CN101828134B - Resin film with adhesive and optical laminate using the same - Google Patents

Resin film with adhesive and optical laminate using the same Download PDF

Info

Publication number
CN101828134B
CN101828134B CN200880105125.3A CN200880105125A CN101828134B CN 101828134 B CN101828134 B CN 101828134B CN 200880105125 A CN200880105125 A CN 200880105125A CN 101828134 B CN101828134 B CN 101828134B
Authority
CN
China
Prior art keywords
bonding agent
adhesive phase
methyl
resin
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN200880105125.3A
Other languages
Chinese (zh)
Other versions
CN101828134A (en
Inventor
金圣敏
许智惠
崔汉永
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Publication of CN101828134A publication Critical patent/CN101828134A/en
Application granted granted Critical
Publication of CN101828134B publication Critical patent/CN101828134B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133632—Birefringent elements, e.g. for optical compensation with refractive index ellipsoid inclined relative to the LC-layer surface
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133633—Birefringent elements, e.g. for optical compensation using mesogenic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—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 the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/50—Protective arrangements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

Abstract

Provided is a resin film with adhesive, having an adhesive layer, which has high antistatic properties without varying with passage of time and excellent durability, provided on a surface of a resin film. The adhesive layer is formed on at least one surface of a resin film such as optical film and surface protection film, to be provided as a resin film with adhesive. The adhesive is formed of a composition containing 0.2 to 8 weight parts of ionic compound (B) having organic cations, which is solid in room temperature, with respect to 100 weight parts of acrylic resin (A) including a structure unit derived from a (meth) acrylic acid ester represented by the following formula (I) as a main component, wherein R1 represents hydrogen atom or methyl group, R2 represents C1-14 alkyl group or aralkyl group which may be substituted by C1-10 alkoxy group respectively.

Description

Resin molding with bonding agent and the optical laminate using it
Technical field
The present invention relates to a kind of resin molding being formed with adhesive phase.As the resin molding being set as object in the present invention, the blooming such as containing polarizing coating and/or phase retardation film can be enumerated and be pasted on the face that is in opposition side with the adhesive phase of this blooming and in use till protect the surface protection film on its surface.The invention still further relates to the liquid crystal display optical laminate that a kind of use is formed with the resin molding of this adhesive phase.
Background technology
Polarizing coating is often installed on liquid crystal indicator and is widely used, and it is with the two sides laminating transparent diaphragm at polaroid, in the surface of at least one diaphragm formation adhesive phase, the state circulation of pasting stripping film on described adhesive phase.In addition, stacked phase retardation film on the polarizing coating being sometimes pasted with the state of diaphragm on the two sides of polaroid, makes elliptic polarization film, and in this phase retardation film side, with the order adhesive layer of adhesive phase/stripping film and stripping film.And then, sometimes on the surface of phase retardation film, with the order adhesive layer of adhesive phase/stripping film and stripping film.Before being pasted on liquid crystal cells, peeling stripping film from these polarizing coatings, elliptic polarization film, phase retardation film etc., be pasted on liquid crystal cells via the adhesive phase exposed.This polarizing coating, elliptic polarization film or phase retardation film produce electrostatic when being pasted on liquid crystal cells peeling off stripping film, and therefore, its Prevent countermeasures is developed in urgent expectation.
As one of its countermeasure; a kind of polarizing coating is proposed in patent No. 3012860 publication; described polarizing coating is at the stacked diaphragm in the surface of polarizer membrane, arrange adhesive phase on the surface of diaphragm; wherein; as bonding agent, use the ionic conductivity composition be made up of electrolytic salt and organopolysiloxane and the composition containing acrylic acid series copolymer.By using this bonding agent, although manifesting antistatic behaviour, may not say that its performance is abundant, in addition, can not say it is sufficient performance in adhesion durability.
Therefore, in Japanese Unexamined Patent Application Publication 2004-536940 publication (WO2003/011958), disclose the antistatic agent coordinating organic salt in pressure adhesive (bonding agent), thus give antistatic behaviour to this bonding agent.In addition, record in Japanese Unexamined Patent Publication 2004-114665 publication and make containing the salt be made up of quaternary ammonium cation and the contain fluorine atoms negative ion of total carbon number 4 ~ 20 in bonding agent etc., thus give its antistatic behaviour.And then, in Japanese Unexamined Patent Publication 2006-307238 publication, record the ionic liquid making to contain for liquid under room temperature (25 DEG C) in bonding agent antistatic to seek.But, when long-time placement is coated with the polarizing coating of bonding agent, sometimes cause antistatic behaviour to be deteriorated because timeliness change.Circulation and the storage time of general polarizing coating are about 6 months to the maximum from making, therefore, require until client use during keep antistatic property.
In addition, the blooming of band bonding agent as above is pasted in liquid crystal cell with its adhesive phase side makes liquid crystal indicator, under being placed in high temperature or hot and humid condition in this condition or when repeatedly carrying out heating and cooling, with the change in size of blooming, sometimes adhesive phase produces to bubble or produce between blooming and adhesive phase or between adhesive phase and liquid crystal cells glass and floats or peel off, therefore, also require not produce such unfavorable condition and excellent in te pins of durability.And then, time upon exposure to elevated temperatures, act on the skewness of the residual stress of blooming, concentrate at the peripheral part generation stress of blooming, its result, what sometimes occur when black display that peripheral part turns white is called as whiting, or produces color spot, therefore, also require to suppress this whiting or color spot.And then, when the blooming of band bonding agent is pasted on liquid crystal cells, in situation defective, need peel this blooming off and then again paste new film, but when this stripping, adhesive phase is followed blooming and is peeled, therefore, also to require on unit glass (Cell glass) not residual adhesive, do not produce the so-called re-workabilities such as fuzzy.
On the other hand, surface protection film generally via being formed at the bonding agent of its one side and the blooming etc. that is pasted on as protected body, for preventing from processing or carry the damage that produces during protected body or pollution etc.Such as, being applied to the bloomings such as the polarizing coating of liquid crystal indicator or phase retardation film to prevent damage or pollution etc., circulating with the state being pasted with described surface protection film in the face being in opposition side with the above-mentioned adhesive phase for being pasted on liquid crystal cells.This surface protection film is stripped removing after blooming is pasted on liquid crystal cells; electrostatic is produced when it is peeled off; when voltage being applied to liquid crystal cells under the state of this electrostatic residual; there is the orientation of infringement liquid crystal molecule or produce the problem of panel defect; therefore, various antistatic treatment implemented by effects on surface diaphragm.
