, therefore the harmful effect brought due to sour ingredient to transparent conductive film can be inhibited.Specifically, electrically conducting transparent can be inhibited
Film corrodes or the resistance value of transparent conductive film changes.
As transparent conductive film, such as the metals such as platinum, gold, silver, copper can be enumerated；Tin oxide, indium oxide, cadmium oxide, oxidation
The oxides such as zinc, zinc oxide；Tin-doped indium oxide (ITO), Zinc oxide doped indium oxide, Fluorin doped indium oxide, Sb doped oxygen
Change the composite oxides such as tin, fluorine-doped tin oxide, aluminium-doped zinc oxide；Chalcogen compound, lanthanum hexaboride, titanium nitride, carbon
Change the transparent conductive film that non-oxidized compounds such as titanium etc. are formed.
The pressure sensitive adhesion sheet 1A for having used polarizer as base material 13 (has the referred to as " polarisation with pressure sensitive adhesive layer below
The situation of plate "), it is preferably 0.1N/25mm~25N/25mm for the bonding force of alkali-free glass, particularly preferably 2N/25mm~
20N/25mm.By making bonding force in above-mentioned scope, then between the adherends such as glass plate, can prevent from heaving or shelling
From etc..Furthermore bonding force said here substantially refers to by being based on JIS Z0237：2009 180 ° of stripping methods are measured
Bonding force, determination sample is cut into wide 25mm, long 100mm, makes the determination sample compared with adherend, 0.5MPa, 50 DEG C,
After pressurization is pasted for 20 minutes, after when placement 24 is small under conditions of 23 DEG C of normal pressure, 50%RH, with peeling rate 300mm/min
It is measured obtained bonding force.
In addition, the above-mentioned polarizer with pressure sensitive adhesive layer is pasted on above-mentioned adherend, in 50 DEG C of normal pressure, the item of 50%RH
Under part, the bonding force after placing 2 days is preferably 0.1N/25mm~25N/25mm, particularly preferably 2N/25mm~20N/25mm.
Like this due to through when generated bonding force rising be suppressed, it is possible thereby to be evaluated as the excellent polarizer of re-workability.
In addition, bonding force mentioned here also substantially refers to by being based on JIS Z0237：2009 180 ° of stripping methods are measured viscous
With joint efforts, but determination sample is cut into wide 25mm, long 100mm, makes the determination sample compared with adherend, 0.5MPa, 50 DEG C,
After pressurization is pasted for 20 minutes, after being placed 2 days under above-mentioned condition (50 DEG C of normal pressure, 50%RH), with peeling rate 300mm/min
It is measured obtained bonding force.
Embodiments described above describes to be readily appreciated that the present invention, is not that the present invention is carried out
The description for limiting and carrying out.Therefore, each element disclosed in the above embodiment also includes the technical scope for belonging to the present invention
All design alterations and equivalent.
For example, the stripping film 12 of pressure sensitive adhesion sheet 1A can be omitted, in stripping film 12a, 12b in pressure sensitive adhesion sheet 1B
Either side can also be omitted.
【Embodiment】
Hereinafter, further the present invention is specifically described by embodiment etc., but the scope of the present invention and from this
The restriction of a little embodiments etc..
(embodiment 1)
The modulation of (1. methyl) acrylate polymer
Into the reaction vessel with mixer, thermometer, reflux cooler, dripping device and nitrogen ingress pipe, it is packed into
87.5 mass parts of n-butylacrylate, 5 mass parts of methyl acrylate, 5 mass parts of acrylic acid 2- phenylethylesters, acrylic acid
0.08 mass parts of 2.5 mass parts of 2- hydroxyethyl esters, 200 mass parts of ethyl acetate and 2,2'- azodiisobutyronitrile, will be above-mentioned
Air in reaction vessel is replaced as nitrogen.While stirring under the nitrogen atmosphere, while reaction solution is warming up to 60 DEG C, make
After when reaction progress 16 is small, it is cooled to room temperature.Here, by a part for the solution of gained, molecular weight is measured with aftermentioned method,
Confirming generation has (methyl) acrylate polymer (A) of weight average molecular weight 2,000,000.
2. the modulation of pressure-sensitive-adhesive composition
(solid constituent converts 100 mass parts of (methyl) acrylate polymer (A) that will be obtained in above-mentioned steps (1)
Value；It is the same below)；As isocyanates system crosslinking agent (B), trimethylolpropane is modified benzene dimethylene diisocyanate (three
Well force field ケ ミ カ Le society system, trade name " タ ケ ネ ー ト D110N ") 0.2 mass parts；As with sulfydryl as with organic material
The cocondensation of the silane coupling agent (C) of the functional group of reaction, 3-mercaptopropyi trimethoxy silane and methyltriethoxysilane
Object (chemistry society of SHIN-ETSU HANTOTAI system, trade name " X41-1810 ") 0.2 mass parts；And as antistatic agent (D), pyridiniujm system from
0.2 mass parts of sub- liquid (wide Rong Huaxue societies system, trade name " IL-P18 ") are mixed, fully stirred, by using acetic acid second
Ester is diluted, and obtains the coating solution of pressure-sensitive-adhesive composition.
