CN108473838A - Adhesive composition - Google Patents

Adhesive composition Download PDF

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Publication number
CN108473838A
CN108473838A CN201680073164.4A CN201680073164A CN108473838A CN 108473838 A CN108473838 A CN 108473838A CN 201680073164 A CN201680073164 A CN 201680073164A CN 108473838 A CN108473838 A CN 108473838A
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China
Prior art keywords
methyl
weight
film
adhesive composition
parts
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Granted
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CN201680073164.4A
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CN108473838B (en
Inventor
浅津悠司
阪上智惠
陈文崇
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Adhesive Tapes (AREA)

Abstract

A kind of adhesive composition is provided, can be formed even if the adhesive phase for also showing that excellent durability under the conditions of harsh durable.In the adhesive composition comprising (methyl) acrylic resin (A), crosslinking agent (B) and silane compound (C), above-mentioned (methyl) acrylic resin (A) includes the structural unit from hydroxyl (methyl) acrylate shown in following formula (a1) and following formula (a2), and above-mentioned crosslinking agent (B) is the addition product based on polyol compound of toluene di-isocyanate(TDI) based compound and/or toluene di-isocyanate(TDI) based compound.

Description

Adhesive composition
Technical field
The present invention relates to resistance to for being formed in optical film of subsidiary adhesive phase that liquid crystal display device etc. is utilized etc. Useful adhesive composition for the excellent adhesive phase of long property.
Background technology
Using polarization plates made of fitting transparent resin film is laminated in the one or two sides of polarizing film as the optical film quilt of representative It is widely used as constituting the optical component of the image display devices such as liquid crystal display device.The optical film of polarization plates etc is mostly by viscous Mixture layer and fit in other components (such as liquid crystal cells etc. in liquid crystal display device) to use (referring to patent document 1). Therefore, as optical film, it is known that one of which face pre-sets the optics of subsidiary adhesive phase obtained from adhesive phase Film.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2010-229321 bulletins
Invention content
Problems to be solved by the invention
In recent years, mobile device purposes of the liquid crystal display device representated by smart mobile phone or panel type terminal, automobile are led Vehicle-mounted equipment expansion application on the way representated by boat system.It is used on the way, with previous indoor TV purposes phase such Than being possible to be exposed under harsh environment, therefore, improving the durability of device becomes project.
The optical film of subsidiary adhesive phase for constituting liquid crystal display device etc. similarly requires durability.That is, group The adhesive phase being filled in liquid crystal display device etc. is placed under hot environment or under hot and humid environment sometimes, or is put It is placed in the environment of high temperature and low temperature is presented repeatedly, the optical film of subsidiary adhesive phase is required even if under these circumstances Can inhibit the interface of the adhesive phase optical component to be bonded with it float or peel off, the foaming of adhesive phase etc. it is bad Situation, in addition, also optical characteristics is required not deteriorate.Especially, in the case where optical film is polarization plates, due to high temperature ring Strong shrinkage stress under border, thus, endurance quality more higher than general optical film is required to adhesive phase.It is above-mentioned due to improving The raising of the demand of the durability of liquid crystal display device, thus, the durability required recently adhesive phase becomes very strict.
It is excellent even if being also showed that under the conditions of this harsh durable therefore, the purpose of the present invention is to provide that can be formed The adhesive composition of the adhesive phase of durability.
The method for solving problem
The present inventor has made intensive studies in order to solve the above problems, as a result completes the present invention.
That is, the present invention includes the following contents.
[1] a kind of adhesive composition, it includes (methyl) acrylic resin (A), crosslinking agent (B) and silane compounds (C),
Above-mentioned (methyl) acrylic resin (A) includes to be originated from hydroxyl (methyl) acrylate shown in following formula (a1) Structural unit and structural unit from hydroxyl (methyl) acrylate shown in following formula (a2),
Above-mentioned crosslinking agent (B) is the base of toluene di-isocyanate(TDI) based compound and/or toluene di-isocyanate(TDI) based compound In the addition product of polyol compound.
[changing 1]
(in formula, n indicates 1~4 integer；A1Indicate hydrogen atom or alkyl；X1Indicate the optionally methylene with substituent group； When n is 2 or more, above-mentioned substituent group is optionally identical or different)
[changing 2]
(in formula, m indicates 5 or more integer；A2Indicate hydrogen atom or alkyl；X2Indicate the optionally methylene with substituent group Base, above-mentioned substituent group are optionally identical or different)
[2] according to the adhesive composition described in [1], wherein the whole relative to composition (methyl) acrylic resin 100 parts by weight of structural unit, the ratio for being originated from the structural unit of hydroxyl (methyl) acrylate shown in formula (a1) are 1.5 weights The parts by weight of part~4.5 are measured, the ratio for being originated from the structural unit of hydroxyl (methyl) acrylate shown in formula (a2) is 0.25 weight Measure the parts by weight of part~1.0.
[3] according to the adhesive composition described in [1] or [2], wherein (methyl) acrylic resin includes to be originated from propylene The structural unit of acid alkyl ester (a3), the alkyl acrylate (a3) are contained the glass transition temperature from homopolymer and are less than The propylene that the structural unit of 0 DEG C of alkyl acrylate (a3-1) and the glass transition temperature from homopolymer are 0 DEG C or more The structural unit of acid alkyl ester (a3-2).
[4] according to the adhesive composition described in [3], wherein the glass transition temperature for being originated from homopolymer is less than 0 DEG C The acrylic acid alkyl that the structural unit of alkyl acrylate (a3-1) is 0 DEG C or more with the glass transition temperature from homopolymer The ratio (weight ratio) of the structural unit of ester (a3-2) is (a3-1)/(a3-2)=20/80~95/5.
[5] adhesive composition according to any one of [1]~[4], wherein the weight of (methyl) acrylic resin Average molecular weight is scaled 6.0 × 10 with polystyrene5~2.5 × 106。
[6] according to the adhesive composition described in any one of [1]~[5], wherein the ratio of crosslinking agent (B) relative to 100 parts by weight of (methyl) acrylic resin (A) are the parts by weight of 0.01 parts by weight~10.
[7] adhesive composition according to any one of [1]~[6], wherein silane compound (C) is following formula (c1) silane compound shown in.
[changing 3]
(in formula, B indicates the alicyclic type hydrocarbon of the alkane diyl of carbon number 1~20 or the divalent of carbon number 3~20, constitutes above-mentioned - the CH of alkane diyl and above-mentioned alicyclic type hydrocarbon2Optionally it is replaced as-O- or-CO-；R1Indicate the alkyl of carbon number 1~5；R2、 R3、R4、R5And R6Each independently represent the alkyl of carbon number 1~5 or the alkoxy of carbon number 1~5)
[8] according to the adhesive composition described in [7], wherein the B of formula (c1) is the alkane diyl of carbon number 1~10；R1For The alkyl of carbon number 1~5；R2、R3、R4、R5And R6It is each independently the alkoxy of carbon number 1~5.
[9] adhesive composition according to any one of [1]~[8], wherein the ratio phase of silane compound (C) It is the parts by weight of 0.01 parts by weight~10 for 100 parts by weight of (methyl) acrylic resin (A).
[10] adhesive composition according to any one of [1]~[9], wherein formed by adhesive composition The gel fraction of adhesive is 50%~95%.
[11] adhesive composition according to any one of [1]~[10], wherein be bonded on the glass substrate by upper The adhesive phase for stating adhesive composition formation, it is above-mentioned viscous under conditions of 23 DEG C of temperature, relative humidity 50%, after 24 hours The bonding force of mixture layer is 0.5N/25mm~10N/25mm under 300mm/ minutes peeling rates.
[12] adhesive composition according to any one of [1]~[11], is used to form optical film to be laminated in Adhesive phase.
The effect of invention
What the adhesive composition of the present invention can be formed under the conditions of harsh durable with excellent durability Adhesive phase.
Description of the drawings
Fig. 1 is an example for the optical film for indicating the subsidiary adhesive phase formed by adhesive composition of the present invention Summary sectional view.
Fig. 2 is the summary sectional view of an example for indicating that the layer of polarization plates is constituted.
Fig. 3 is the other summary sectional views for indicating the layer of polarization plates and constituting.
Fig. 4 is the light for indicating the optical film comprising the subsidiary adhesive phase formed by adhesive composition of the present invention Learn the summary sectional view of an example of laminated body.
Fig. 5 is the light for indicating the optical film comprising the subsidiary adhesive phase formed by adhesive composition of the present invention Learn the summary sectional view of an example of laminated body.
Fig. 6 is the light for indicating the optical film comprising the subsidiary adhesive phase formed by adhesive composition of the present invention Learn another other summary sectional view of laminated body.
Fig. 7 is the light for indicating the optical film comprising the subsidiary adhesive phase formed by adhesive composition of the present invention Learn other summary sectional view of laminated body.
Fig. 8 is the light for indicating the optical film comprising the subsidiary adhesive phase formed by adhesive composition of the present invention Learn another other summary sectional view of laminated body.
Specific implementation mode
[1] adhesive composition
The adhesive composition of the present invention includes (methyl) acrylic resin (A), crosslinking agent (B), silane compound (C)。
[1-1] (methyl) acrylic resin (A)
(methyl) acrylic resin (A) is to be originated from the structural unit of (methyl) acrylic monomer as principal component The polymer or copolymer of (preferably comprising 50 weight % or more), including from hydroxyl shown in following formula (a1) and (a2) The structural unit of (methyl) acrylate.
[changing 4]
(in formula, n indicates 1~4 integer；A1Indicate hydrogen atom or alkyl；X1Indicate the optionally methylene with substituent group； When n is 2 or more, above-mentioned substituent group is optionally identical or different)
[changing 5]
(in formula, m indicates 5 or more integer；A2Indicate hydrogen atom or alkyl；X2Indicate the optionally methylene with substituent group Base, above-mentioned substituent group are optionally identical or different)
That is, (methyl) acrylic resin (A) of the present invention in side chain due to having the different hydroxyl of carbon chain lengths (n and m) Base alkyl, thus deducibility：For the adhesive phase formed by adhesive composition, (methyl) acrylic acid series tree can be made Crosslink density between fat optimizes.By the optimization of the crosslink density, the balancing good of hardness and pliability can be formed The adhesive phase of (or with optimal hardness), therefore durability can be improved, it even in a high temperature environment also can be effectively Inhibit the stripping (or floating) and foaming at interface.Moreover, even if can effectively be mitigated if generating strong shrinkage stress adhesive phase The stress, therefore the whiting associated with the contraction of optical film (such as polarization plates) can be prevented.In turn, pass through the crosslink density It optimizes, weight processability (fissility) can also improve.It should be noted that in the present specification, durability refers to：Such as in height Under warm environment, under hot and humid environment, repeatedly present in the environment of high temperature and low temperature etc., adhesive phase can be inhibited and be adjacent to The characteristic (sometimes referred to as peel resistance) for floating or peeling off of the interface of its optical component and adhesive phase can be inhibited Foaming a problem that characteristic (sometimes referred to as resistance to foaminess).In addition, in the present invention, resistance to cohesive failure refers to： It can inhibit the characteristic of the cohesional failure (or damaged) of adhesive phase.
In formula (a1) and formula (a2), X1And X2Indicate the optionally methylene with substituent group.As the substituent, it can lift Go out such as halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl (such as methyl, ethyl, propyl, isopropyl, fourth The C such as base, sec-butyl, tertiary butyl, amyl, hexyl1-10Alkyl；Preferably C1-6Alkyl；Further preferably C1-3Alkyl), cycloalkanes Base (cyclopenta, cyclohexyl etc.), aryl [phenyl, alkyl phenyl (tolyl, xylyl etc.)], aralkyl (benzyl etc.), Alkoxy (such as the C such as methoxyl group, ethyoxyl1-4Alkoxy), polyoxy alkylidene (such as dioxyethylene etc.), cycloalkyloxy (example Such as cyclohexyloxy C5-10Cycloalkyloxy etc.), aryloxy group (such as phenoxy group etc.), aralkoxy (such as benzyl oxygroup etc.), Alkyl sulfenyl (such as the C such as methylsulfany, ethylsulfanyl1-4Alkyl sulfenyl etc.), cycloalkylsulfanyl (such as cyclohexylthio etc.), Artyl sulfo (such as thio phenoxy group etc.), aromatic alkyl sulfurio (such as benzylthio etc.), acyl group (such as acetyl group etc.), nitre Base, cyano etc..Among these, preferably halogen atom, alkyl, alkoxy, aryloxy group etc., particularly preferably alkyl (such as first Base, ethyl etc.).
A1And A2Hydrogen atom or alkyl are indicated respectively；Alkyl can be X1And X2The alkyl (preferably methyl etc.) of middle illustration.
In formula (a1), n indicates 1~4 integer, preferably 1~3 integer, further preferably 2.In addition, in formula (a2) in, the integer (such as 5~20 integer) that m is 5 or more, preferably 5~15 (such as 5~11 integer) are further excellent 5~9 are selected as (such as 5~7 integer), specifically for 5.In addition, m can be 5 or more even number (such as 6,8,10,12 etc.), it can Think 5 or more odd number (such as 5,7,9,11 etc.).