Problem of the present invention is, there is provided a kind of resin molding with bonding agent, the resin molding of described band bonding agent is provided with on the surface of resin molding and has been endowed high antistatic behaviour, simultaneously this antistatic behaviour and is difficult to change along with the time and the also excellent adhesive phase of permanance.The present inventor etc. concentrate on studies to solve above-mentioned problem, found that, be relatively that the bonding agent of principal ingredient is combined with under room temperature (25 DEG C) as the composition of the specific ionic compound of solid is as adhesive phase with acryl resin by arranging on the surface of resin molding, antistatic behaviour, the timeliness change of antistatic behaviour and the resin molding of band bonding agent of excellent in te pins of durability can be obtained, complete the present invention thus.
Summary of the invention
The present inventor etc. concentrate on studies to achieve these goals, found that, by the adhesive phase formed by adhesive composition being arranged on the surface of blooming, excellent result can be obtained, wherein, in described adhesive composition, the acryl resin of the principal ingredient becoming bonding agent is made up of the material with specific molecular weight and molecular weight distribution, coordinate specific 2 kinds of materials as crosslinking chemical simultaneously, and and then coordinate the oligomer with specific functional group as silane compound.
That is, according to the present invention, provide a kind of resin molding with bonding agent, it is formed with adhesive phase at least one side of resin molding, and this adhesive phase is formed by the composition containing following composition (A) and (B).
(A) with from following formula (I)
(in formula, R 1represent hydrogen atom or methyl, R 2represent alkyl or the aralkyl of carbon number 1 ~ 14, or respectively by the alkyl of the carbon number 1 ~ 14 of the alkoxy of carbon number 1 ~ 10 replacement or aralkyl.) structural unit of (methyl) acrylate that represents is that acryl resin 100 weight portion of principal ingredient and (B) have organic cation and be at room temperature ionic compound 0.2 ~ 8 weight portion of solid.
Thus, the present invention finds, for the acryl resin (A) forming bonding agent, the adhesive phase that imparting is formed by this bonding agent is with antistatic behaviour, simultaneously, as the antistatic agent of the suppression of the timeliness change for realizing antistatic behaviour, for the ionic compound (B) of solid is effective especially under room temperature (25 DEG C).
The resin molding forming this adhesive phase can be the blooming containing polarizing coating and/or phase retardation film.In addition, also can be pasted on this blooming with adhesive phase be in the face of opposition side until protect the surface protection film on its surface when using.
When resin molding is blooming, glass substrate can be laminated in its adhesive phase side, makes liquid crystal display optical laminate.Therefore, according to the present invention, also provide a kind of optical laminate, it is that the blooming being formed with the band bonding agent of above-mentioned adhesive phase at blooming is laminated in glass substrate with its adhesive phase side.
Embodiment
Below, the present invention is described in detail.The resin molding of band bonding agent of the present invention is formed with adhesive phase at least one side of resin molding, and this adhesive phase is by containing
(A) acryl resin and
(B) there is organic cation and at room temperature for solid ionic compound composition formed.First, each composition forming adhesive composition is described.
[acryl resin (A)]
In the resin molding of band bonding agent of the present invention, for the acryl resin (A) of adhesive phase with the structural unit of (methyl) acrylate represented from above-mentioned formula (I) for principal ingredient, specifically, on the basis of the structural unit from described (methyl) acrylate, can also containing from having based on the monomer of the heterocyclic radical isopolarity functional group of free carboxy, hydroxyl, amino, epoxide ring, preferably from the structural unit of (methyl) acrylic compounds with polar functional group.At this, so-called (methyl) acrylic acid, refers to be any one in acrylic or methacrylic acid, and " methyl " when in addition, being called (methyl) acrylate etc. is also the same meaning.
In the above-mentioned formula (I) of the main composition unit for acryl resin (A), R 1for hydrogen atom or methyl, R 2for alkyl or the aralkyl of carbon number 1 ~ 14, be preferably alkyl.R 2represent alkyl or aralkyl each group in hydrogen atom can be replaced by the alkoxy of carbon number 1 ~ 10.
As (methyl) acrylate that formula (I) represents, particular instantiation: the alkyl acrylate of the straight-chain of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl, lauryl acrylate and so on; The alkyl acrylate of the branched of isobutyl acrylate, 2-EHA, Isooctyl acrylate monomer and so on; The alkyl methacrylate of the straight-chain of methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, n-BMA, n octyl methacrylate, lauryl methacrylate and so on; The alkyl methacrylate etc. of the branched of isobutyl methacrylate, 2-Ethylhexyl Methacrylate, EHMA and so on.
As R 2for alkoxy replace alkyl time, R 2for (methyl) acrylate that the formula (I) during alkoxyalkyl represents, particular instantiation acrylic acid 2-methoxy acrylate, ethioxy methyl esters, methacrylic acid 2-methoxy acrylate, methacrylic acid ethoxy methyl esters etc.As R 2for (methyl) acrylate that the formula (I) during aralkyl represents, particular instantiation benzyl acrylate and benzyl methacrylate etc.
These (methyl) acrylate can individually use, and in addition, different multiple (methyl) acrylate can be used to make its copolymerization.
As the example of monomer with polar functional group, can enumerate: the monomer with free carboxy of acrylic acid, methacrylic acid, β-acryloxypropionic acid and so on; The monomer with hydroxyl of (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 2-or 3-chlorine-2-hydroxyl propyl ester, diethylene glycol one (methyl) acrylate and so on; Acryloyl morpholine, caprolactam, NVP, (methyl) acrylic acid tetrahydrofuran ester, caprolactone modification tetrahydrofuran acrylate, 3, the monomer with heterocyclic radical of 4-epoxycyclohexylmethyl (methyl) acrylate, (methyl) glycidyl acrylate, DHF and so on; The monomer etc. with the amino different from heterocycle of N, N-dimethyl aminoethyl (methyl) acrylate and so on.The monomer with these polar functional groups can individually use, and also can use different various of monomers.