Here, the cooperation of the pressure-sensitive-adhesive composition is shown in table 1.In addition, dummy suffix notation recorded in table 1 etc. is detailed
Details condition is as described below.
[(methyl) acrylate polymer]
BA：N-butylacrylate
MA：Methyl acrylate
PhEA：Acrylic acid 2- phenoxyethyl acrylates
HEA：Acrylic acid 2- hydroxyethyl esters
4HBA：Acrylic acid 4- hydroxybutyl esters
AS agent 1：Pyridiniujm system ionic liquid (wide Rong Huaxue societies system, trade name " IL-P18 ")
AS agent 2：The equimolar melange of double (trifluoromethanesulfonimide) lithiums and tetraethyleneglycol dimethyl ether (three photoinitiator chemical societies
System, trade name " サ Application コ ノ ー Le TGR ")
AS agent 3：Equimolar melange (the first industrial pharmaceutical society of double (fluorine sulfimide) potassium and tetraethyleneglycol dimethyl ether
System, trade name " AS-804 ")
3. the manufacture of the polarizer with pressure sensitive adhesive layer
By the coating solution of obtained pressure-sensitive-adhesive composition, it is coated on Scraper applicator by poly terephthalic acid second
One face of diol ester film has carried out stripping film (Lindeke Co., Ltd's system, the SP- of lift-off processing with silicon-type remover
PET3811, thickness：38 μm) lift-off processing face, make dried thickness for after 25 μm, heating in 1 minute is carried out with 90 DEG C
And form pressure sensitive adhesive layer.
Then, by with a face of the polarization element that is formed of tri acetyl cellulose membrane protection polyvinyl alcohol film, use cyclenes
The COP polarizers that hydrocarbon polymer film protects the thickness obtained by another face to be 100 μm are bonded with above-mentioned pressure sensitive adhesive layer, are made
The exposed surface for stating pressure sensitive adhesive layer is in contact with the surface of above-mentioned cyclo-olefin-polymer films, is carried out under 23 DEG C, 50%RH environment
Thus maturation 7 days obtains the polarizer with pressure sensitive adhesive layer.
(embodiment 2~14, comparative example 1~3)
Except the species and ratio of each monomer that will form (methyl) acrylate polymer (A), (methyl) acrylate
Weight average molecular weight, isocyanates system crosslinking agent (B), the use level and antistatic agent of silane coupling agent (C) of polymer (A)
(D) species and use level, it is outer according to being changed shown in table 1, it is operated similarly to Example 1, manufacture is with pressure-sensitive
The polarizer of adhesive phase.
Here, above-mentioned weight average molecular weight (Mw), for gel permeation chromatography (GPC) is used to measure under the following conditions
The weight average molecular weight of the polystyrene conversion of (GPC measure).
＜ determination conditions ＞
GPC measurement devices：Dong ソ ー societies system, HLC-8020
GPC columns (pass through) according to following order：Dong ソ ー societies system
TSK guard columnHXL-H
TSK gel GMHXL(×2)
TSK gel G2000HXL
Measure flux：Tetrahydrofuran
Measuring temperature：40℃
(test example 1) (measure of gel fraction)
In embodiment or comparative example, instead of polarizer used in polarizer of the making with pressure sensitive adhesive layer, make
With one face of polyethylene terephthalate film has been carried out the stripping film of lift-off processing with silicon-type remover, (beautiful jade obtains
Section's Co. Ltd. system, SP-PET3801, thickness：38 μm), make pressure sensitive adhesion sheet.Specifically, with embodiment or comparative example
The obtained stripping film of manufacturing process/pressure sensitive adhesive layer (thickness：25 μm) what is formed forms the pressure-sensitive viscous of the exposing of body
It is in a manner of being connected by lift-off processing surface side, above-mentioned stripping film is laminated in mixture layer.It is viscous by stripping film/pressure-sensitive to make as a result,
The pressure sensitive adhesion sheet that the composition of mixture layer/stripping film is formed.
The pressure sensitive adhesion sheet that will be obtained carries out maturation in 7 days under conditions of 23 DEG C, 50%RH.Afterwards, by the pressure-sensitive adhesion
The sample of 80mm × 80mm sizes is made in piece, and pressure sensitive adhesive layer polyester net (net size 200) is wrapped up, only will be pressure-sensitive
The quality of adhesive is weighed with precision balance.Using quality at this time as M1.