As the concrete example of hydroxyl (methyl) acrylate (a1), (methyl) acrylic acid 1- hydroxy methyls, (first can be enumerated Base) acrylic acid 1- hydroxy methacrylates, (methyl) acrylic acid 1- hydroxyls heptyl ester, (methyl) acrylic acid 1- hydroxybutyls, (methyl) propylene Sour 1- hydroxyls pentyl ester etc. (methyl) acrylic acid 1- hydroxyls C1-8Arrcostab；(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 2- hydroxyls pentyl ester, (methyl) acrylic acid 2- hydroxyls oneself Ester etc. (methyl) acrylic acid 2- hydroxyls C2-9Arrcostab；(methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxyl fourths (the first such as ester, (methyl) acrylic acid 3- hydroxyls pentyl ester, the own ester of (methyl) acrylic acid 3- hydroxyls, (methyl) acrylic acid 3- hydroxyl heptyl esters Base) acrylic acid 3- hydroxyls C3-10Arrcostab；(methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 4- hydroxyls pentyl ester, (first Base) (methyl) propylene such as the own ester of acrylic acid 4- hydroxyls, (methyl) acrylic acid 4- hydroxyls heptyl ester, (methyl) acrylic acid 4- hydroxyl monooctyl esters Sour 4- hydroxyls C4-11Arrcostab；(methyl) acrylic acid 2- chlorine-2-hydroxyls propyl ester, (methyl) acrylic acid 3- chlorine-2-hydroxyls propyl ester, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls etc..Among these, from the viewpoint of durability, preferably acrylic acid 2- The hydroxyl (methyl) third that the n such as hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls are 2 Olefin(e) acid ester；(methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxybutyls, (methyl) acrylic acid 3- hydroxyl pentyl esters etc. Hydroxyl (methyl) acrylate that n is 3.Hydroxyl (methyl) acrylate that the particularly preferred n is 2, among these, preferably For (methyl) acrylic acid 2- hydroxy methacrylates.
As the concrete example of hydroxyl (methyl) acrylate (a2), (methyl) acrylic acid 5- hydroxyls pentyl ester, (first can be enumerated Base) the own ester of acrylic acid 5- hydroxyls, (methyl) acrylic acid 5- hydroxyls heptyl ester, (methyl) acrylic acid 5- hydroxyls monooctyl ester, (methyl) propylene (methyl) acrylic acid 5- hydroxyls such as sour 5- hydroxyls nonyl ester C5-12Arrcostab；The own ester of (methyl) acrylic acid 6- hydroxyls, (methyl) propylene Sour 6- hydroxyls heptyl ester, (methyl) acrylic acid 6- hydroxyls monooctyl ester, (methyl) acrylic acid 6- hydroxyl nonyls ester, (methyl) acrylic acid 6- hydroxyls Last of the ten Heavenly stems ester etc. (methyl) acrylic acid 6- hydroxyls C6-13Arrcostab；(methyl) acrylic acid 7- hydroxyls heptyl ester, (methyl) acrylic acid 7- hydroxyls Monooctyl ester, (methyl) acrylic acid 7- hydroxyl nonyls ester, (methyl) acrylic acid 7- hydroxyls last of the ten Heavenly stems ester, (methyl) acrylic acid 7- hydroxyundecyls Ester etc. (methyl) acrylic acid 7- hydroxyls C7-14Arrcostab；(methyl) acrylic acid 8- hydroxyls monooctyl ester, (methyl) acrylic acid 8- hydroxyl nonyls Ester, (methyl) acrylic acid 8- hydroxyls last of the ten Heavenly stems ester, (methyl) acrylic acid 8- hydroxyundecyls ester, (methyl) acrylic acid 8- hydroxyls 12 Arrcostab etc. (methyl) acrylic acid 8- hydroxyls C8-15Arrcostab；(methyl) acrylic acid 9- hydroxyl nonyls ester, (methyl) acrylic acid 9- hydroxyls Base last of the ten Heavenly stems ester, (methyl) acrylic acid 9- hydroxyundecyls ester, (methyl) acrylic acid 9- hydroxy dodecyl acrylates, (methyl) acrylic acid 9- hydroxy tridecyl base esters etc. (methyl) acrylic acid 9- hydroxyls C9-16Arrcostab；(methyl) acrylic acid 10- hydroxyls last of the ten Heavenly stems ester, (methyl) Acrylic acid 10- hydroxyundecyls ester, (methyl) acrylic acid 10- hydroxy dodecyl acrylates, acrylic acid 10- hydroxy tridecyl bases (methyl) acrylic acid 10- hydroxyls C such as ester, (methyl) acrylic acid 10- hydroxy-tetradecyl base esters10-17Arrcostab；(methyl) acrylic acid 11- hydroxyundecyls ester, (methyl) acrylic acid 11- hydroxy dodecyl acrylates, (methyl) acrylic acid 11- hydroxy tridecyl bases (methyl) acrylic acid such as ester, (methyl) acrylic acid 11- hydroxy-tetradecyls base ester, (methyl) acrylic acid 11- hydroxypentadecanoic base esters 10- hydroxyls C11-18Arrcostab；(methyl) acrylic acid 12- hydroxy dodecyl acrylates, (methyl) acrylic acid 12- hydroxy tridecyl bases Ester, (methyl) acrylic acid 12- hydroxy-tetradecyl base esters etc. (methyl) acrylic acid 12- hydroxyls C12-19Arrcostab；(methyl) propylene Sour 13- hydroxy tridecyls base ester, (methyl) acrylic acid 13- hydroxy-tetradecyls base ester, (methyl) acrylic acid 13- hydroxypentadecanoic bases Ester etc. (methyl) acrylic acid 13- hydroxyls C13-20Arrcostab；(methyl) acrylic acid 14- hydroxy-tetradecyls base ester, (methyl) acrylic acid 14- hydroxypentadecanoic base esters etc. (methyl) acrylic acid 14- hydroxyls C14-21Arrcostab；(methyl) acrylic acid 15- hydroxypentadecanoic bases (methyl) acrylic acid 15- hydroxyls C such as ester, (methyl) acrylic acid 15- hydroxyl heptadecane base esters15-22Arrcostab etc..Among these, from From the viewpoint of durability, preferably (methyl) acrylic acid 5- hydroxyls pentyl ester, the own ester of (methyl) acrylic acid 5- hydroxyls, (methyl) third Hydroxyl (the first that the n such as olefin(e) acid 5- hydroxyls heptyl ester, (methyl) acrylic acid 5- hydroxyls monooctyl ester, (methyl) acrylic acid 5- hydroxyl nonyl esters are 5 Base) acrylate, particularly preferably (methyl) acrylic acid 5- hydroxyl pentyl esters.
Relative to 100 parts by weight of entire infrastructure unit of composition (methyl) acrylic resin, it is originated from shown in formula (a1) The ratio of the structural unit of hydroxyl (methyl) acrylate is preferably the parts by weight of 1.5 parts by weight~4.5, is originated from shown in formula (a2) The ratio of structural unit of hydroxyl (methyl) acrylate be preferably the parts by weight of 0.25 parts by weight~1.0.As long as in addition, source The structural unit of hydroxyl (methyl) acrylate shown in formula (a1) with from hydroxyl (methyl) third shown in formula (a2) The ratio (weight ratio) of the structural unit of olefin(e) acid ester is above range, there is no particular limitation, preferably (a1)/(a2)=13/1 ~3/1 (such as 11/1~3/1), further preferably 9/1~4/1, especially it is possible to be 7/1~5/1.If in above-mentioned Range is then advantageous for forming best cross-linked structure, and then can improve the characteristics such as durability.
(methyl) acrylic resin (A) can include structural unit from alkyl acrylate (a3) and from containing taking The structural unit of the alkyl acrylate (a4) of Dai Ji.
Among alkyl acrylate (a3), 0 DEG C of alkyl acrylate is less than as the glass transition temperature (Tg) of homopolymer Base ester (a3-1) can enumerate such as ethyl acrylate, n-propyl and isopropyl acrylate, n-butyl acrylate and propylene Sour isobutyl ester, acrylic acid n-pentyl ester, the just own ester of acrylic acid and the positive heptyl ester of Isohexyl acrylate, acrylic acid, n-octyl and The positive nonyl ester of Isooctyl acrylate monomer, 2-EHA, the acrylic acid and different nonyl ester of acrylic acid, the positive last of the ten Heavenly stems ester of acrylic acid and acrylic acid The straight-chain or branched alkyl acrylate that the carbon number of the alkyl such as isodecyl ester, acrylic acid n-dodecane base ester is 2~12 or so Deng.Alkyl acrylate (a3) can be the alkyl acrylate (acrylate base ester) with ester ring type structure, from for From the viewpoint of tracing ability (or flexibility, adhesiveness) of optical film etc., preferably the carbon number of acrylic acid be 2~10 alkyl It is Arrcostab that the carbon number of Arrcostab, further preferred acrylic acid that the carbon number of ester, preferably acrylic acid is 3~8 is 4~6, especially excellent It is selected as acrylic acid normal-butyl Arrcostab.If using acrylic acid normal-butyl Arrcostab, tracing ability can be improved, such as resistance to It is advantageous for fissility etc..These alkyl acrylates (a3-1) can be used alone, or be applied in combination two or more.
The alkyl acrylate (a3-2) that Tg as homopolymer is 0 DEG C or more, can enumerate methyl acrylate, acrylic acid ring Arrcostab (such as cyclohexyl acrylate, isobornyl acrylate), stearyl acrylate, tert-butyl acrylate etc., in particular, special It You Xuanwei not methyl acrylate.If using methyl acrylate, intensity can be improved, such as cohesional failure is to have Profit.These alkyl acrylates (a3-2) can be used alone, or be applied in combination two or more.It should be noted that acrylic acid The Tg of the homopolymer of Arrcostab is referred to the literature value such as POLYMER HANDBOOK (Wiley-Interscience).
About the ratio of the structural unit from alkyl acrylate in (methyl) acrylic resin (A), from bonding From the viewpoint of the durability of oxidant layer and again processing (rework) property, relative to the complete of composition (methyl) acrylic resin (A) 100 parts by weight of portion's structural unit, more than for example, 40 parts by weight (such as 50 parts by weight~98 parts by weight), preferably 60 parts by weight Above (such as 70 parts by weight~95 parts by weight), more than further preferably 70 parts by weight the (weight of such as 80 parts by weight~90 Part).
If the alkyl acrylate that the Tg of the alkyl acrylate and homopolymer by the Tg of homopolymer less than 0 DEG C is 0 DEG C or more Base ester is used in combination, then can take into account resistance to cohesive failure and tracing ability (resistance to foaminess and peel resistance), can improve optical film (example Such as polarization plates) for the durability of change in size.
Glass transition temperature from homopolymer less than 0 DEG C of alkyl acrylate (a3-1) structural unit be originated from The ratio (weight ratio) of the structural unit for the alkyl acrylate (a3-2) that glass transition temperature is 0 DEG C or more be (a3-1)/ (a3-2)=20/80~95/5 (such as 30/70~90/10), preferably 40/60~85/15, further preferably 55/45~ 75/25.If being in above range, durability can be further increased.It is less than 0 DEG C of propylene from glass transition temperature The ratio of the structural unit of acid alkyl ester (a3-1) is bigger, then tracing ability can more improve.From glass transition temperature be 0 DEG C with On alkyl acrylate (a3-2) structural unit ratio it is bigger, then resistance to cohesive failure more can improve.
As the alkyl acrylate (a4) containing substituent group, can enumerate for example in above-mentioned alkyl acrylate (a3-1) Alkyl is imported with (hydrogen atom of alkyl is substituted with a substituent) alkyl acrylate of substituent group.The substituent group can be for example Aryl (phenyl etc.), aryloxy group (phenoxy group), alkoxy (such as methoxyl group, ethyoxyl etc.) etc..As the propylene containing substituent group Acid alkyl ester (a3-3) can enumerate such as alkoxyalkyl acrylate (such as acrylic acid 2- methoxy acrylates, acrylic acid ethoxy Base methyl esters etc.), acrylic acid aryloxy group alkyl base ester (such as phenoxyethyl acrylate etc.), aryloxy group polyalkylene glycol mono propylene Acid esters, polyalkylene glycol mono acrylate etc..These alkyl acrylates (a3-3) may be used singly or in combin It is two or more.By the way that comprising the alkyl acrylate with aromatic rings such as aryl, aryloxy group, polarization plates when endurance test can be improved Whiting.In addition, the alkylidene of aryloxy group polyalkylene glycol mono acrylate and polyalkylene glycol mono acrylate can be with For C such as such as methylene, ethylidene, propylidene1-6Alkylidene (preferably ethylidene etc.) etc., forms from by adhesive composition Adhesive layer durability from the viewpoint of, the repetitive unit of oxyalkylene for example can be 2~7, preferably 2~5 (specifically for 2).In the present invention, due in adhesive composition include (methyl) acrylic resin (A) and aftermentioned crosslinking agent (B), being capable of shape At best cross-linked structure (or crosslink density), therefore, even if the number of repeat unit of oxyalkylene is smaller, also show that good Weight processability.Specifically, two C of phenoxy group such as phenoxy group diethylene glycol acrylate can be enumerated1-3Aklylene glycol-the third Seven C of olefin(e) acid ester or even phenoxy group1-3Two C such as aklylene glycol-acrylate, diethylene glycol monoacrylate1-3Alkylidene two Alcohol-mono acrylic ester or even seven C1-3Aklylene glycol-mono acrylic ester etc..