Wherein, what preferably the monomer with hydroxyl is used as formation acryl resin (A) contains one of polar functional group monomer.In addition, on the basis of monomer with hydroxyl, and be also effective with the monomer with other polar functional group, the monomer such as with free carboxy.
For acryl resin (A) its nonvolatile component 100 weight portion relatively of adhesive phase, the structural unit of (methyl) acrylate represented from above-mentioned formula (I) is contained with usual 60 ~ 99.9 weight portions, the preferably ratio of 80 ~ 99.6 weight portions, in addition, the structural unit from the monomer with polar functional group is contained with usual 0.1 ~ 20 weight portion, the preferably ratio of 0.4 ~ 10 weight portion.
For acryl resin of the present invention (A) can containing from formula described above (I) (methyl) acrylate and there is polar functional group monomer beyond the structural unit of monomer.As these examples, can enumerate from the structural unit of (methyl) acrylate in molecule with ester ring type structure, the structural unit from styrene monomer, the structural unit from vinyl monomer, from the structural unit etc. of monomer in molecule with multiple (methyl) acryloyl group.
So-called ester ring type structure is the usual cycloolefin structure of more than 5, preferably about 5 ~ 7 of carbon number.As the concrete example of acrylate with ester ring type structure, can enumerate: isobornyl acrylate, cyclohexyl acrylate, acrylic acid dicyclo pentyl ester, acrylic acid cyclo-dodecyl ester, acrylic methyl cyclohexyl, acrylic acid 3-methyl cyclohexanol ester, t-butylcyclohexyl ester, α-ethoxy-c olefin(e) acid cyclohexyl, acrylate base phenyl ester etc., as the concrete example of methacrylate with ester ring type structure, can enumerate: isobornyl methacrylate, cyclohexyl methacrylate, methacrylic acid dicyclo pentyl ester, methacrylic acid cyclo-dodecyl ester, methyl methacrylate base cyclohexyl, methacrylic acid 3-methyl cyclohexanol ester, t-butyl cyclohexyl ester, methacrylic acid cyclohexyl phenyl ester etc.
As the example of styrene monomer, except styrene, can enumerate: the ring-alkylated styrenes of methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl, triethylbenzene ethene, propylstyrene, butylstyrene, hexyl benzene ethene, heptyl benzene ethene, octyl styrene and so on; The halogenated styrenes of fluorobenzene ethene, chlorostyrene, bromstyrol, Dowspray 9, iodobenzene ethene and so on; And nitrostyrolene, acetylbenzene ethene, methoxy styrene, divinylbenzene etc.
As the example of vinyl monomer, can enumerate: the fatty acid vinyl ester of vinyl acetate, propionate, vinyl butyrate, 2 ethyl hexanoic acid vinyl acetate, vinyl laurate and so on; The vinyl halides of vinyl chloride or bromine ethene and so on; The meta-halo ethylene of vinylidene chloride and so on; The nitrogenous aromatic ethenyl of vinylpyridine, vinyl pyrrolidone, vinylcarbazole and so on; The conjugate diene monomer of butadiene, isoprene, chlorbutadiene and so on; And vinyl cyanide, methacrylonitrile etc.
As the example of monomer in molecule with multiple (methyl) acryloyl group, can enumerate: 1,4-butylene glycol two (methyl) acrylate, 1, there is in the molecule of 6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, tripropylene glycol two (methyl) acrylate and so on the monomer of 2 (methyl) acryloyl groups; There is in the molecule of trimethylolpropane tris (methyl) acrylate and so on the monomer etc. of 3 (methyl) acryloyl groups.
(methyl) acrylate of formula (I) and there is polar functional group monomer beyond monomer can individually or two or more combinationally use.For in the acryl resin (A) of bonding agent, relatively nonvolatile component 100 weight portion of this resin, with usual 0 ~ 20 weight portion, the preferably ratio of 0 ~ 10 weight portion contain from formula (I) (methyl) acrylate and there is polar functional group monomer beyond the structural unit of monomer.
The effective constituent of bonding agent for principal ingredient, can comprise the acryl resin that two or more contains the structural unit from the monomer with polar functional group with the structural unit of (methyl) acrylate represented from formula (I) as above.And then, the acryl resin different from it, concrete example can be mixed as there is the structural unit from (methyl) acrylate of formula (I) and the acryl resin etc. not containing polar functional group in aforesaid propylene acid resin.With the structural unit of (methyl) acrylate from formula (I) be principal ingredient, containing from there is the acryl resin of structural unit of monomer of polar functional group in acryl resin is overall, be preferably set to more than 60 % by weight, more preferably more than 80 % by weight.
With the structural unit of (methyl) acrylate from formula (I) be principal ingredient, the weight-average molecular weight (Mw) that preferably utilizes the polystyrene standard of gel permeation chromatography (GPC) to convert containing the acryl resin of structural unit from the monomer with polar functional group is 1,000,000 ~ 2, the scope of 000,000.The weight-average molecular weight that polystyrene standard converts is 1,000, when more than 000, cementability under hot and humid improves, and produces the possibility of floating or peeling off and tend to step-down between glass substrate and adhesive phase, and, re-workability tends to improve, therefore preferably.In addition, this weight-average molecular weight is 2,000, when less than 000, even if the size being pasted on the blooming of this adhesive phase changes, adhesive phase also follows this change in size and changes, therefore, there is no difference between the light levels of the periphery of liquid crystal cells and the light levels of central part, there is the tendency suppressing whiting or color spot, therefore preferably.The molecular weight distribution represented with the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) usually about 2 ~ 10 scope.
This acryl resin also can be only made up of the acryl resin of higher molecular weight as above, also can on the basis of described acryl resin by and the potpourri of the acryl resin different from it form.As acryl resin that can be used in combination, can enumerate is such as that principal ingredient, weight-average molecular weight are 50 with the structural unit of (methyl) acrylate represented from above-mentioned formula (I), the acryl resin of the scope of 000 ~ 300,000.
Acryl resin (combining the potpourri that situation of more than two kinds is for both) preferably makes it be dissolved in ethyl acetate and the solution being adjusted to nonvolatile component concentration 20 % by weight shows below 20Pas, is the viscosity of 0.1 ~ 7Pas further at 25 DEG C.When viscosity is now below 20Pas, the cementability under hot and humid improves, and produces the possibility of floating or peeling off and tend to step-down between glass substrate and adhesive phase, and re-workability tends to improve, therefore preferably.Viscosity can utilize rich strangling to fly viscosity meter and measure.