Then, the contact adhesive above-mentioned polyester net wrapped up, at room temperature under (23 DEG C), carries out in ethyl acetate
24 impregnate when small.The contact adhesive is taken out afterwards, in the environment of 23 DEG C of temperature, relative humidity 50%, wind when progress 24 is small
It is dry, it is dried when further progress 12 is small in 80 DEG C of baking oven.Only by the quality precision balance of dried contact adhesive
It is weighed.Using quality at this time as M2.Gel fraction (%) is represented with (M2/M1) × 100.Show the result in table 1.
(test example 2) (measure of haze value)
As determination sample, prepare with measuring the same pressure sensitive adhesion sheet (maturation of pressure sensitive adhesion sheet used in gel fraction
7 days).Pressure sensitive adhesive layer (thickness on the pressure sensitive adhesion sheet：25 μm), use (the Japan's electricity color industry of haze measurement meter
Company system, NDH2000), based on JISK7136：2000, haze value (%) is measured.Show the result in table 1.
(test example 3) (measure of storage modulus)
The pressure sensitive adhesion sheet being made of stripping film/pressure sensitive adhesive layer/stripping film is made in the same manner as test example 1.It will
Stripping film is removed from the pressure sensitive adhesion sheet, and contact adhesive layer thickness is made to be carried out multiple-layer laminated for 3mm.It is pressure-sensitive viscous from what is obtained
The lamilate of mixture layer stamps out the hole of the cylinder (height 3mm) of diameter 8mm, as sample.
To above-mentioned sample, according to JIS K7244-6, determination of viscoelasticity instrument (REOMETRIC societies system, DYNAMIC are used
ANALAYZER storage modulus (MPa)) is measured with following condition using torsional shear method.Show the result in table 1.
Measurinng frequency：1Hz
Measuring temperature：23℃、80℃
(test example 4) (measure of bonding force)
By the obtained polarizer severing with pressure sensitive adhesive layer in embodiment or comparative example, width 25mm, length are made
The sample of 100mm.It is removed from the sample by stripping film, by the pressure sensitive adhesive layer of exposing, which is pasted onto alkali-free glass
Glass (コ ー ニ Application グ society , イ ー グ Le XG) on after, with the former autoclave for making society of institute of chestnut, 0.5MPa, 50 DEG C,
Pressurization 20 minutes.Thereafter, under conditions of 23 DEG C, 50%RH, place 24 it is small when after, use cupping machine (オ リ エ Application テ ッ Network
Society's system, テ Application シ ロ Application), based on JISZ0237：2009, with peeling rate 300mm/min, the condition of 180 ° of peel angle, survey
Determine the bonding force (bonding force after pasting 1 day；N/25mm).
In addition, by the sample as described above 0.5MPa, 50 DEG C, pressurize 20 minutes, be pasted on the alkali-free glass
Afterwards, under conditions of 50 DEG C of normal pressure, 50%RH, place 2 days, measure bonding force at this time as described above (after pasting 2 days
Bonding force；N/25mm).Show the result in table 1.
(test example 5) (durability evaluation)
By the obtained polarizer severing with pressure sensitive adhesive layer in embodiment or comparative example, make 233mm ×
The sample of 309mm sizes.As sample, prepare (to carry pressure-sensitive adhesion from making after forming pressure sensitive adhesive layer on polarizer
The polarizer of oxidant layer rises), the sample after being preserved 7 days in the environment of 23 DEG C, 50%RH.It removes, passes through from the sample stripping film
The pressure sensitive adhesive layer of exposing is pasted onto alkali-free glass (コ ー ニ Application グ society , イ ー グ Le XG) on after, make institute with chestnut is former
The autoclave of system, 0.5MPa, 50 DEG C, pressurize 20 minutes.
Afterwards, put into the environment of following durable conditions, 250 it is small when after, using 10 times of magnifying glasses, to heaving or
The presence or absence of stripping is confirmed.Evaluation criteria is as follows.Show the result in table 1.
◎：It does not confirm and heaves or remove.
○：Confirm heaving or removing for below 0.5mm sizes.
×：Confirm heaving or removing for more than 0.6mm sizes.
The durable condition ＞ of ＜
85 DEG C of dryings
60 DEG C, relative humidity 90%RH
(test example 6) (measure of surface resistivity)
By in embodiment or comparative example the obtained polarizer with pressure sensitive adhesive layer with the big of 50mm × 50mm
Small severing, by obtained sample when placement 24 is small under conditions of 23 DEG C of temperature, humidity 50%RH.Afterwards, stripping film is shelled
From on the contact adhesive layer surface of exposing, using resistivity meter (Mitsubishi Chemical ア Na リ テ ッ Network society system, Ha イ レ ス タ
UP MCP-HT450 types), based on JIS K6911, measure sheet resistance value (Ω/sq).Show the result in table 1.