The ratio of structural unit from the alkyl acrylate containing substituent group is relative to composition (methyl) acrylic acid series tree 100 parts by weight of entire infrastructure unit of fat (A) are, for example, the parts by weight of 0 parts by weight~30 (such as 1 parts by weight~25 parts by weight), excellent It is selected as the parts by weight of the parts by weight of 3 parts by weight~20, further preferably 5 parts by weight~15.
(methyl) acrylic resin (A) can include be originated from addition to hydroxyl (methyl) acrylate (a1) and (a2), The structural unit of other monomers (a5) except alkyl acrylate (a3) and alkyl acrylate (a4) containing substituent group.It is other Monomer may be used singly or in combin two or more.As other monomers (a5), can enumerate with other than hydroxyl Polar functional group monomer (a5-1), acrylamide monomer (a5-2), methacrylate (methylpropenoic Acid ester) (a5-3), methacryl amine system monomer (a5-4), styrenic monomers (a5-5), vinyl monomer (a5-6), intramolecular has the monomer (a5-7) etc. of multiple (methyl) acryloyl groups.
As the monomer (a5-1) with the polar functional group other than hydroxyl, can enumerate with carboxyl, substitution or not (methyl) acrylate of the substituent groups such as the heterocycles such as substituted-amino, epoxy group.Specifically, can enumerate acryloyl morpholine, Caprolactam, n-vinyl-2-pyrrolidone, vinylpyridine, (methyl) tetrahydrofurfuryl acrylate, caprolactone modification Tetrahydrofurfuryl acrylate, (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates, (methyl) glycidyl acrylate, 2,5- dihydros Furans etc. has the monomer of heterocycle；(methyl) acrylate, (methyl) acrylic acid N, N- dimethylamino ethyl ester, (methyl) acrylate propyl ester etc. has the monomer of substitution or unsubstituted amino；(methyl) acrylic acid, maleic acid, horse Come acid anhydrides, fumaric acid, crotonic acid, (methyl) acrylic acid carboxyalkyl ester (such as (methyl) carboxyethyl acrylates, (methyl) third Olefin(e) acid carboxyl pentyl ester) etc. with carboxyl monomer.These monomers can be used alone, or be applied in combination two or more.It should Illustrate, from the viewpoint of the reduction of the fissility for the diaphragm for preventing to be laminated in adhesive phase, is preferably substantially free of from tool There is the structural unit of the monomer of amino.It is referred to it should be noted that being substantially free of：Relative to composition (methyl) acrylic resin (A) 100 parts by weight of entire infrastructure unit are less than 1.0 parts by weight.
In the present invention, even if without being considered making the increased structural unit for being originated from the monomer with carboxyl of ITO corrosivity The structural unit of (be originated from containing carboxyl (methyl) acrylate), also shows high durability, therefore can take into account durability and resistance to ITO corrosivity.
If in addition, [being originated from the knot containing carboxyl (methyl) acrylate containing the structural unit for being originated from the monomer with carboxyl Structure unit], then it can further increase durability.In the present invention, even if from the structure containing carboxyl (methyl) acrylate The ratio of unit is few, can also effectively improve durability, therefore can inhibit the corrosion of ITO and durability is made to improve.
Ratio from the structural unit containing carboxyl (methyl) acrylate is relative to the knot from (methyl) acrylate 100 parts by weight of structure unit are, for example, 5.0 parts by weight or less (such as 0 parts by weight~3 parts by weight), below preferably 1.0 parts by weight (such as 0.001 parts by weight~0.5 parts by weight) below (such as 0 parts by weight~0.8 parts by weight), more preferably 0.5 parts by weight, into One step be preferably 0.3 parts by weight or less (such as 0.005 parts by weight~0.3 parts by weight), specifically for below 0.2 parts by weight (such as The parts by weight of 0.01 parts by weight~0.2), (such as 0.05 parts by weight~0.15 parts by weight) below in particular 0.15 parts by weight.If For upper limit value hereinafter, can then inhibit ITO corrosivity, more than lower limiting value, durability can be improved.
As acrylamide monomer (a5-2), for example, N hydroxymethyl acrylamide, N- (2- hydroxyethyls) acryloyl Amine, N- (3- hydroxypropyls) acrylamide, N- (4- hydroxybutyls) acrylamide, N- (5- Hydroxy pentyls) acrylamide, N- (6- Hydroxyl hexyl) acrylamide, N, N- dimethacrylamide, N, N- acrylamides, n-isopropyl acrylamide, N- (3- dimethylaminopropyls) acrylamide, N- (1,1- dimethyl -3- oxa-s butyl) acrylamide, N- (2- (2- oxa-s -1- Imidazolidinyl) ethyl) acrylamide, 2- Acryloyl aminos -2- methyl-1s-propane sulfonic acid, N- (methoxy) acrylamide, N- (ethoxyl methyl) acrylamide, N- (propoxy methyl) acrylamide, N- (1- methylethoxies ylmethyl) acrylamide, N- (1- methyl propoxy methyl) acrylamide, N- (2- methyl propoxy methyl) acrylamide (alias：N- (isobutoxymethyl) Acrylamide), N- (butoxymethyl) acrylamide, N- (1,1- dimethylethoxies ylmethyl) acrylamide, N- (2- methoxyl groups Ethyl) acrylamide, N- (2- ethoxyethyl groups) acrylamide, N- (2- Amongs) acrylamide, N- (2- (1- methyl Ethyoxyl) ethyl) acrylamide, N- (2- (1- methyl propoxyl group) ethyl) acrylamide, N- (2- (2- methyl propoxyl group) second Base) acrylamide (alias：N- (2- isobutoxyethies) acrylamide), N- (2- butoxyethyl groups) acrylamide, N- (2- (1,1- dimethylethyloxies) ethyl) acrylamide etc..Among these, preferably N- (methoxy) acrylamide, N- (second Oxygroup methyl) acrylamide, N- (propoxy methyl) acrylamide, N- (butoxymethyl) acrylamide, N- (2- methyl-prop oxygen Ylmethyl) acrylamide etc..
As methacrylate (methylpropenoic acid ester) (a5-3), such as metering system can be enumerated Sour methyl esters, ethyl methacrylate, propyl methacrylate, n-BMA, n octyl methacrylate, methyl-prop The methacrylic acids straight-chain alkyl ester such as olefin(e) acid lauryl；Isobutyl methacrylate, 2-Ethylhexyl Methacrylate, methyl The methacrylic acids branched-chain alkyl ester such as Isooctyl acrylate monomer；Isobornyl methacrylate, cyclohexyl methacrylate, methyl Dicyclopentanyl acrylate, methacrylic acid cyclododecane base ester, methyl methacrylate base cyclohexyl, methacrylic acid front three basic ring Methacrylic acids monocycle Arrcostab or the methyl such as own ester, t-butyl cyclohexyl ester, methacrylic acid cyclohexyl phenyl ester Acrylic acid bicyclic alkyl ester；The methacrylic acids alcoxyls such as methacrylic acid 2- methoxy acrylates, methacrylic acid ethyoxyl methyl esters Base Arrcostab；Methacrylic acids aralkyl ester such as benzyl methacrylate etc..
As methacryl amine system monomer (a5-4), can enumerate for example with the acrylamide monomer described in (a5-2) Corresponding methacryl amine system monomer etc..
As styrenic monomers (a5-5), such as styrene can be enumerated；Methyl styrene, dimethyl styrene, front three Base styrene, ethyl styrene, diethyl, triethylbenzene ethylene, propylstyrene, butylstyrene, hexyl benzene second The ring-alkylated styrenes such as alkene, heptyl styrene, octyl styrene；Fluorobenzene ethene, chlorostyrene, bromstyrol, Dowspray 9, iodine The halogenated styrenes such as styrene；Nitrostyrolene；Acetylbenzene ethylene；Methoxy styrene；Divinylbenzene etc..
As vinyl monomer (a5-6), such as vinyl acetate, vinyl propionate, vinyl butyrate, 2- can be enumerated The fatty acid vinyl esters such as ethyl hexanoate, vinyl laurate；The vinyl halides such as vinyl chloride, vinyl bromide；Vinylidene chloride Etc. inclined dihalo ethylene；The nitrogenous aromatic ethenyl such as vinylpyridine, vinyl pyrrolidone, vinyl carbazole；Butadiene, Isoprene, chlorobutadiene equiconjugate diene monomers；Unsaturated nitriles such as acrylonitrile, methacrylonitrile etc..
The monomer (a5-7) as intramolecular with multiple (methyl) acryloyl groups, can enumerate such as 1,4-butanediol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, tripropylene glycol two Monomer with 2 (methyl) acryloyl groups in (methyl) acrylate equimolecular；Trimethylolpropane tris (methyl) acrylic acid Monomer etc. with 3 (methyl) acryloyl groups in ester equimolecular.
In addition, from the viewpoint of the heavy processability of adhesive phase, (methyl) acrylic resin (A) preferably originates from methyl The metering systems such as acrylate (methylpropenoic acid ester) (a5-3), methacryl amine system monomer (a5-4) The ratio (or content) of the structural unit of acid system monomer is small.That is, the ratio of the structural unit is relative to composition (methyl) acrylic acid 100 parts by weight of entire infrastructure unit for being resin (A) are preferably 10 parts by weight hereinafter, further preferably 5 parts by weight are hereinafter, spy It can be 1 parts by weight or less not to be.
In addition, the ratio of the structural unit from other monomers (a5) is relative to composition (methyl) acrylic resin (A) 100 parts by weight of entire infrastructure unit for example can be the parts by weight of 0 parts by weight~20, the parts by weight (example of preferably 0 parts by weight~10 Such as the parts by weight of 0.001 parts by weight~10), the parts by weight of the further preferably 0 parts by weight~5 (weight of such as 0.01 parts by weight~3 Part) left and right.
The standard polystyren conversion based on gel permeation chromatography GPC of (methyl) acrylic resin (A) is divided equally again Son amount (Mw) is, for example, 6.0 × 105~2.5 × 106(such as 8.0 × 105~2.5 × 106), preferably 1.0 × 106~2.0 × 106, further preferably 1.2 × 106~1.8 × 106(such as 1.3 × 106~1.6 × 106) range.If Mw is upper limit value Hereinafter, being then advantageous from the viewpoint of coating when adhesive composition to be coated on to base material, if Mw is lower limiting value More than, then be conducive to improve tracing ability of the adhesive phase relative to the change in size of optical film.Weight average molecular weight Mw divides equally with number Molecular weight distribution shown in the ratio between son amount Mn (Mw/Mn) is usually 2~10, preferably 3~8, further preferably 4~6.
In addition, Mw of (methyl) acrylic resin (A) on the exhaust line in GPC is 1.0 × 103~2.5 × 106 In the range of preferably have simple spike.It is viscous for improving if (methyl) acrylic resin (A) for the use of the peak number being 1 It is advantageous for the durability of mixture layer.
" there is simple spike " in the above range of gained exhaust line to refer to：It is 1.0 × 10 in Mw3~2.5 × 106 In the range of only have 1 maximum.In this specification, in GPC exhaust lines, by S/N than being defined as 30 or more peak Peak.It should be noted that the Mw and Mn of the peak number of GPC exhaust lines and (methyl) acrylic resin (A) can pass through embodiment one GPC determination conditions described in are found out.
When the solution of a concentration of 20 weight % is made being dissolved in ethyl acetate in (methyl) acrylic resin (A), 25 Viscosity at DEG C is preferably 20Pas hereinafter, more preferably 0.1Pas~7Pas.If it is the viscosity of the range, from It is advantageous from the viewpoint of coating when adhesive composition to be coated on to base material.It should be noted that viscosity can pass through Brookfield viscosimeters are measured.
The glass transition temperature (Tg) of (methyl) acrylic resin (A) for example can be -60 DEG C~0 DEG C (such as -50 DEG C~-10 DEG C), preferably -50 DEG C~-20 DEG C, further preferably -40 DEG C~-20 DEG C (such as -40 DEG C~-25 DEG C).If For the range, then be conducive to improve durability.It should be noted that glass transition temperature can pass through differential scanning calorimetry (DSC) (DSC) It is measured.
(methyl) acrylic resin (A) can be for example, by solution polymerization process, mass polymerization, suspension polymerization, lotion The known methods such as polymerization are manufactured, particularly preferably solution polymerization process.As solution polymerization process, can enumerate monomer for example It is mixed with organic solvent, adds thermal polymerization in a nitrogen atmosphere, at 40 DEG C~90 DEG C (preferably 50 DEG C~80 DEG C) The method that 3 hours~15 hours or so are stirred under the temperature condition of left and right.In order to control reaction, can it is continuous in polymerization or Add monomer, thermal polymerization with having a rest.The monomer, thermal polymerization can be the state being added in organic solvent.