The acryl resin forming adhesive phase can utilize the known various methods such as such as solution polymerization process, emulsion polymerization, mass polymerization, suspension polymerization to manufacture.In the manufacture of this acryl resin, usually use polymerization initiator.Polymerization initiator, relatively for total 100 weight portion of whole monomers of the manufacture of acryl resin, uses about 0.001 ~ 5 weight portion.
As polymerization initiator, use thermal polymerization or Photoepolymerizationinitiater initiater etc.As Photoepolymerizationinitiater initiater, such as 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone etc. can be enumerated.As thermal polymerization, such as 2 can be enumerated, 2 '-azoisobutyronitrile, 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (cyclohexane-1-nitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (2,4-dimethyl-4-methoxyl-valeronitrile), dimethyl-2,2 '-azo two (2 Methylpropionic acid ester), 2, the azo compound of 2 '-azo two (2-hydroxymethylpropionitrile) and so on; Lauroyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, peroxidized t-butyl perbenzoate, hydrogen phosphide cumene, di-isopropyl peroxydicarbonate, dipropyl peroxydicarbonate, new peroxide tert-butyl caprate, the peroxidating trimethylace tonitric tert-butyl ester, (3,5,5-trimethyl acetyl base) organic peroxide of superoxide and so on; The inorganic peroxide etc. of potassium persulfate, ammonium persulfate, hydrogen peroxide and so on.In addition, and also can be used as polymerization initiator with the redox system initiating agent etc. of superoxide and reductive agent.
As the manufacture method of acryl resin, in above shown method, preferred solution polymerization.When the concrete example enumerating solution polymerization process is described, can enumerates subject monomers and organic solvent mixing, add thermal polymerization under nitrogen atmosphere, in the method etc. of about 40 ~ 90 DEG C, preferably 60 ~ 80 DEG C left and right stirring 3 ~ 10 hours.In addition, in order to control reaction, in polymerization, monomer or thermal polymerization can be added continuously or off and on, or adding under the state being dissolved in organic solvent.At this, as organic solvent, the aromatic hydrocarbon based of such as toluene, dimethylbenzene and so on can be used; The ester class of ethyl acetate, butyl acetate and so on; The aliphatics alcohols of propyl alcohol, isopropyl alcohol and so on; The ketone etc. of acetone, methyl ethyl ketone, methylisobutylketone and so on.
[ionic compound (B)]
In the present invention, on the basis of acryl resin as above (A), as antistatic agent, be the ionic compound (B) of solid under being used in room temperature (25 DEG C).This ionic compound (B) has organic cation.In the present invention, sometimes by described at room temperature for the ionic compound of solid is called ionic solid.
Form ionic compound (B) as long as cation constituent meet and become the organic kation of ionic solid, be not particularly limited except it.Can enumerate such as: glyoxaline cation, pyridylium, ammonium cation, sulfonium cation, phosphonium cation etc., for the situation of the adhesive phase of resin molding, charged from the viewpoint of being difficult to when peeling setting stripping film thereon, preferred pyridylium or glyoxaline cation.
On the other hand, in ionic compound (B), for as long as the anion component of the counterion of above-mentioned cation constituent meets the negative ion becoming ionic solid, be not particularly limited, both can be inorganic negative ion, also can be organic negative ion, such as following negative ion can be enumerated.
Chloride anion [Cl -],
Bromide anions [Br -],
Iodide anion [I -],
Four chloro-aluminate negative ion [AlCl 4 -],
Heptachlor two aluminate negative ion [Al 2cl 7 -],
Tetrafluoro boric acid salt anionic [BF 4 -],
Hexafluorophosphoric acid salt anionic [PF 6 -],
Perchlorate negative ion [ClO 4 -],
Nitrate anions [NO 3 -],
Acetylate anion [CH 3cOO -],
Trifluoroacetic acid salt anionic [CF 3cOO -],
Pyrovinic acid salt anionic [CH 3sO 3 -],
Trifluoromethyl sulfonic acid negative ion [CF 3sO 3 -],
P-toluenesulfonic acid salt anionic [p-CH 3c 6h 4sO 3 -],
Two (trifluoromethyl sulfonyl) imines negative ion [(CF 3sO 2) 2n -],
Three (trifluoromethyl sulfonyl) methyl anion [(CF 3sO 2) 3c -],
Hexafluoroarsenate salt anionic [AsF 6 -],
Hexafluoro-antimonic acid salt anionic [SbF 6 -],
Hexafluoro niobate negative ion [NbF 6 -],
Hexafluoro tantalates negative ion [TaF 6 -],
Dimethyl phosphonite anion [(CH 3) 2pOO -],
(gathering) hydrogen fluorine fluoride anion [F (HF) n -] (n is about 1 ~ 3),
Dicyanamide negative ion [(CN) 2n -],
Thiocyano negative ion [SCN -],
Perfluoro butyl sulfosalt negative ion [C 4f 9sO 3 -],
Two (pentafluoroethyl group sulfonyl) imines negative ion [(C 2f 5sO 2) 2n -],
Perfluorobutyric acid salt anionic [C 3f 7cOO -],
(trifluoromethyl sulfonyl) (Trifluoromethylcarbonyl) imines negative ion [(CF 3sO 2) (CF 3cO) N -] etc.
Wherein, from the viewpoint of the ionic solid giving excellent antistatic property, particularly preferably use the anion component containing fluorine atom, especially preferably hexafluorophosphoric acid salt anionic.
Concrete example for ionic solid of the present invention suitably can be selected from the combination of above-mentioned cation constituent and anion component.As the compound of the combination of concrete cation constituent and anion component, the compound that can be listed below.
N-hexyl pyridine hexafluorophosphate,
N-octylpyridinium hexafluorophosphate,
N-butyl-4-picoline hexafluorophosphate,
N-butyl-N-crassitude hexafluorophosphate,
1-ethyl-3-methylimidazole hexafluorophosphate,
1-ethyl-3-methylimidazole tosilate,
1-butyl-3-methylimidazole metilsulfate,
TBuA hexafluorophosphate,
TBuA tosilate,
(2-hydroxyethyl) trimethyl ammonium dimethyl phosphinate etc.