In addition, sheet resistance value is preferably 3.0 × 1011 Ω/below sq, particularly preferably 1.0 × 1011 Ω/below sq,
Further preferably 8.0 × 1010 Ω/below sq.Sheet resistance value is under described value, then can play good antistatic property.
As shown in Table 1, the contact adhesive of obtained pressure sensitive adhesive layer in embodiment, durability and antistatic property
It is excellent, in addition, while with high gel fraction, all there is good storage modulus at 23 DEG C and 80 DEG C.
【Industrial utilizability】
The contact adhesive of the present invention is suitable for optical component, the bonding of special polarizer, moreover, the present invention's is pressure-sensitive
Bonding sheet suitable for as optical component with, particularly polarizer pressure sensitive adhesion sheet.
Claims (8)
- It is the contact adhesive that following pressure-sensitive-adhesive composition crosslinking forms 1. contact adhesive is characterized in that,The pressure-sensitive-adhesive composition contains：(methyl) acrylate polymer (A), weight average molecular weight are 1,000,000~2,500,000, contain monomer and tool with hydroxyl There is monomeric unit of the monomer as composition polymer of aromatic rings, without monomer of the monomer with carboxyl as composition polymer Unit；Isocyanates system crosslinking agent (B)；Silane coupling agent (C), with sulfydryl as the functional group reacted with organic material；WithAntistatic agent (D)；(methyl) acrylate polymer (A) containing 2.5 mass %~10 there is described in mass % the monomer of hydroxyl, contain There is the monomer with aromatic rings of the mass % of 1 mass %~10 as the monomeric unit for forming the polymer,The content of the antistatic agent (D) is more than 1 mass %, below 5 mass %,The contact adhesive is from pressure sensitive adhesive layer formation, the gel point after being preserved 7 days in the environment of 23 DEG C, 50%RH Rate is 80%~95%.
- 2. contact adhesive according to claim 1, which is characterized in that described different in the pressure-sensitive-adhesive composition The content of cyanate system crosslinking agent (B) is 0.1 mass compared with 100 mass parts of (methyl) acrylate polymer (A) Part~1 mass parts.
- 3. contact adhesive according to claim 1, which is characterized in that the silicon in the pressure-sensitive-adhesive composition The content of alkane coupling agent (C) is 0.01 mass parts~1 compared with 100 mass parts of (methyl) acrylate polymer (A) Mass parts.
- 4. contact adhesive according to claim 1, which is characterized in that 23 DEG C of storage modulus (G ') be 0.05MPa ~0.20MPa is 0.05MPa~0.15MPa in 80 DEG C of storage modulus (G ').
- 5. pressure sensitive adhesion sheet is the pressure sensitive adhesion sheet with base material and pressure sensitive adhesive layer, which is characterized in that described pressure-sensitive viscous Mixture layer includes contact adhesive according to any one of claims 1 to 4.
- 6. pressure sensitive adhesion sheet according to claim 5, which is characterized in that the base material is optical component.
- 7. pressure sensitive adhesion sheet according to claim 6, which is characterized in that the optical component is polarizer.
- 8. pressure sensitive adhesion sheet, for two panels stripping film and in a manner that the release surface with the two panels stripping film connects by institute State the pressure sensitive adhesion sheet of the pressure sensitive adhesive layer of stripping film clamping, which is characterized in that the pressure sensitive adhesive layer will including right Seek the contact adhesive any one of 1~4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013026093A JP6097589B2 (en) | 2013-02-13 | 2013-02-13 | Adhesive composition, adhesive and adhesive sheet |
| JP2013-026093 | 2013-02-13 |
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| Publication Number | Publication Date |
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| CN103980845A CN103980845A (en) | 2014-08-13 |
| CN103980845B true CN103980845B (en) | 2018-05-25 |
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| CN201410049204.4A Active CN103980845B (en) | 2013-02-13 | 2014-02-13 | Pressure-sensitive-adhesive composition, contact adhesive and pressure sensitive adhesion sheet |
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| Country | Link |
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| JP (1) | JP6097589B2 (en) |
| KR (1) | KR102246034B1 (en) |
| CN (1) | CN103980845B (en) |
| TW (1) | TWI600733B (en) |
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| Publication number | Publication date |
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| CN103980845A (en) | 2014-08-13 |
| TWI600733B (en) | 2017-10-01 |
| JP6097589B2 (en) | 2017-03-15 |
| JP2014152319A (en) | 2014-08-25 |
| KR102246034B1 (en) | 2021-04-28 |
| KR20140102132A (en) | 2014-08-21 |
| TW201435025A (en) | 2014-09-16 |
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