As polymerization initiator, thermal polymerization, Photoepolymerizationinitiater initiater etc. can be used.As Photoepolymerizationinitiater initiater, It can enumerate such as 4- (2- hydroxyl-oxethyls) phenyl (2- hydroxyl -2- propyl) ketone.As thermal polymerization, can enumerate for example 2,2 '-azobis isobutyronitriles, 2,2 '-azos bis- (2- methylbutyronitriles), 1,1 '-azos bis- (hexamethylene -1- formonitrile HCNs), 2,2 '-are occasionally Nitrogen bis- (2,4- methyl pentane nitriles), 2,2 '-azos bis- (2,4- dimethyl -4- methoxyl-valeronitriles), dimethyl -2,2 '-azo are double The azo compounds such as (2 Methylpropionic acid ester), 2,2 '-azos bis- (2- hydroxymethyls propionitrile)；Lauryl peroxide, tertiary fourth Base hydrogen peroxide, benzoyl peroxide, peroxidized t-butyl perbenzoate, cumyl hydroperoxide, dicetyl peroxydicarbonate diisopropyl Ester, dipropyl peroxydicarbonate, new peroxide tert-butyl caprate, the peroxidating pivalic acid tert-butyl ester, peroxidating (3,5,5- front threes Base caproyl) etc. organic peroxides；Inorganic peroxides such as potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide etc..In addition, also may be used To use the redox series initiators etc. of peroxide and reducing agent.
The ratio of polymerization initiator is relative to 100 parts by weight of total amount of the monomer of composition (methyl) acrylic resin Parts by weight of 0.001 parts by weight~5 or so.The polymerization of (methyl) acrylic resin can use and be based on active energy beam (example Such as ultraviolet light) polymerization.
As organic solvent, can enumerate aromatic hydrocarbon such as toluene, dimethylbenzene；The esters such as ethyl acetate, butyl acetate Class；The aliphatic alcohols such as propyl alcohol, isopropanol；Ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc..
[1-2] crosslinking agent (B)
Adhesive composition includes crosslinking agent (B).The crosslinking agent (B) includes with (methyl) acrylic resin (A) The polar functional group of hydroxyl reacts.
Crosslinking agent (B) is toluene di-isocyanate(TDI) based compound and/or toluene di-isocyanate(TDI) based compound based on more The addition product (adduct) of first alcoholic compound (such as glycerine, trimethylolpropane etc.).As toluene di-isocyanate(TDI) system chemical combination It is single can to enumerate such as 2,6- toluene di-isocyanate(TDI)s, 2,4- toluene di-isocyanate(TDI)s, 3,5- toluene di-isocyanate(TDI)s etc. for object Methyl phenylene diisocyanate etc..In the present invention, what is imported to the side chain of (methyl) acrylic resin (A) has different carbon chain long The OH bases (hydroxyl) of hydroxy alkyl for spending (n and m) react with crosslinking agent (B), formed for durability and weigh processability and Say advantageous cross-linked structure.In particular, crosslinking agent (B) is by above-mentioned toluene di-isocyanate(TDI) based compound and/or above-mentioned toluene two The polyol compound of isocyanates based compound is formed, therefore can estimate the balance that can form intensity and flexibility (flexibility) Superior cross-linked structure can further increase durability.That is, not only applied to glass substrate, applying (stacking) can also embody high durability in the case of such as ito substrate.It should be noted that crosslinking agent (B) is isocyanates Based compound, therefore, from the term of validity of crosslinking rate and adhesive composition from the viewpoint of be also advantageous.
The ratio of crosslinking agent (B) for example can be 0.01 weight relative to 100 parts by weight of (methyl) acrylic resin (A) Part~parts by weight of 10 parts by weight (such as 0.05 parts by weight~5 parts by weight), preferably 0.1 parts by weight~3 (such as 0.1 parts by weight ~2 parts by weight), further preferably parts by weight of 0.2 parts by weight~1 (such as 0.3 parts by weight~0.8 parts by weight).Upper limit value is got over Small, then more advantageous for improving tracing ability (or peel resistance), lower limiting value is bigger, then (or resistance to for improving resistance to cohesion Foaminess), weight processability for it is more advantageous.
[1-3] silane compound (C)
Adhesive composition includes silane compound (C).By the way that comprising the silane compound (C), adhesive can be improved The adaptation (or cementability) of layer and metal layer, transparent electrode, glass substrate etc..As silane compound (C), as long as can The silane compound being bonded with the reactive group (such as OH yls of hydroxyl) of (methyl) acrylic resin (A), can lift Go out such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyl three (2- methoxy ethoxies) silane, 3- rings Oxygen propoxypropyl trimethoxy silane, 3- glycidoxypropyl groups triethoxysilane, 3- glycidoxypropyls two Methoxy silane, 3- glycidoxypropyl group ethyoxyls dimethylsilane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silicon Alkane, 3- chloropropylmethyldimethoxysilanes, 3- r-chloropropyl trimethoxyl silanes, 3- methacryloxypropyl trimethoxies Bis- (3 '-trimethoxy propyl) ureas of silane, 3-mercaptopropyi trimethoxy silane, 1,3- etc..
In addition, silane compound (C) can be the compound of silicone oligomers type, if with monomer combination with one another come The silicone oligomers are stated, then can enumerate such as 3- mercaptopropyis two or trimethoxy silane-tetramethoxy-silicane oligomer, 3- - four methoxy of mercapto methyl two or trimethoxy silane-tetraethoxysilane oligomer, 3- mercaptopropyis two or triethoxysilane Base silane oligomer, 3- mercapto methyls two or triethoxysilane-tetraethoxysilane oligomer etc. is containing the oligomeric of mercaptoalkyl Object；Mercaptoalkyl in the oligomer containing mercaptoalkyl is replaced as other substituent groups [3- glycidoxypropyl groups, (methyl) Acryloxypropyl, vinyl, amino etc.] obtained from oligomer etc..
Silane compound (C) is preferably silane compound shown in following formula (c1).If adhesive composition includes Silane compound shown in following formula (c1) can then further increase adaptation (or cementability), therefore can form resistance to stripping The adhesive phase excellent from property.In turn, the heavy processability of the adhesive phase is also excellent.In particular, under high temperature environment will bonding Oxidant layer application (or stacking) is also able to maintain that adaptation (or cementability) in the case of transparent electrode (such as ito substrate etc.), It can show high-durability.
[changing 6]
(in formula, B indicates the alicyclic type hydrocarbon of the alkane diyl of carbon number 1~20 or the divalent of carbon number 3~20, constitutes above-mentioned - the CH of alkane diyl and above-mentioned alicyclic type hydrocarbon2Optionally it is replaced as-O- or-CO-；R1Indicate the alkyl of carbon number 1~5；R2、 R3、R4、R5And R6Each independently represent the alkyl of carbon number 1~5 or the alkoxy of carbon number 1~5)
In formula (c1), B indicates methylene, ethylidene, trimethylene, tetramethylene, hexa-methylene, heptamethylene, eight The alkane diyl that the carbon numbers such as methylene are 1~20；(such as 1,2- is sub- for sub- cyclobutyl (such as the Asias 1,2- cyclobutyl), cyclopentylene Cyclopenta), cyclohexylidene (such as 1,2- cyclohexylidenes), the carbon numbers such as cyclooctylene (such as 1,2- cyclooctylenes) be 3~20 The alicyclic type hydrocarbon of divalent；Or constitute the-CH of these alkane diyls and above-mentioned alicyclic type hydrocarbon2It is replaced as-O- or-CO- Obtained from group.B is preferably the alkane diyl of carbon number 1~10.R1Indicate methyl, ethyl, propyl, isopropyl, butyl, Zhong Ding The alkyl that the carbon numbers such as base, tertiary butyl, amyl are 1~5；R2、R3、R4、R5And R6Each independently represent above-mentioned R1Illustrated by carbon The alkyl of number 1~5；Or the carbon numbers such as methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, sec-butoxy, tert-butoxy 1~5 alkoxy.R2、R3、R4、R5And R6The preferably alkoxy of carbon number 1~5.These silane compounds (C) can individually make With, or be applied in combination two or more.
As specific silane compound (c1), such as (trimethoxysilyl) methane, the bis- (front threes of 1,2- can be enumerated Oxygroup silicyl) ethane, bis- (triethoxysilyl) ethane of 1,2-, bis- (trimethoxysilyl) propane of 1,3-, Bis- (triethoxysilyl) propane of 1,3-, bis- (trimethoxysilyl) butane of 1,4-, bis- (the triethoxy first silicon of 1,4- Alkyl) butane, bis- (trimethoxysilyl) pentanes of 1,5-, bis- (triethoxysilyl) pentanes of 1,5-, 1,6- bis- (three Methoxysilyl) hexane, bis- (triethoxysilyl) hexanes of 1,6-, 1,6- bis- (tripropoxy-silicane bases) oneself Bis- (trimethoxysilyl) octanes of alkane, 1,8-, bis- (triethoxysilyl) octanes of 1,8-, the bis- (tripropoxies of 1,8- Silicyl) bis- (three C such as octane1-5Alkoxysilyl) C1-10Alkane；Bis- (dimethoxy-methyl silicyl) methane, Bis- (dimethoxy-methyl silicyl) ethane of 1,2-, bis- (dimethoxy-ethyl silicyl) ethane of 1,2-, the bis- (diformazans of 1,4- Oxygen butylmethylsilyl) butane, bis- (dimethoxy-ethyl silicyl) butane of 1,4-, bis- (the dimethoxy-methyl first of 1,6- Silylation) hexane, bis- (dimethoxy-ethyl silicyl) hexanes of 1,6-, 1,8- bis- (dimethoxy-methyl silicyls) be pungent Bis- (two C such as bis- (dimethoxy-ethyl silicyl) octanes of alkane, 1,8-1-5Alkoxy C1-5AIkylsilyl groups) C1-10Alkane； Bis- (single C such as bis- (methoxyl group dimetylsilyl) hexanes of 1,6-, bis- (methoxyl group dimetylsilyl) octanes of 1,8-1-5Alkane - two C of oxygroup1-5AIkylsilyl groups) C1-10Alkane etc..Among these, bis- (trimethoxysilyl) second of preferably 1,2- Bis- (trimethoxysilyl) propane of alkane, 1,3-, bis- (trimethoxysilyl) butane of 1,4-, the bis- (trimethoxies of 1,5- Silicyl) pentane, bis- (trimethoxysilyl) hexanes of 1,6-, bis- (trimethoxysilyl) octanes of 1,8- etc. are double (three C1-3Alkoxysilyl) C1-10Bis- (trimethoxysilyl) hexanes of alkane, particularly preferably 1,6-, 1,8- are bis- (trimethoxysilyl) octane.
The ratio of silane compound (C) is, for example, 0.01~10 relative to 100 parts by weight of (methyl) acrylic resin (A) Parts by weight (such as 0.03~5 parts by weight), preferably 0.05~3 parts by weight, further preferably 0.1~1 parts by weight (such as 0.2~0.5 parts by weight).If it is upper limit value hereinafter, then for inhibiting silane compound (C) for being oozed out in adhesive phase It is advantageous, more than lower limiting value, the adaptation for being easy to improve adhesive phase and metal layer, glass substrate etc. (or is glued Connecing property), it is advantageous for improving peel resistance etc..
[1-4] antistatic agent
Adhesive composition can further include antistatic agent.(inhibited for example by that comprising antistatic agent, can improve The unfavorable condition etc. caused by electrostatic generated when by strippings such as mold release film, protective films) adhesive antistatic property.As anti-quiet Electric agent can enumerate usual substance, be suitably for ionic antistatic agent.As constitute the cation of ionic antistatic agent at Point, organic cation, inorganic cation etc. can be enumerated.As organic cation, such as pyridylium, imidazoles can be enumerated Cation, ammonium cation, sulfonium cation, phosphorus cation etc..As inorganic cation, such as lithium cation, potassium sun can be enumerated The alkali metal cations such as ion, sodium cation, caesium cation；Alkaline earth metal cations such as magnesium cation, calcium cation etc..As The anion component of ionic antistatic agent is constituted, can be any one of inorganic anion and organic anion, from anti-quiet From the viewpoint of excellent electrical property, preferably include the anion component of fluorine atom.As the anion component comprising fluorine atom, Such as hexafluorophosphoric acid salt anionic (PF can be enumerated6), bis- (trifyl) imide anion [(CF3SO2)2N-], it is double (fluorosulfonyl) imide anion [(FSO2)2N-], four (pentafluorophenyl group) borate anion [(C6F5)4B-] etc..These are anti- Electrostatic agent can be used alone, or be applied in combination two or more.Particularly preferably bis- (trifyl) acid imide the moon from Son [(CF3SO2)2N-], bis- (fluorosulfonyl) imide anion [(FSO2)2N-], four (pentafluorophenyl group) borate anions [(C6F5)4B-]。
Preferably it is solid at room temperature from the viewpoint of the ageing stability of the antistatic property of adhesive composition is excellent The ionic antistatic agent of body.
The ratio of antistatic agent for example can be 0.01 weight relative to 100 parts by weight of (methyl) acrylic resin (A) Part~parts by weight of parts by weight of 10 parts by weight, preferably 0.1 parts by weight~5, further preferably 1 parts by weight~3.