This ionic solid can individually or two or more combinationally use.The example of ionic solid is not limited to the above material enumerated.
As mentioned above, be at room temperature that the ionic compound (B) of solid gives antistatic behaviour to the adhesive phase that formed by the composition containing acryl resin (A), meanwhile, in maintenance as being effective in the various physical property of bonding agent.Particularly compared with under using normal temperature being the ionic compound of liquid, antistatic property can be kept for a long time.During from the viewpoint of the long-time stability of this antistatic behaviour, ionic compound (B) preferably has the fusing point of more than 30 DEG C, further more than 35 DEG C.On the other hand, when its fusing point is too high, with the poor compatibility of acryl resin (A), therefore, preferably there is the fusing point of less than 90 DEG C, further less than 80 DEG C.
Nonvolatile component 100 weight portion (using situation of more than two kinds for its total weight) of relative aforesaid propylene acid resin (A), contains ionic compound (B) with the ratio of 0.2 ~ 8 weight portion.Nonvolatile component 100 weight portion of relative acryl resin (A), during containing 0.2 weight portion above ionic compound (B), antistatic property improves, therefore preferred, in addition, when its amount is below 8 weight portions, easy maintenance permanance, therefore preferably.The amount of the ionic compound (B) of nonvolatile component 100 weight portion of relative acryl resin (A) also can be set as the scope of 0.2 ~ 5 weight portion, is preferably more than 0.5 weight portion, below other 3 weight portions.
[forming other composition of bonding agent]
In acryl resin as above (A) and ionic compound (B), usually coordinate crosslinking chemical (C) further, make adhesive composition.Crosslinking chemical (C) can with the compound from the functional group be particularly cross-linked containing the structural unit of polar functional group monomer in acryl resin (A) for having at least 2 in molecule, particular instantiation isocyanate ester compound, epoxy compounds, metallo-chelate compounds, aziridines compound etc.
Isocyanate ester compound is the compound in molecule with at least 2 isocyanos (-NCO), can enumerate such as: tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, methyl diphenylene diisocyanate, hydrogenated diphenyl methane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate etc.In addition, the adduct making these isocyanate compounds and the polyol reaction such as glycerine or trimethylolpropane generate or the material making isocyanate compound form dipolymer, trimer etc. and obtain also can become the crosslinking chemical for bonding agent.Also isocyanate ester compound can be mixed with two or more.
Epoxy compounds is the compound in molecule with at least 2 epoxy radicals, can enumerate such as: the epoxy resin of bisphenol A-type, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, T 55,1,6-hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, N, N-diglycidylaniline, N, N, N ' N '-four glycidyl group-m-xylene diamine, 1,3-pair (N, N '-diglycidyl amino methyl) cyclohexane etc.Also epoxy compounds can be mixed with two or more.
As metallo-chelate, can enumerate such as: in the polyvalent metals such as aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium, coordination has the compound etc. of diacetone or ethyl acetoacetate.
Aziridines compound is have at least 2 in molecule to be called as the compound that second embraces 3 membered ring skeleton be made up of 1 nitrogen-atoms and 2 carbon atoms of imines, can enumerate such as: diphenyl methane-4, 4 '-bis-(1-aziridine carboxylic acid amides), Toluene-2,4-diisocyanate, 4-two (1-aziridine carboxylic acid amides), triethylenemelanin, two-the 1-(2-methylaziridine) of isophthaloyl, three-1-aziridinyl phosphine oxides, hexa-methylene-1, 6-two (1-aziridine carboxylic acid amides), trimethylolpropane-three-β-aziridine propionate, tetramethylol methane-three-β-aziridine propionate etc.
In these crosslinking chemicals, preferably use isocyanate ester compound, especially xylylene diisocyanate, tolylene diisocyanate or hexamethylene diisocyanate or make these isocyanate compounds and the polyol reaction such as glycerine or trimethylolpropane and the potpourri of the adduct generated or the material that makes isocyanate compound form dipolymer, trimer etc. and obtain, the material etc. that is mixed into by these isocyanate compounds.As preferred isocyanate ester compound, can enumerate: tolylene diisocyanate, make tolylene diisocyanate and polyol reaction and the adduct, the dipolymer of tolylene diisocyanate and the trimer of tolylene diisocyanate that generate or hexamethylene diisocyanate, make hexamethylene diisocyanate and polyol reaction and the adduct, the dipolymer of hexamethylene diisocyanate and the trimer of hexamethylene diisocyanate that generate.
Relative acryl resin (A) 100 weight portion (use situation of more than two kinds for its amount to weight), coordinates crosslinking chemical (C) with the ratio about usual 0.01 ~ 10 weight portion, preferably about 0.1 ~ 5 weight portion.When being more than 0.01 weight portion relative to the amount of the crosslinking chemical (C) of acryl resin (A) 100 weight portion, the permanance of adhesive phase is tended to improve, therefore preferred, in addition, when it is below 10 weight portions, the whiting when blooming of band bonding agent being applied to liquid crystal indicator becomes not obvious, therefore preferably.
When the resin molding of band bonding agent of the present invention is pasted on glass substrate with its adhesive phase side, improve to make the adaptation of adhesive phase and glass substrate, preferably in for the formation of the bonding agent of this adhesive phase, contain silane compound, containing silane compound in especially preferred acryl resin before coordinating crosslinking chemical.
As silane compound, can enumerate: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, APTES, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl dimethoxysilane, 2-(3, 4-expoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl group triethoxysilane, 3-glycidoxypropyl group dimethoxymethylsilane, 3-glycidoxypropyl group ethoxy dimethylsilane etc.Two or more silane compound can be used.
Silane compound can be the silane compound of silicone oligomers type.When representing silicone oligomers by the form of (monomer) oligomer, such as following material can be enumerated.
3-mercaptopropyl trimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-mercaptopropyl trimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-mercaptopropyltriethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer containing mercapto propyl group of 3-mercaptopropyltriethoxysilane-tetraethoxy-silicane alkyl copolymer and so on;
Thiopurine methyltransferase trimethoxy silane-tetramethoxy-silicane alkyl copolymer,
Thiopurine methyltransferase trimethoxy silane-tetraethoxy-silicane alkyl copolymer,
Thiopurine methyltransferase triethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer containing thiopurine methyltransferase of thiopurine methyltransferase triethoxysilane-tetraethoxy-silicane alkyl copolymer and so on;
3-methacryloxypropyl trimethoxy silane-tetramethoxy-silicane alkyl copolymer,
3-methacryloxypropyl trimethoxy silane-tetraethoxy-silicane alkyl copolymer,
3-methacryloxypropyl-tetramethoxy-silicane alkyl copolymer,
3-methacryloxypropyl-tetraethoxy-silicane alkyl copolymer,
3-methacryloyloxypropyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-methacryloyloxypropyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-methacryloyloxypropyl methyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,
The multipolymer containing methacryloxypropyl of 3-methacryloyloxypropyl methyl diethoxy silane-tetraethoxy-silicane alkyl copolymer and so on;
3-acryloxypropyl trimethoxy silane-tetramethoxy-silicane alkyl copolymer,
3-acryloxypropyl trimethoxy silane-tetraethoxy-silicane alkyl copolymer,
3-acryloxypropyl triethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-acryloxypropyl triethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-acryloxypropyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-acryloxypropyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-acryloxypropyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,
The multipolymer containing acryloxypropyl of 3-acryloxypropyl diethoxy silane-tetraethoxy-silicane alkyl copolymer and so on;
Vinyltrimethoxy silane-tetramethoxy-silicane alkyl copolymer,
Vinyltrimethoxy silane-tetraethoxy-silicane alkyl copolymer,
Vinyltriethoxysilane-tetramethoxy-silicane alkyl copolymer,
Vinyltriethoxysilane-tetraethoxy-silicane alkyl copolymer,
Vinyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
Vinyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
Vinyl methyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,
The multipolymer containing vinyl of vinyl methyl diethoxy silane-tetraethoxy-silicane alkyl copolymer and so on;
3-TSL 8330-tetramethoxy-silicane alkyl copolymer,
3-TSL 8330-tetraethoxy-silicane alkyl copolymer,
APTES-tetramethoxy-silicane alkyl copolymer,
APTES-tetraethoxy-silicane alkyl copolymer,
3-amino propyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-amino propyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-amino propyl methyl diethoxy silane-tetramethoxy-silicane alkyl copolymer,
The multipolymer etc. containing amino of 3-amino propyl methyl diethoxy silane-tetraethoxy-silicane alkyl copolymer and so on.
These silane compounds are in most cases liquid.The use level of the silane compound in bonding agent is relative to nonvolatile component 100 weight portion (use situation of more than two kinds for its amount to weight) of acryl resin (A), about being generally 0.01 ~ 10 weight portion, preferably use with the ratio of 0.05 ~ 5 weight portion.When being more than 0.01 weight portion relative to the amount of the silane compound of nonvolatile component 100 weight portion of acryl resin, the adaptation of adhesive phase and glass substrate improves, therefore preferably.In addition, when its amount is below 10 weight portions, there is the tendency suppressing silane compound to ooze out from adhesive phase, therefore preferably.
The resin etc. beyond crosslinking catalyst, weathering stabilizers, bonding agent, plastifier, softening agent, dyestuff, pigment, inorganic filler, acryl resin (A) can also be coordinated further in bonding agent described above.In addition, in bonding agent combined with ultraviolet radiation curability compound, after adhesive phase is formed irradiation ultraviolet radiation make it solidify, form harder adhesive phase to be also useful.Wherein, if coordinate crosslinking catalyst in bonding agent together with crosslinking chemical, then can prepare adhesive phase by the slaking of short time, and can suppress to produce between resin molding and adhesive phase in the resin molding of the band bonding agent obtained to float or peel off or produce in adhesive phase and bubble, in addition, re-workability is also better sometimes.As crosslinking catalyst, can enumerate such as: the aminated compounds etc. of hexamethylene diamine, ethylenediamine, polyethylene imine based, hexamethylene tetramine, diethylene triamine, trien, isophorone diamine, trimethylene diamine, poly-amino resins, melamine resin and so on.When coordinating the aminated compounds as crosslinking chemical in bonding agent, as crosslinking chemical, preferred isocyanate compounds.
These each compositions forming bonding agent make adhesive composition being dissolved under the state in solvent, to be coated on suitable base material and to make it dry, making adhesive phase.
In the resin molding of band bonding agent of the present invention, preferably make the gel fraction of adhesive phase be 50 ~ 99 % by weight scope.At this, gel fraction is the value measured according to following (I) ~ (IV).
(I) adhesive phase pasting about 8cm × about 8cm area and the metallic screen (be Wm by its weight set) be made up of the SUS304 of about 10cm × about 10cm.
(II) weighing the weight of the paste obtained by above-mentioned (I), is Ws by this weight set, then, fold 4 times in the mode wrapping into adhesive phase, after fixing together with stapler (staple gun), weighing, is Wb by this weight set.
(III) in glass container, put into the sieve that above-mentioned (II) gets up with stapler nail, add after ethyl acetate 60ml floods, this glass container is at room temperature taken care of 3 days.
(IV) take out sieve from glass container, at 120 DEG C after dry 24 hours, weigh, be Wa by this weight set, divide rate based on following formula calculated for gel.
Gel fraction (% by weight)=[Wa-(Wb-Ws)-Wm}/(Ws-Wm)] × 100
When the gel fraction of adhesive phase is more than 50 % by weight, the permanance of adhesive phase is tended to improve, and therefore preferably, in addition, when its gel fraction is below 99 % by weight, easily manufactures, therefore preferably.
When the gel fraction of adhesive phase is adjusted to 50 ~ 99 % by weight, also different because of the kind of the acryl resin of the effective constituent as adhesive phase, if increase the amount of crosslinking chemical, then gel fraction raises, therefore, according to the amount adjustment gel fraction of crosslinking chemical.Specifically, scope from about 0.01 ~ 10 weight portion, suitably selects the use level of the crosslinking chemical of nonvolatile component 100 weight portion (using situation of more than two kinds to be that it always measures) relative to the acryl resin forming adhesive phase according to the kind of acryl resin.More preferably making the gel fraction of adhesive phase be more than 65 % by weight, more preferably more than 75 % by weight, is less than 95 % by weight in addition.