[1-5] other ingredients
Adhesive composition can include individually solvent, crosslinking catalyst, ultra-violet absorber, weathering stabilizers, thickening The additives such as agent, plasticizer, softening agent, dyestuff, pigment, inorganic filler, light scattering particle include two or more.In addition, Coordinate ultra-violet solidified compound into adhesive composition after forming adhesive phase, irradiate ultraviolet light and make its solidification, It is also useful that harder adhesive phase, which is made,.As crosslinking catalyst, such as hexamethylene diamine can be enumerated, ethylenediamine, gathered It is aziridine, hexa, diethylenetriamines, trien, isophorone diamine, trimethylene diamine, more Amine compounds such as amino resins and melmac etc..
From the viewpoint of the resistance to metal protection for improving adhesive phase, adhesive composition can include antirust agent.Make For antirust agent, three azole compounds such as benzotriazole based compound can be enumerated；The thiazole systems such as benzothiazole based compound Close object；The imidazole compounds such as benzylimidazole based compound；Imidazoline based compound；Quinoline based compound；Pyridine system chemical combination Object；Pyrimidine compound；Indoles based compound；Amine compound；Urea based compound；Sodium benzoate；Benzyl mercaptan base system Close object；Di-sec-butyl sulphur；And diphenyl sulfoxide etc..
[2] composition and manufacturing method of the optical film of adhesive phase and subsidiary adhesive phase
The adhesive composition of the present invention can be by implementing surface activation process (such as corona treatment, sided corona treatment Deng) etc. form adhesive phase.In general, the adhesive phase is laminated at least one face of optical film.
Fig. 1 is an example for the optical film for indicating the subsidiary adhesive phase formed by adhesive composition of the present invention Summary sectional view.The optical film 1 of subsidiary adhesive phase shown in FIG. 1 is optical film 10 and the adhesive positioned at the optical film single side 20 optical film through being laminated of layer.The adhesive phase 20 is typically directly laminated in the surface of optical film 10.It should be noted that bonding Oxidant layer 20 can be laminated in the two sides of optical film 10.
When adhesive phase 20 is laminated in the surface of optical film 10, preferably in the binding face and/or adhesive of optical film 10 The binding face of layer 20 forms prime coat or implements above-mentioned surface activation process (such as corona treatment, sided corona treatment etc.), Particularly preferably implement sided corona treatment.
As shown in Fig. 2, in the case where optical film 10 is that single side protects polarization plates, the usually stacking of adhesive phase 20 is (preferably To be directly laminated) polarizing unilateral, i.e. polarizing film 2 the face with 3 opposite side of the first resin film.As shown in figure 3, in optical film In the case that 10 protect polarization plates for two sides, adhesive phase 20 can be laminated in the first resin film 3, the second resin film 4 and be appointed The outer surface of one can also be laminated in the outer surface of the two.
Antistatic layer can also be separately set between optical film 10 and adhesive phase 20.As antistatic layer, can make With the silicon systems material such as polysiloxanes；The inorganic metals based materials such as the indium oxide of doped tin, the antimony oxide of doped tin；Polythiophene gathers The organic polymers based material such as styrene sulfonic acid, polyaniline.
The optical film 1 of subsidiary adhesive phase can include the diaphragm (stripping film) for the outer surface for being layered in adhesive phase 20. Usually (such as when being laminated in transparent conductive electrode, glass substrate) is stripped removal to the diaphragm when using adhesive phase 20.Every Film can be to for example by polyethylene terephthalate, polybutylene terephthalate (PBT), makrolon, polyarylate etc. it is each Implement substance obtained from the demouldings such as silicone-treated processing in the surface that form adhesive phase 20 for the film that kind resin is formed.
The optical film 1 of subsidiary adhesive phase can obtain as follows：Each ingredient dissolving of above-mentioned adhesive composition will be constituted Or be dispersed to solvent and solvent-laden adhesive composition is made, next, being coated on the surface of optical film 10 and drying And adhesive phase 20 is formed, thus obtain.In addition, the optical film 1 of subsidiary adhesive phase can also obtain as follows：As described above Ground forms adhesive phase 20 in the demoulding process face of diaphragm, by the adhesive phase 20 stacking (transfer) to the surface of optical film 10, Thus it obtains.
The thickness of adhesive phase is usually 2 μm~40 μm, durability, subsidiary bonding from the optical film of subsidiary adhesive phase From the viewpoint of heavy processability of the optical film of oxidant layer etc., preferably 5 μm~30 μm, further preferably 10 μm~25 μm.Such as Fruit is upper limit value hereinafter, then adhesive phase becomes good for the tracing ability (or trackability) of optical film change in size, if it is More than lower limiting value, then weighing processability becomes good.
Adhesive phase preferably shows the storage modulus of 0.1MPa~5MPa within the temperature range of 23 DEG C~80 DEG C.By This, can more effectively improve the durability of the optical film of subsidiary adhesive phase.It " is showed within the temperature range of 23 DEG C~80 DEG C Go out the storage modulus of 0.1MPa~5MPa " it refers to：Under the arbitrary temp of the range, storage modulus is in above range Value.Storage modulus is usually successively decreased with the rising of temperature, thus, if the storage modulus at 23 DEG C and 80 DEG C is in above-mentioned model In enclosing, then it is contemplated that showing the storage modulus in above range at a temperature of the range.The storage modulus of adhesive phase can Use commercially available determination of viscoelasticity device, the determination of viscoelasticity device " DYNAMIC of such as REOMETRIC companies manufacture ANALYZER RDA II " are measured.
As an index of crosslink density, gel fraction can be used.It is formed by the adhesive composition of the present invention Adhesive phase has defined crosslink density, therefore shows defined gel fraction.That is, the gel fraction example of the adhesive phase Such as can be 50 weight of weight %~95 % (such as 55 weight % of weight %~93), preferably 60 weight of weight %~90 % (such as 65 weight % of weight %~90), further preferably 70 weight of weight %~85 % (such as 80 weights of weight %~85 Measure %).If gel fraction be lower limiting value more than, for adhesive phase resistance to foaminess (resistance to cohesive failure), process again Property for be advantageous, if gel fraction be upper limit value hereinafter, being advantageous for peel resistance.It should be noted that solidifying Glue point rate can be measured by the method described in embodiment one.
There is defined bonding force by the adhesive phase that the adhesive composition of the present invention is formed.That is, on the glass substrate It is bonded above-mentioned adhesive phase, the bonding of above-mentioned adhesive phase under conditions of 23 DEG C of temperature, relative humidity 50%, after 24 hours Power for example can be 0.5N~25N (such as 0.5N~20N), preferably 0.5N~10N under 300mm/ minutes peeling rates (such as 1N~10N), further preferably 1N~8N.If bonding force is lower limiting value or more, adhesiveness (or cementability) carries Height is advantageous for peel resistance etc., if bonding force be upper limit value hereinafter, if for weight processability for be advantageous 's.It should be noted that bonding force can be measured by the method described in embodiment one.
[2-1] optical film
The optical film 10 for constituting the optical film 1 of subsidiary adhesive phase can be that can be assembled to the images such as liquid crystal display device Various optical films (film with optical characteristics) in display device.The optical film 10 can be single layer structure (such as polarizing film, Optical functionals films such as phase difference film, brightness improving film, antiglare film, antireflection film, diffusion barrier, light harvesting film etc.), or it is more Layer structure (such as polarization plates, phase plate etc.).Optical film 10 preferably polarization plates, polarizer, phase difference board or phase difference film, Particularly preferably polarization plates or polarizing film.It should be noted that in this specification, optical film refers to：In order to show image (display picture Face etc.) and the film (such as the film functioned to improve image degree of being clear to) that functions.In addition, in this specification, partially Vibration plate refers to：The polarization plates of resin film or resin layer are laminated at least one face of polarizing film, phase plate refers to： At least one face of phase difference film is laminated with the phase plate of resin film or resin layer.
[2-2] polarization plates
Fig. 2 and Fig. 3 is the summary sectional view for the example for indicating that the layer of polarization plates is constituted.Polarization plates 10a shown in Fig. 2 be The face stacking (or stacking fitting) of polarizing film 2 has the single side protection polarization plates of the first resin film 3, polarization plates shown in Fig. 3 10b is that (or stacking fitting) is further laminated in another face of polarizing film 2 to have the two sides of the second resin film 4 to protect polarization plates. First resin film 3, the second resin film 4 can fit in polarizing film 2 by adhesive layer (not shown), adhesive phase.It should Illustrate, polarization plates 10a, 10b can include other films, the layer other than the first resin film 3, the second resin film 4.
Polarizing film 2 is the film for having following properties, and the property is：It absorbs with the vibration plane parallel with its absorption axis Rectilinearly polarized light, and the rectilinearly polarized light with (with the axis of homology parallel) vibration plane orthogonal with absorption axiss is transmitted, such as can To use polyvinyl alcohol resin film gas absorption quantity to have the film of dichroism pigment.As dichroism pigment, can enumerate such as iodine, Dichroic organic dye etc..
Polyvinyl alcohol resin can be obtained by the way that polyvinyl acetate system resin is carried out saponification.As polyvinyl acetate Ester system resin, can enumerate such as vinyl acetate homopolymer i.e. polyvinyl acetate, can be with the list of vinyl acetate copolymerization Body (such as unsaturated carboxylic acid, alkene, vinyl ethers, unsaturated sulfonic acid, (methyl) acrylamide etc. with ammonium) and acetic acid The copolymer etc. of vinyl acetate.
The saponification degree of polyvinyl alcohol resin is usually 85~100 moles of %, preferably 98 moles of % or more.Polyvinyl alcohol It is resin to be modified, can is the polyvinyl formal being for example modified with aldehydes or polyvinyl alcohol contracting second Aldehyde etc..The average degree of polymerization of polyvinyl alcohol resin is usually 1000~10000, preferably 1500~5000.It should be noted that poly- The average degree of polymerization of vinyl alcohol resin can be found out according to JIS K 6726.
In general, product made of polyvinyl alcohol resin is film-made is used as the former material film of polarizing film 2.Polyvinyl alcohol resin It can be film-made by known method.The thickness of former material film is usually 1 μm~150 μm, if it is considered that stretch easness etc., then it is excellent It is selected as 10 μm or more.
For example by implementing following process and most being manufactured afterwards through dry, the process is polarizing film 2：Former material film is carried out Film is dyed with dichroism pigment and it is made to adsorb the process of the dichroism pigment, uses boric acid aqueous solution by the process that is uniaxially stretched The process that film is handled and the process for being washed film.The thickness of polarizing film 2 is usually 1 μm~30 μm, from incidentally From the viewpoint of the filming of the optical film 1 of adhesive phase, preferably 20 μm or less, further preferably 15 μm or less, special It is 10 μm or less.
Polarizing film 2 can also be obtained by following methods made of making polyvinyl alcohol resin film gas absorption quantity dichroism pigment ：1) it uses the independent film of polyvinyl alcohol resin film as former material film, processing and dichroism color is uniaxially stretched to film implementation The method of the dyeing processing of element；And 2) coating fluid (aqueous solution etc.) containing polyvinyl alcohol resin is coated with to base material film, make After its drying obtains the base material film with polyvinyl alcohol resin layer, it is uniaxially stretched together with base material film, to drawing Polyvinyl alcohol resin layer after stretching implements the dyeing processing of dichroism pigment, the method for next removing base material film stripping. As base material film, can use identical by aftermentioned with the first resin film 3, the thermoplastic resin of the second resin film 4 can be constituted Thermoplastic resin formed film, preferably by the polyester based resins such as polyethylene terephthalate, polycarbonate-based resin, The cyclic polyolefins hydrocarbon system such as the cellulose-based resins such as tri acetyl cellulose, norbornene resin resin, polystyrene resin The film of equal formation.If utilizing the above method 2), it is easy to make the polarizing film 2 of film, such as be also easy to make thickness to be 7 μm Polarizing film 2 below.
First resin film 3, the second resin film 4 can be by the thermoplastic resin, preferably with translucency each independently Optically transparent thermoplastic resin gathers such as chain polyolefin-based resins (polyethylene-based resin, polypropylene-based resin), ring-type The polyolefin-based resins such as olefin-based resin (norbornene resin etc.)；Cellulose-based resin (cellulose esters system resin etc.)；It is poly- Ester system resin (polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate (PBT) etc.)；Poly- carbon Acid esters system resin (such as makrolon etc. derived from the bis-phenols such as bis- (4- hydroxy phenyls) propane of 2,2-)；(methyl) acrylic acid series Resin；Polystyrene resin；Polyether-ether-ketone system resin；The formation such as polysulfones system resin or their mixture, copolymer Film.Among these, the first resin film 3, the second resin film 4 respectively preferably by cyclic polyolefin hydrocarbon system resin, polycarbonate-based resin, The film of the formation such as cellulose-based resin, polyester based resin and (methyl) acrylic resin, particularly preferably by cellulose-based resin With the film of the formation such as cyclic polyolefin hydrocarbon system resin.
As chain polyolefin-based resins, the homopolymerization of the chain olefin such as polyvinyl resin, acrylic resin can be enumerated Object；The copolymer etc. formed by two or more chain olefins.
Cyclic polyolefin hydrocarbon system resin is comprising with norbornene, tetracyclododecane (alias：Dimethano octahydro naphthalene) or it Derivative be typical example cyclic olefin as polymerized unit resin general name.It, can as cyclic polyolefin hydrocarbon system resin It enumerates open loop (copolymerization) polymer of cyclic olefin and its adds hydrogen object；The addition polymers of cyclic olefin；Cyclic olefin and ethylene, propylene Etc. chain olefins or the aromatic compound with vinyl copolymer；And they are used into unsaturated carboxylic acid or derivatives thereof Modification (copolymerization) polymer being modified etc..Among these, it is preferable to use norbornene, polycyclic orbornene-based monomer Etc. norbornene resin of the orbornene-baseds monomer as cyclic olefin.