[resin molding of band bonding agent]
The resin molding of band bonding agent of the present invention is provided with at least one side of resin molding the adhesive phase formed by adhesive composition as above.Resin molding used herein can enumerate blooming containing the film be selected from polarizing coating and phase retardation film or, be pasted on blooming etc. as protected body and with the surface protection film etc. protecting its surface to use from objects such as damage or pollutions.
So-called polarizing coating, for having the blooming of the function of injection polarized light to incident lights such as natural lights.Polarizing coating has: have absorb there is the rectilinearly polarized light of the vibration plane in certain direction and transmission have the character of the rectilinearly polarized light of perpendicular vibration plane linear polarization film, there is reflection there is the rectilinearly polarized light of the vibration plane in certain direction and transmission has the polarized light separation membrane of the character of the rectilinearly polarized light of perpendicular vibration plane, is laminated with the elliptic polarization film etc. of polarizing coating and phase retardation film described later.As the preferred concrete example of polarizing coating, particularly linear polarization film (being sometimes referred to as polaroid or polarizer membrane), the polarizing coating adsorbing the dichromatism such as iodine or dichroic dye pigment orientation in the polyvinyl alcohol resin film of uniaxial tension one-tenth can be set forth in.
So-called phase retardation film, for the anisotropic blooming of display optical, can enumerate such as by the polymeric membrane be made up of polyvinyl alcohol (PVA), polycarbonate, polyester, polyarylate, polyimide, polyolefin, cyclic polyolefin, polystyrene, polysulfones, polyethersulfone, Kynoar/polymethylmethacrylate, liquid crystal polyester, cellulose acetate, ethylene-vinyl acetate copolymer saponated material, Polyvinylchloride etc. being stretched to about 1.01 ~ 6 times and the stretched film etc. that obtains.Wherein, the polymeric membrane of preferred uniaxial tension or biaxial stretch-formed polycarbonate membrane or cyclic polyolefin hydro carbons film.Have the film being called as uniaxial retardation film, wide viewing angle phase retardation film, low modulus of photoelasticity phase retardation film etc., any one can be suitable for.
In addition, manifest optically anisotropic film by the coating of liquid crystal compounds, orientation or manifest optically anisotropic film by the coating of inorganic layered compounds and also can be used as phase retardation film.This phase retardation film has: the film being called as temperature compensating type phase retardation film, or the film to be become with the rod shaped liquid crystal twisted-oriented of the sold of " LC film " by Shin Nihon Oil Co., Ltd, the same film become with the rod shaped liquid crystal tilted alignment of the sold of " NH film " by Shin Nihon Oil Co., Ltd, the film become with the disc-like liquid crystal tilted alignment of the sold of " WV film " by Fuji Photo Film Co., Ltd., by Sumitomo Chemical Co with the film of the complete biaxially oriented version of the sold of " VAC film ", same by Sumitomo Chemical Co with the film etc. of the biaxially oriented version of the sold of " new VAC film ".
And then the film being pasted with diaphragm on these bloomings also can be used as blooming.As diaphragm; use transparent resin molding; as this transparent resin, can enumerate such as with Triafol T or the cellulose diacetate cellulose acetate resinoid that is representative, take polymethylmethacrylate as the methacrylic resin, vibrin, polyolefin resin, polycarbonate resin, polyether-ether-ketone resin, polysulfone resin etc. of representative.The ultraviolet light absorbers such as bigcatkin willow acid esters compound, benzophenone compound, benzotriazole compound, compound in triazine class, cyanoacrylate compound, nickel complex salt compounds can be coordinated in the resin forming diaphragm.As diaphragm, preferably use the cellulose acetate resin films such as three cellulose acetate membrane.
In blooming described above, linear polarization film mainly with forming its polaroid, the state of the one or both sides bonding protective film of polarizer membrane that is such as made up of polyvinyl alcohol resin uses.In addition, above-mentioned elliptic polarization film is the film being laminated with linear polarization film and phase retardation film, and this polarizing coating also large state mainly with the one or both sides bonding protective film at polarizer membrane uses.When this elliptic polarization film forms adhesive phase of the present invention, usually form adhesive phase in its phase retardation film side.
So-called surface protection film; for the film using protection as the surface of the blooming of protected body etc. from use for the purpose of damage or pollution; such as expand for the polarizing coating of the production of liquid crystal indicator, phase retardation film, light and penetrate the various blooming such as sheet, reflector plate usually (there is in one side the situation of adhesive phase on its surface; for being in the face of opposition side with this adhesive phase) state of adhesive surface diaphragm circulates; after making it be pasted on liquid crystal cells etc., peel off this surface protection film of removing.As the base material of surface protection film, can enumerate such as: the polyolefin resin of tygon, polypropylene, polymethylpentene and so on; The fluorinated polyallyl hydrocarbon resin of polyvinyl fluoride base, Kynoar, polyvinyl fluoride and so on; The polyester based resin of PEN, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate/isophthalic copolymers and so on; The polyamide of nylon 6, nylon 6,6 and so on; The polyvinyl of Polyvinylchloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol (PVA), vinylon and so on; The cellulosic resin of Triafol T, cellulose diacetate, viscose paper and so on; The acrylic resin of polymethylmethacrylate, polyethyl methacrylate, polyethyl acrylate, butyl polyacrylate and so on; And polystyrene, polycarbonate, polyarylate, polyimide etc.
In the resin molding of band bonding agent of the present invention, preferably paste stripping film until carry out temporary protection when using in its adhesive layer surface.Stripping film used herein can for such as the film be made up of the various resin such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate is set as base material and to this base material and the demoulding process of silicone-treated and so on is implemented on the composition surface of adhesive phase and the film etc. obtained.
Resin molding with bonding agent can utilize such as following method manufacture, that is, stripping film as above applies the adhesive composition illustrated above, form adhesive phase, the method for further laminated resin film on the adhesive phase obtained; Resin molding applies adhesive composition, forms adhesive phase, stripping film protection is pasted in this bonding agent face, make the method etc. of the resin molding of band bonding agent.