Cellulose-based resin is preferably cellulose esters system resin, i.e. the partial esterification object of cellulose or complete carboxylate etc., It can enumerate such as the acetic acid esters of cellulose, propionic ester, butyrate, their mixed ester.Among these, preferably triacetyl Cellulose, diacetyl cellulose, cellulose-acetate propionate, cellulose acetate-butyrate etc..
Polyester based resin is the resin other than above-mentioned cellulose esters system resin for having ester bond, usually by polynary carboxylic The resin that the condensation polymer of acid or derivatives thereof and polyalcohol is formed.As polyester based resin, such as poly terephthalic acid can be enumerated Glycol ester, polyethylene naphthalate, polybutylene naphthalate, gathers to benzene two polybutylene terephthalate (PBT) Formic acid 1,3- propylene glycol esters, poly- naphthalenedicarboxylic acid 1,3- propylene glycol esters, polycyclohexylene's diformazan alcohol ester, poly- naphthalenedicarboxylic acid Cyclohexanedimethanoester ester etc..
Polycarbonate-based resin is the polyester formed by carbonic acid and glycol or bis-phenol.Among these, from heat resistance, weatherability From the viewpoint of acid resistance, the aromatic copolycarbonate with diphenyl alkane preferably in strand.As makrolon, It can enumerate for example by bis- (4- hydroxy phenyls) propane (alias of 2,2-：Bisphenol-A), bis- (4- hydroxy phenyls) butane of 2,2-, 1,1- it is bis- The bis-phenols such as bis- (4- hydroxy phenyls) iso-butanes of (4- hydroxy phenyls) hexamethylene, 1,1-, bis- (4- hydroxy phenyls) ethane of 1,1- derive Makrolon etc..
It may make up the first resin film 3, (methyl) acrylic resin of the second resin film 4 can be to be originated from metering system The polymer of (such as including the structural unit of 50 weight % or more), preferably the structure list based on the structural unit of acid esters Copolymer made of first copolymerization with other copolymer compositions.
(methyl) acrylic resin can include the two or more structural unit from methacrylate.As first Base acrylate can enumerate the C of the methacrylic acids such as methyl methacrylate, ethyl methacrylate, butyl methacrylate1 ~C4Arrcostab.
As acrylate can be enumerated with the copolymer composition of methacrylate copolymers.Acrylate is preferably third The C of the acrylic acid such as e pioic acid methyl ester, ethyl acrylate, butyl acrylate, 2-EHA1~C8Arrcostab.As other The concrete example of copolymer composition can enumerate the unsaturated acids such as (methyl) acrylic acid；Styrene, halogenated styrenes, Alpha-Methyl benzene second The aromatic ethenyl compounds such as alkene, vinyltoluene；The vinyl cyan compounds such as (methyl) acrylonitrile；Maleic anhydride, lemon The unsaturated acid anhydrides such as health acid anhydrides；Unsaturated acyls imines such as phenyl maleimide, N-cyclohexylmaleimide etc. has in the molecule There is the compound other than acrylate of 1 polymerism carbon-to-carbon double bond.Intramolecular can be had to 2 or more polymerizations Property carbon-to-carbon double bond compound be used as copolymer composition.Copolymer composition can be used alone, or be applied in combination two or more.
From the viewpoint of the durability that can improve film, (methyl) acrylic resin can have in high polymer main chain Ring structure.Ring structure is preferably the heterocycle structures such as cyclic acid anhydride structure, cyclic imide structure, lactone ring structure.As ring-type The concrete example of acid anhydride structure can enumerate glutaric anhydride structure, succinic anhydride structure etc., as the specific of cyclic imide structure Example, can enumerate glutarimide structure, succinimide structure etc., as the concrete example of lactone ring structure, can enumerate butyrolactone Ring structure, valerolactone ring structure etc..
From the viewpoint of the Film making properties of film, impact resistance of film etc. is made, (methyl) acrylic resin can contain Acrylic rubber particle.Acrylic rubber particle refers to：By the elastomeric polymer based on acrylate as must The particle of palpus ingredient can enumerate the particle for the single layer structure being substantially only made of the elastomeric polymer, make elastomeric polymer For the particle of the multilayered structure of 1 layer.As the example of elastomeric polymer, can enumerate using alkyl acrylate as principal component, And copolymerization has the crosslinking elastocopolymer of the other vinyl monomers and cross-linkable monomer that can be copolymerized with it.As elasticity The alkyl acrylate of polymer principal component can enumerate such as methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid The C of the acrylic acid such as 2- ethylhexyls1~C8Arrcostab.The carbon number of alkyl is preferably 4 or more.
As can with other vinyl monomers of alkyl acrylate copolymer, can enumerate in the molecule have 1 polymerization More specifically the compound of property carbon-to-carbon double bond can enumerate the methacrylate, styrene of methyl methacrylate etc Etc aromatic ethenyl compound, (methyl) acrylonitrile etc vinyl cyan compound etc..As cross-linkable monomer, More specifically the cross-linked compound at least two polymerism carbon-to-carbon double bond in the molecule, which can be enumerated, can enumerate second two (methyl) acrylate of the polyalcohols such as alcohol two (methyl) acrylate, butanediol two (methyl) acrylate；(methyl) propylene The alkenyl esters of allyl propionate etc. (methyl) acrylic acid；Divinylbenzene etc..
The content of acrylic rubber particle is preferably 5 parts by weight relative to 100 parts by weight of (methyl) acrylic resin Above, 10 parts by weight or more are more preferably.If the content of acrylic rubber particle is excessive, the case hardness of film reduces, In addition, in the case of implementing surface treatment to film, the solvent resistance for the organic solvent in surface conditioning agent can be reduced.Cause This, the content of acrylic rubber particle relative to 100 parts by weight of (methyl) acrylic resin be usually 80 parts by weight hereinafter, Below preferably 60 parts by weight.
First resin film 3, the second resin film 4 can contain the common additive in the technical field of the present invention.As Additive can enumerate such as ultra-violet absorber, infrared absorbent, organic based dye, pigment, inorganic system's pigment, anti-oxidant Agent, antistatic agent, surfactant, lubricant, dispersant, heat stabilizer etc..As ultra-violet absorber, salicylic acid can be enumerated Ester compounds, benzophenone cpd, benzotriazole cpd, triaizine compounds, (methyl) acrylic acid cyano ester compound, nickel Complex salt etc..
First resin film 3, the second resin film 4 can be respectively unstretched film or through being uniaxially stretched or twin shaft is drawn Any one of film stretched.First resin film 3 and/or the second resin film 4 can be the protections for the effect for undertaking protection polarizing film 2 Film can also be the protective film of optical function as having both aftermentioned phase difference film.It should be noted that the first resin film 3 and second Resin film 4 can be identical or different film.
In addition, the first resin film 3 and/or the second resin film 4 can be in its outer surface (tables with 2 opposite side of polarizing film Face) have (painting of the surface-treated layers such as hard conating, antiglare layer, anti-reflection layer, light diffusion layer, antistatic layer, stain-proofing layer, conductive layer Layer of cloth).Typically respectively 1 μm~150 μm, preferably 5 μm~100 μm of the thickness of first resin film 3 and the second resin film 4 (such as 5 μm~60 μm), further preferably 50 μm or less (such as 1 μm~40 μm) and then can be 30 μm or less (such as 5 μ M~25 μm).
In particular, for the polarization plates of the middle-size and small-size purposes of smart mobile phone, panel type terminal etc, for filming Requirement as the first resin film 3 and/or the second resin film 4 the use of thickness is mostly 30 μm of films below, but such The power of the convergent force of the inhibition polarizing film 2 of polarization plates is weak, and durability is easy insufficient.Even if such polarization plates are used as light In the case of learning film 10, the optical film 1 of subsidiary adhesive phase of the invention also has good durability.
First resin film 3, the second resin film 4 can fit in polarizing film 2 by adhesive layer, adhesive phase.As The bonding agent for forming adhesive layer, can use water system bonding agent or active energy ray-curable bonding agent.
As water system bonding agent, usual water system bonding agent can be enumerated (such as comprising polyvinyl alcohol resin aqueous solution Bonding agent, water system two-liquid type carbamate system emulsion adhesive, aldehyde compound, epoxide, melamine based compound, Crosslinking agents such as methylol compound, isocyanate compound, amine compounds, multivalent metal salt etc.).It, can be compatibly among these Use the water system bonding agent comprising polyvinyl alcohol resin aqueous solution.It should be noted that when using water system bonding agent, by polarizing film After 2 are bonded with the first resin film 3, the second resin film 4, in order to remove the water for including in water system bonding agent, it is preferably implemented dry Drying process.After drying process, the maintenance process for example conserved with 20 DEG C~45 DEG C or so of temperature can be set.
Above-mentioned active energy ray-curable bonding agent refers to：By irradiating ultraviolet light, electron ray isoreactivity energy Ray and carry out cured bonding agent, can enumerate for example comprising the curability of polymerizable compound and Photoepolymerizationinitiater initiater combine Object, the solidification compound comprising light reactive resin are combined comprising the curability of binder resin and photoreactivity crosslinking agent Object etc., preferably ultra-violet solidified bonding agent.
Using active energy ray-curable bonding agent, by polarizing film 2 and the first resin film 3, the second tree After adipose membrane 4 is bonded, process is dried as needed, then, carries out making active energy by irradiating active energy beam The curing process that amount ray-curable bonding agent is cured.The light source of active energy beam is not particularly limited, preferably in wave Long 400nm or less has the ultraviolet light for the distribution that shines.
As the method for being bonded polarizing film 2 with the first resin film 3, the second resin film 4, can enumerate in these The binding face of at least either implements the method etc. of the surface activation process such as saponification process, sided corona treatment, corona treatment. In the case of the two sides fitting resin film of polarizing film 2, the bonding agent for being bonded these resin films can be bonding agent of the same race, Or bonding agent not of the same race.
Polarization plates 10a, 10b can further include other films or layer.Its concrete example in addition to aftermentioned phase difference film it Outside, also brightness improving film, antiglare film, antireflection film, diffusion barrier, light harvesting film, the adhesive phase other than adhesive phase 20, Coating layer, protective film etc..Protective film is made for the purpose protected the surface of the optical films such as polarization plates 10 not to be damaged, polluted Film, common example are that the optical film 1 for being attached to adhesive phase is fitted on such as metal layer, substrate, are then shelled It leaves away and removes.
The adhesive phase that protective film generally comprises base material film and is laminated thereon.Base material film can by thermoplastic resin, for example The polyolefin-based resins such as polyethylene-based resin, polypropylene-based resin；Polyethylene terephthalate, poly- naphthalenedicarboxylic acid ethylene glycol The polyester based resins such as ester；Polycarbonate-based resin；The formation such as (methyl) acrylic resin.
[2-3] phase plate
The phase difference film for including in phase plate is to show optically anisotropic optical film as shown above, and can be will By the thermoplastic resin and example as above exemplified as the substance that can be used in the first resin film 3, the second resin film 4 Such as polyvinyl alcohol resin, polyarylate system resin, polyimides system resins, polyether sulfone system resin, polyvinylidene fluoride/poly- methyl Methyl acrylate system resin, liquid crystal polyester system resin, ethylene-acetidin copolymer saponification material, polyvinyl chloride resin etc. Stretched film obtained from the resin film of formation is stretched to 1.01 times~6 times or so.Among these, preferably by polycarbonate-based tree Adipose membrane, annular ethylene series resin film, (methyl) acrylic resin film or cellulose-based resin film is uniaxially stretched or twin shaft Stretched film obtained from stretching.In addition, in this specification, zero-lag film, which is also included in phase difference film, (but also serves as protection Film).In addition to this, it is referred to as the film of uniaxiality phase difference film, wide viewing angle phase difference film, low modulus of photoelasticity phase difference film etc. It can be used as phase difference film.
Zero-lag film refers to：Phase difference value R in faceeWith thickness direction phase difference value RthIt is the film of -15nm~15nm. The phase difference film is applicable to the liquid crystal display device of IPS patterns.Phase difference value R in faceeWith thickness direction phase difference value RthIt is excellent Choosing is -10nm~10nm, is more preferably -5nm~5nm.Phase difference value R in face mentioned hereineWith thickness direction phase Difference RthIt is the value at wavelength 590nm.
Phase difference value R in faceeWith thickness direction phase difference value RthIt is defined respectively with following formula：
Re=(nx-ny)×d
Rth=((nx+ny)/2-nz〕×d
In formula, nxIt is the refractive index of the slow-axis direction (x-axis direction) in film surface, nyIt is the fast axis direction in film surface (in face The y-axis direction orthogonal with x-axis) refractive index, nzIt is the refractive index in film thickness direction (the z-axis direction vertical with film surface), d is film Thickness.
Zero-lag film can use for example by cellulose-based resin, chain polyolefin-based resins and cyclic polyolefin hydrocarbon system resin The resin film that equal polyolefin-based resins, PET series resin or (methyl) acrylic resin are formed.It is special Be not, due to be easy to control phase difference value and be easy obtain, thus it is preferable to use cellulose-based resin, polyolefin-based resins or (methyl) acrylic resin.
In addition, showing optically anisotropic film, by inorganic by coating and/or the orientation of liquid crystal compounds The coating of lamellar compound and show optically anisotropic film and also be used as phase difference film.Such phase difference film has：Quilt Referred to as the film of temperature compensating type phase difference film or sold with the trade name of " NH FILM " by JX Kuang stones energy companies Rod shaped liquid crystal is through film obtained from tilted alignment, the discoid liquid sold with the trade name of " WV FILM " by Fuji Photo Film Co., Ltd. Crystalline substance is through film obtained from tilted alignment, the complete biaxially oriented version sold with the trade name of " VAC FILM " by sumitomo chemical company Film, the biaxially oriented version film etc. equally sold with the trade name of " new VAC FILM " by sumitomo chemical company.It should be noted that The resin film of at least one face stacking of phase difference film can be for such as said protection film.
[3] optical laminate
Fig. 4~Fig. 8 is the optics for indicating to include the subsidiary adhesive phase formed by adhesive composition of the present invention The summary sectional view of the example of the optical laminate of film.
Optical laminate 5 shown in Fig. 4 is metal layer 30 (or metallic wiring layer 30) stacking that will be laminated on the substrate 40 It is formed in the surface of the adhesive phase side of the optical film 1a (or polarization plates 1a of subsidiary adhesive phase) of above-mentioned subsidiary adhesive phase Optical laminate.The optical film 1a of above-mentioned subsidiary adhesive phase is laminated on the surface of 2 side of polarizing film of above-mentioned polarization plates 10a Adhesive phase 20.
Optical laminate 6 shown in fig. 5 is that the metal layer 30 of stacking on the substrate 40 is laminated in subsidiary adhesive phase Optical laminate made of the surface of the adhesive phase side of optical film 1b (or polarization plates 1b of subsidiary adhesive phase).It is above-mentioned subsidiary The optical film 1b of adhesive phase is to be laminated with the light of adhesive phase 20 on the surface of 4 side of the second resin film of above-mentioned polarization plates 10b Learn film.
Optical laminate 5,6 can be subsidiary viscous by being bonded to the metal layer 30 of stacking on the substrate 40 by adhesive phase 20 The optical film (1a, 1b) of mixture layer and obtain.
As the method for forming metal layer 30 on the substrate 40, can enumerate such as sputtering method.Substrate 40 can be to constitute The transparent substrate of liquid crystal cells contained by touch-control input element, preferably glass substrate.It, can be with as the material of the glass substrate Use soda-lime glass, glass with lower alkali content, alkali-free glass etc..Metal layer 30 can be formed in the whole face of substrate 40, can also be formed in A part therein.
Metal layer 30 can be for example comprising selected from aluminium, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead and contain these In two or more metal alloy at least one kind of metallic element layer.It, can be with from the viewpoint of electric conductivity among these The layer for preferably including at least one kind of metallic element in aluminium, copper, silver and gold can from the viewpoint of electric conductivity and cost More preferably to include the layer of aluminium element, further preferably (metal layer 30 can be constituted as principal component comprising aluminium element The 50 weight % or more of whole metal components) layer.
Metal layer 30 can be the transparent electrode layer such as ITO (indium oxide of doped tin), can also be with metal Also there is the transparent electrode layer formed by metal oxides such as ITO while layer 30.It should be noted that can also use filament Metal mesh made of metallic wiring layer configures on substrate；Metal nanoparticle, metal nanometer line are added in binder and At layer.
The preparation method of metal layer 30 is not particularly limited, and can be metal foil, can also be by vacuum vapour deposition, splashes Method, ion plating method, ink jet printing method, gravure printing method and the metal layer formed are penetrated, preferably by sputtering method, ink jet printing Method, gravure printing method and the metal layer formed, the metal layer more preferably formed by sputtering.The thickness of metal layer 30 does not have It is particularly limited to, usually 3 μm or less, preferably 1 μm or less, more preferably 0.8 μm hereinafter, usually 0.01 μm or more.In turn, In the case where metal layer 30 is metallic wiring layer (such as metal mesh), the line width of the metal wiring is usually 10 μm or less, excellent 5 μm or less, further preferably 3 μm are selected as hereinafter, usually 0.5 μm or more.
Optical laminate 7 shown in fig. 6 is the adhesive for the optical film 1 that above-mentioned subsidiary adhesive phase is laminated on the substrate 40 Optical laminate obtained from layer 20.
Optical laminate 8 shown in Fig. 7 be will be laminated it is (opposite with substrate 40 on the surface of metal layer 30 on the substrate 40 On the surface of side) resin layer 50 that is further laminated be laminated in above-mentioned subsidiary adhesive phase optical film 1 adhesive phase 20 Optical laminate obtained from the surface of side.As the resin for forming resin layer 50, it can enumerate and for example constitute foregoing illustrative the The resin etc. of one resin film or the second resin film.
Optical laminate 9 shown in Fig. 8 is laminated with multiple metal layers at predetermined intervals along direction in length and breadth on the substrate 40 30, (on the surface of 40 opposite side of substrate) on (or gap) and the surface of the metal layer 30 between multiple metal layer 30 Forming (or stacking) has resin layer 50, in addition to this, identical as optical laminate 7.In the form (metal of the optical laminate 8 30 pattern of layer are formed as the form of regulation shape) in the case of, metal layer 30 can fill for such as touch-control input type liquid crystal display The metallic wiring layer (i.e. electrode layer) of touch-control input element possessed by setting.
In optical laminate 8, multiple metal layers 30 can contact adhesive layer 20 in whole or in part, can not also connect It touches.In addition, metal layer 30 can be the continuous film for including above-mentioned metal or alloy.It should be noted that resin layer 50 can also be omitted.
Sometimes for so-called heavy processing operation, i.e., by the optical film of subsidiary adhesive phase (1,1a, 1b) and 40 (glass of substrate Glass substrate, transparent substrate etc.) or metal layer 30 (transparent electrode layer) fitting and after making optical laminate, occurring, certain is bad When situation, the optical film of subsidiary adhesive phase is removed from substrate 40 or metal layer 30, and by other subsidiary adhesive phases Optical film 1 fits in substrate 40 or metal layer 30 again.The adhesive phase that the subsidiary adhesive composition by the present invention is formed Optical film 1 is not easy the glass substrate after stripping or fuzzy, residue glue etc., weight excellent in workability occur for the surface of transparent electrode.
[4] liquid crystal display device
The liquid crystal display device of the present invention includes the subsidiary adhesive phase formed by the adhesive composition of aforementioned present invention Optical film 1, it is more typical for, including above-mentioned optical laminate.
Therefore, liquid crystal display device of the invention has excellent durability.
The liquid crystal display device of the present invention can be the touch-control input type liquid crystal display device with touch panel function.It touches Control input type liquid crystal display device has backlight and the touch-control input element comprising liquid crystal cells.The composition of touch panel can be Well known mode (such as OUT-CELL types, ON-CELL types, IN-CELL types etc.), in addition, the manner of execution of touch panel can be with For well known mode [such as resistive film mode, electrostatic capacity (surface type electrostatic capacity, projection type static capacity side Formula) etc.].The optical film 1 of the subsidiary adhesive phase of the present invention can be only fitted to the observation side of touch-control input element (liquid crystal cells), It can also be configured at backlight side, both sides can also be configured at.The type of drive of liquid crystal cells can be TN modes, VA modes, IPS The conventionally known any ways such as mode, multidomain mode, OCB modes.It should be noted that in the liquid crystal display device of the present invention, light It can be the substrate (being typically glass substrate) that above-mentioned liquid crystal cells include to learn substrate 40 possessed by laminated body.
Embodiment
Hereinafter, showing embodiment and comparative example, the present invention is further illustrated, but the present invention is not limited by these examples It is fixed.Hereinafter, indicating that dosage, part of content and % are weight basis in the case of no especially record.
<Production Example 1：The manufacture of adhesive phase (methyl) acrylic resin (A-1)>
Into the reaction vessel for having cooling tube, nitrogen ingress pipe, thermometer and blender, input will form shown in table 1 The monomer and 81.8 parts of solution being mixed to get of ethyl acetate of (numerical value of table 1 is parts by weight).Air in reaction vessel is used After nitrogen displacement, internal temperature is set as 60 DEG C.Thereafter, addition makes 0.12 part of azobis isobutyronitrile be dissolved in 10 parts of ethyl acetate Obtained from solution.At the same temperature keep 1 hour after, internal temperature is remained 54 DEG C~56 DEG C on one side, on one side with The adding speed of 17.3 parts/Hr continuously adds ethyl acetate into reaction vessel so that the concentration of polymer approximately reaches 35%. From starting to add ethyl acetate until by 12 hours, after internal temperature is remained 54 DEG C~56 DEG C, further add Ethyl acetate adjusts to the concentration of polymer and reaches 20%, and the ethyl acetate for obtaining (methyl) acrylic resin (A-1) is molten Liquid.The weight average molecular weight Mw of obtained (methyl) acrylic resin (A-1) is that 1,390,000, weight average molecular weight Mw divides equally with number The ratio between son amount Mn (Mw/Mn) is 5.32.
<Production Example 2-12：The manufacture of adhesive phase (methyl) acrylic resin (A-2~12)>
The composition of monomer is set as forming shown in table 1, in addition to this, (methyl) propylene is got similarly with Production Example 1 Ethyl acetate solution (the resin concentration of acid system resin (A-2~12)：20%).Obtained (methyl) acrylic resin (A-2 ~12) weight average molecular weight Mw is 1,300,000~1,500,000 range, the range that Mw/Mn is 4~6.
In above-mentioned Production Example, weight average molecular weight Mw and number-average molecular weight Mn are measured as follows：The arranged in series in GPC devices " the Shodex GPC KF- of " TSKgel XL " and the manufacture of 1 Showa electrician company that 4 Tosoh companies as column manufacture 802 " is 5 total, tetrahydrofuran is used as eluent, in sample solution concentration 5mg/mL, 100 μ L of sample import volume, temperature 40 DEG C, flow velocity is under conditions of 1mL/ minutes, be measured using standard polystyren conversion.Obtain the item when exhaust line of GPC Part is also identical with this.
The differential scanning calorimetry (DSC) (DSC) that glass transition temperature Tg is manufactured using SII NanoTechnology Inc. " EXSTAR DSC6000 ", in a nitrogen atmosphere, ranging from -80~50 DEG C of measuring temperature, heating rate be 10 DEG C/min of item It is measured under part.
The monomer composition being shown in table 1 in each Production Example (numerical value of table 1 is parts by weight).
[table 1]
Abbreviation in " monomer composition " column of table 1 refers to following monomers.
BA：Butyl acrylate (the glass transition temperature of homopolymer：-54℃)、
MA：Methyl acrylate (the glass transition temperature of homopolymer：10℃)、
HEA：Acrylic acid 2- hydroxy methacrylates.
4HBA：Acrylic acid 4- hydroxybutyls
5HPA：Acrylic acid 5- hydroxyl pentyl esters
PEA：Phenoxyethyl acrylate
PEA2：Phenoxy group diethylene glycol acrylate
BMAA：Butoxy methyl acrylamide
AA：Acrylic acid
<Embodiment 1~12, comparative example 1~9>
(1) preparation of adhesive composition
In the ethyl acetate solution (resin concentration of (methyl) acrylic resin obtained by above-mentioned Production Example：20%) In, mixed phase is for crosslinking agent (B), the silane compound that 100 parts of the solid constituent of the solution is the amount of Table 2 (parts by weight) (C) and ionic compound (D), ethyl acetate is further added so that solid component concentration reaches 14%, to be bonded Agent composition.In the case where used commodity include solvent etc., the use level of each gradation composition is wherein shown in table 2 It is included as the parts by weight of active ingredient.
[table 2]
It is as follows with the detailed content of each gradation composition referred to as indicated in table 2.
(crosslinking agent)
B-1：(solid component concentration is the ethyl acetate solution of the trimethylolpropane adduct of toluene di-isocyanate(TDI) 75%), the trade name " CORONATE L " obtained from Tosoh company.
B-2：(solid constituent is dense for the ethyl acetate solution of the trimethylolpropane adduct of benzene dimethylene diisocyanate Spend the trade name " TAKENATE D-110N " 75%), from Mitsui Chemicals, Inc. to obtain.
(silane compound)
C-1：Bis- (trimethoxysilyl) hexanes of 1,6-, C-2：Bis- (trimethoxysilyl) hexanes of 1,8-, C- 3：Silicone oligomers containing methyl/methoxyl group, the trade name " X-40-9250 " from the acquisition of chemical industrial company of SHIN-ETSU HANTOTAI, C-4：1, Bis- (the 3 '-trimethoxy propyl) ureas of 3-.
(ionic compound)
D-1：Bis- (fluorosulfonyl) acid imides of N- decyl pyridines, D-2：Bis- (fluorosulfonyl) acid imides of potassium, D-3：Lithium is double (trifyl) acid imide, D-4：N- decyls pyridine four (pentafluorophenyl group) borate.
(2) making of adhesive phase
Using applicator, each adhesive composition prepared in above-mentioned (1) is reached with the thickness after drying to 20 μm of side Formula is coated on the diaphragm formed by the polyethylene terephthalate film for implementing demoulding processing and (is obtained from LINTEC companies Trade name " PLR-382051 ") demoulding process face, it is 1 minute dry with 100 DEG C, to make adhesive phase (adhesive sheet).
(3) making of the optical film (P-1) of subsidiary adhesive phase
It is about 2400 by average degree of polymerization, the polyvinyl alcohol film (Kuraray that saponification degree is 99.9 moles of %, thickness is 60 μm Company manufacture trade name " Kuraray vinylon VF-PE#6000 ") be impregnated in 37 DEG C of pure water after, including iodine and iodine Change and is impregnated with 30 DEG C in the aqueous solution (iodine/potassium iodide/water (weight ratio)=0.04/1.5/100) of potassium.Thereafter, comprising It is impregnated with 56.5 DEG C in the aqueous solution (potassium iodide/boric acid/water (weight ratio)=12/3.6/100) of potassium iodide and boric acid.It will It after film is cleaned with 10 DEG C of pure water, is dried with 85 DEG C, it is about 23 μm that obtaining, which makes polyvinyl alcohol gas absorption quantity have iodine and thickness, Polarizing film.It stretches and is mainly carried out in the process that iodine staining and boric acid are handled, total stretching ratio is 5.3 times.
It is bonded by thickness by the bonding agent formed by the aqueous solution of polyvinyl alcohol resin in the single side of gained polarizing film Transparent protective film (the trade name of Konica Minolta Opto companies manufacture that the tri acetyl cellulose film of 25 μm of degree is formed “KC2UA”〕.Then, on the surface with tri acetyl cellulose film opposite side of above-mentioned polarizing film, by by polyethenol series The bonding agent that the aqueous solution of resin is formed, the zero phase difference film (day that fitting is formed by the cyclic polyolefin hydrocarbon system resin of 23 μm of thickness The trade name " ZEONOR " of this ZEON companies manufacture), to make polarization plates.Then, zero phase difference film with contact polarization After the Corona discharge Treatment for improving adaptation is implemented on the surface of the face opposite side of piece, it is bonded using laminating machine above-mentioned (2) behind the face (adhesive level) with diaphragm opposite side of the adhesive phase made in, in 23 DEG C of temperature, relative humidity 65% Under conditions of conserve 7 days, to obtain the optical film (P-1) of subsidiary adhesive phase.
(4) durability evaluation of the optical film of subsidiary adhesive phase
The optical film (P-1) of the subsidiary adhesive phase made in above-mentioned (3) is become into length with the stretching axis direction of polarization plates The mode on side is cut into the size of 300mm × 220mm and peels diaphragm off, by the adhesive phase face paste of exposing together in glass substrate or attached Glass substrate with ITO (indium oxide of doped tin).The obtained test film for being fitted with glass substrate (is fitted with glass base The optical film of the subsidiary adhesive phase of plate) in autoclave with 50 DEG C of temperature, 5kg/cm2The pressure pressurization 20 of (490.3kPa) Minute.The alkali-free glass trade name " Eagle XG " that glass substrate is manufactured using Corning companies.In addition, as subsidiary ITO's Glass substrate is formed using being deposited by ITO on the alkali-free glass [trade name " Eagle XG "] that Corning companies manufacture The ITO layer of 30nm substrate obtained from.
For obtained optical laminate, 3 kinds of durability tests below are implemented.
(durability test)
1000 hours heat resistant tests, (glass substrates) are kept in the case where temperature is 95 DEG C of drying condition
1000 hours heat resistant test, (glass of subsidiary ITO) are kept in the case where temperature is 95 DEG C of drying condition
1000 hours hot resistance test (glass bases are kept in the environment of temperature is 60 DEG C, relative humidity is 90% Plate),
It is kept under will being 85 DEG C of drying condition in temperature 30 minutes, then in the case where temperature is -40 DEG C of drying condition The operation kept for 30 minutes is set as 1 cycle, and by it, (glass substrate) is tested in 1000 heat shock resistances (HS) recycled repeatedly.
Optical laminate after each experiment is visually observed, and observe the floating of adhesive phase by visual observation, shell It the presence or absence of the cosmetic variations such as falls, foam, durability is evaluated according to following evaluation criteria.It is shown in table 3 result.
5：Do not observe completely and the cosmetic variations such as floats, peels off, foaming；
4：It is barely perceivable and the cosmetic variations such as floats, peels off, foaming；
3：It is slightly apparent the cosmetic variations such as to float, peel off, foaming；
2：It is apparent the cosmetic variations such as to float, peel off, foaming；
1：It significantly observes and the cosmetic variations such as floats, peels off, foaming.
(5) the bonding force evaluation of the optical film of subsidiary adhesive phase
The optical film (P-1) of the subsidiary adhesive phase made in above-mentioned (3) is cut into the experiment of 25mm × 150mm sizes Piece.Spacer is peeled off from test film, by its adhesive face paste together in glass substrate.By the obtained glass substrate of being fitted with Test film (optical film for being fitted with the subsidiary adhesive phase of glass substrate) is in autoclave with 50 DEG C of temperature, 5kg/cm2 The pressure of (490.3kPa) is pressurizeed 20 minutes.After being taken care of 24 hours in 23 DEG C of temperature, the atmosphere of relative humidity 50%, by optics Film is removed with 300mm/ minutes speed along 180 ° of directions together with adhesive phase from test film.It will be flat when removing Equal peeling force is shown in table 3 as bonding force.It is that 10N is below in bonding force, weight excellent in workability, in addition, viscous In the case that resultant force is 0.5N or more, stripping is difficult to happen when being impacted from polarization plates end.
[the ITO erosion analysis of optical laminate]
Utilize the low-resistivity meter (trade name " Loresta- of Mitsubishi Chemical Analytech companies manufacture AX "), measure the sheet resistance (sheet resistance value before experiment) on the surface of the ITO layer in the glass substrate of subsidiary ITO layer.It connects It, the formation made in above-mentioned (3) is had into the test film that the polarization plates of adhesive phase are cut into 20mm × 40mm sizes, by bonding Oxidant layer and the ITO layer side for fitting in glass substrate.By obtained optical laminate in temperature 60 C, the baking of relative humidity 90% After being taken care of 500 hours in case, under 23 DEG C of temperature, the atmosphere of relative humidity 50%, shelled between ITO layer and adhesive phase From.Measure the sheet resistance (sheet resistance value after experiment) of the ITO layer after stripping.It is calculated before and after experiment by following formula Resistance change rate, and evaluated according to following benchmark.Resistance change rate is smaller, then ITO corrosivity is lower.It is shown in table 3 As a result.
Resistance change rate (%)=[(sheet resistance value after experiment)-(sheet resistance value before experiment)]/[before experiment Sheet resistance value] × 100
The corrosive evaluation criteria ＞ of ＜ ITO
○：Resistance change rate is less than the good optical laminate of 50% and ITO corrosivity.
×：Resistance change rate is 50% or more and the ITO corrosivity of optical laminate is bad.
(6) the antistatic property evaluation of the optical film of subsidiary adhesive phase
After spacer on the polarizing coating of obtained subsidiary adhesive phase is peeled off, is measured and filled using surface intrinsic resistance Set the sheet resistance value that (" Hiresta-up MCP-HT450 " (trade name) of Mitsubishi Chemical Ind's manufacture) measures adhesive. Apply voltage to be 250V, implement to measure under the determination condition that application time is 10 seconds.If sheet resistance value is 1.0 × 1012Ω/ Is hereinafter, can then obtain good antistatic property.
(gel fraction of adhesive sheet)
The gel fraction evaluation method of the adhesive sheet of the present invention is shown.Gel fraction is bigger, then is got in adhesive More cross-linking reactions, can be as the benchmark of crosslink density.Gel fraction is the value measured according to (1) below~(4).
(1) by the metal of adhesive sheet and about 10cm × about 10cm that area is about 8cm × about 8cm formed by SUS304 Net (its weight is denoted as Wm) is bonded.
(2) the fitting object obtained in above-mentioned (1) is weighed, its weight is denoted as Ws, next to be packed in the side of adhesive sheet Formula folds four times, after being used in combination HOTCHKISS (stapler) fixed, is weighed, its weight is denoted as Wb.
(3) in above-mentioned (2) in the fixed net input glass containers of HOTCHKISS, ethyl acetate 60mL will be added and soaked After stain, which is taken care of 3 days at room temperature.
(4) net is taken out from glass container, after being dried 24 hours with 120 DEG C, is weighed, its weight is denoted as Wa, And divide rate based on following formula come calculated for gel.
Gel fraction (weight %)=({ Wa- (Wb-Ws)-Wm }/(Ws-Wm)) × 100
[table 3]
Reference sign
1,1a, 1b ... be attached to the optical film of adhesive phase, 2 ... polarizing films, 3 ... first resin films, 4 ... second resin films, 5,6,7,8,9 ... optical laminates, 10 ... optical films, 10a, 10b ... polarization plates, 20 ... adhesive phases, 30 ... metal layers, 40 ... Substrate, 50 ... resin layers.

Claims (12)

1. a kind of adhesive composition, it includes (methyl) acrylic resin A, crosslinking agent B and silane compound C,
(methyl) the acrylic resin A includes the structure for being originated from hydroxyl (methyl) acrylate shown in following formula (a1) Unit and the structural unit for being originated from hydroxyl (methyl) acrylate shown in following formula (a2),
The crosslinking agent B is toluene di-isocyanate(TDI) based compound and/or toluene di-isocyanate(TDI) based compound based on polynary The addition product of alcoholic compound,
In formula (a1), n indicates 1~4 integer；A1Indicate hydrogen atom or alkyl；X1Indicate the optionally methylene with substituent group；n When being 2 or more, the substituent group is optionally identical or different,
In formula (a2), m indicates 5 or more integer；A2Indicate hydrogen atom or alkyl；X2Indicate the optionally methylene with substituent group, The substituent group is optionally identical or different.
2. adhesive composition according to claim 1, wherein the whole relative to composition (methyl) acrylic resin 100 parts by weight of structural unit, the ratio for being originated from the structural unit of hydroxyl (methyl) acrylate shown in formula (a1) are 1.5 weights The parts by weight of part~4.5 are measured, the ratio for being originated from the structural unit of hydroxyl (methyl) acrylate shown in formula (a2) is 0.25 weight Measure the parts by weight of part~1.0.
3. adhesive composition according to claim 1 or 2, wherein (methyl) acrylic resin includes to be originated from propylene The structural unit of acid alkyl ester a3, the alkyl acrylate a3 contain the glass transition temperature from homopolymer and are less than 0 DEG C Alkyl acrylate a3-1 structural unit and glass transition temperature from homopolymer be 0 DEG C or more acrylic acid alkyl The structural unit of ester a3-2.
4. adhesive composition according to claim 3, wherein the glass transition temperature for being originated from homopolymer is less than 0 DEG C Alkyl acrylate a3-1 structural unit and the glass transition temperature from homopolymer be 0 DEG C or more of acrylic acid alkyl The ratio of the structural unit of ester a3-2 is with weight ratio meter for (a3-1)/(a3-2)=20/80~95/5.
5. adhesive composition according to any one of claims 1 to 4, wherein the weight of (methyl) acrylic resin Average molecular weight is scaled 6.0 × 10 with polystyrene5~2.5 × 106。
6. adhesive composition according to any one of claims 1 to 5, wherein the ratio of crosslinking agent B is relative to 100 Parts by weight (methyl) acrylic resin A is the parts by weight of 0.01 parts by weight~10.
7. according to adhesive composition according to any one of claims 1 to 6, wherein silane compound C is following formula (c1) Shown in silane compound,
In formula (c1), B indicates the alicyclic type hydrocarbon of the alkane diyl of carbon number 1~20 or the divalent of carbon number 3~20, constitutes the alkane - the CH of hydrocarbon diyl and the alicyclic type hydrocarbon2Optionally it is replaced as-O- or-CO-；R1Indicate the alkyl of carbon number 1~5；R2、R3、 R4、R5And R6Each independently represent the alkyl of carbon number 1~5 or the alkoxy of carbon number 1~5.
8. adhesive composition according to claim 7, wherein the B of formula (c1) is the alkane diyl of carbon number 1~10；R1For The alkyl of carbon number 1~5；R2、R3、R4、R5And R6It is each independently the alkoxy of carbon number 1~5.
9. according to adhesive composition according to any one of claims 1 to 8, wherein the ratio of silane compound C relative to 100 parts by weight (methyl) acrylic resin A is the parts by weight of 0.01 parts by weight~10.
10. according to adhesive composition according to any one of claims 1 to 9, wherein formed by adhesive composition viscous The gel fraction of mixture is 50%~95%.
11. according to adhesive composition according to any one of claims 1 to 10, wherein be bonded on the glass substrate by institute The adhesive phase for stating adhesive composition formation, it is described viscous under conditions of 23 DEG C of temperature, relative humidity 50%, after 24 hours The bonding force of mixture layer is 0.5N/25mm~10N/25mm under 300mm/ minutes peeling rates.
12. the adhesive composition according to any one of claim 1~11 is used to form optical film to be laminated in Adhesive phase.
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