The thickness of adhesive phase is not particularly limited, and is preferably generally less than 30 μm, in addition, is preferably more than 10 μm, more preferably 10 ~ 20 μm.When the thickness of adhesive phase is below 30 μm, cementability under hot and humid improves, between glass substrate and adhesive phase, produce the possibility of floating or peeling off tend to step-down, and, re-workability tends to improve, therefore preferred, in addition, when its thickness is more than 10 μm, even if the size of pasting blooming thereon changes, bonding coat also follows this change in size and changes, therefore, there is no difference between the light levels of the periphery of liquid crystal cells and the light levels of central part, there is the tendency suppressing whiting or color spot, therefore preferably.At present, the thickness being pasted on the adhesive phase of liquid crystal cells glass generally with 25 μm for standard, in the present invention, even if this thickness is set as less than 20 μm, also play sufficient performance as adhesive phase.
The resin molding of band bonding agent of the present invention is being pasted on glass substrate after making optical laminate, when this resin molding being peeled off from glass substrate there is any unfavorable condition, adhesive phase is followed resin molding and is stripped, fuzzy or paste is produced hardly residual etc. on the surface of the glass substrate contacted with adhesive phase, therefore, the resin molding of adhesive band bonding agent again again on the glass substrate easily after stripping.That is, so-called re-workability is excellent.
[optical laminate]
The resin molding of band bonding agent of the present invention can be the resin molding comprising blooming, is laminated in glass substrate, makes optical laminate with its adhesive phase.Make optical laminate in order to the resin molding of band bonding agent is laminated in glass substrate, such as, peel stripping film from the resin molding of the band bonding agent obtained as described above, the adhesive phase exposed is pasted on the surface of glass substrate.At this, as glass substrate, can enumerate such as: the glass substrate of liquid crystal cells, anti-dazzle glass, sunglasses glass etc.Wherein, on the glass substrate of the front face side (identification side) of liquid crystal cells laminated belt bonding agent blooming (upper polarizing coating), on the glass substrate of the rear side of liquid crystal cells, the optical laminate of the blooming (lower polarizing coating) of other band bonding agent stacked can be used as liquid crystal indicator, therefore preferably.As the material of glass substrate, can enumerate such as: soda-lime glass, glass with lower alkali content, alkali-free glass etc.
Optical laminate of the present invention can be used as the liquid crystal cells of liquid crystal indicator.
The liquid crystal indicator formed by optical laminate of the present invention may be used for comprising the notebook computer liquid crystal display, televisor, vehicle display, e-dictionary, digital camera, digital camera, electronic desktop computer, clock and watch etc. of such as notebook type, desk-top, PDA (Personal Digital Assistance) etc.
Below, enumerate embodiment and specifically describe the present invention further, but the present invention does not limit by these examples.In example, representing " part " and " % " of use amount or content, unless otherwise specified, is just weight basis.
In the following examples, nonvolatile component is the value with measuring according to the method for JIS K 5407.Specifically, put into binder solution with any weight to water glass with cover, be shown in explosion-proof baking oven the residual nonvolatile component weight make its dry 2 hours at 115 DEG C after with the schedule of proportion of the weight with the solution measured at first.In addition, being determined as follows of weight-average molecular weight is carried out, namely, " the TSK gel GMHHR-H (S) " of configuration 2 Gen East ソ mono-system is connected in series as chromatographic column in GPC device, use tetrahydrofuran as dissolution fluid, under the condition of sample solution concentration 5mg/ml, sample import volume 100 μ l, temperature 40 DEG C, flow velocity 1ml/ minute, converted by polystyrene standard and carry out.
First, the Production Example of exemplary propylene acid resin.
[polymerization example 1]
Having cooling tube, nitrogen ingress pipe, temperature take into account in the reaction vessel of stirring machine the mixed solution adding ethyl acetate 81.8 parts, butyl acrylate 98.6 parts, acrylic acid 2-hydroxyl ethyl ester 1.0 parts and 0.4 part, acrylic acid, while be set as oxygen-free with the air in nitrogen replaceable equipment, internal temperature is risen to 55 DEG C.Thereafter, total amount adds the solution making azoisobutyronitrile (polymerization initiator) 0.14 part be dissolved in ethyl acetate 10 parts and formation.After initiating agent adds 1 hour, while with the concentration of the acryl resin removing monomer be 35% mode in reaction vessel, add ethyl acetate with interpolation speed 17.3 parts/hr continuously, while be incubated 12 hours at internal temperature 54 ~ 56 DEG C, finally, add ethyl acetate to regulate, to make the concentration of acryl resin for 20%.It is 3.9 that the acryl resin obtained utilizes the weight-average molecular weight Mw of the polystyrene conversion of GPC to be 1,230,000, Mw/Mn.Set it to acryl resin A1.The structural unit from the acrylic acid 2-hydroxyl ethyl ester as hydroxyl monomer in acryl resin A1 is 1%, in addition, is 0.4% from the acrylic acid structural unit as carboxyl group-containing monomer.
[polymerization example 2]
Monomer composition is changed to ethyl acetate 81.8 parts, butyl acrylate 78.6 parts, methyl acrylate 20.0 parts, acrylic acid 2-hydroxyl ethyl ester 1.0 parts and 0.4 part, acrylic acid, in addition, operates in the same manner as polymerization example 1, manufacture acryl resin.It is 4.1 that the acryl resin obtained utilizes the weight-average molecular weight Mw of the polystyrene conversion of GPC to be 1,648,000, Mw/Mn.Set it to acryl resin A2.In acryl resin A2, the ratio from the structural unit of the acrylic acid 2-hydroxyl ethyl ester as hydroxyl monomer is 1%, and the ratio from the acrylic acid structural unit as carboxyl group-containing monomer is 0.4%.
Then illustrate and use the above acryl resin manufactured prepare bonding agent and be applied to embodiment and the comparative example of blooming.In the following examples, use following compound as ionic compound.The mark of each compound is in order to mark additional for reference later, is called that the compound of ionic solid 1 ~ ionic solid 5 is solid under the room temperature of 25 DEG C, is called that the compound of ionic solid 1 is liquid under the room temperature of 25 DEG C.
Ionic solid 1:N-butyl-4-picoline hexafluorophosphoric acid ester (there is the structure of following formula, fusing point 48 DEG C)
Ionic solid 2:N-hexyl pyridine hexafluorophosphoric acid ester (there is the structure of following formula, fusing point 45 DEG C)
Ionic solid 3:N-octyl group-4-picoline hexafluorophosphoric acid ester (there is the structure of following formula, fusing point 44 DEG C)
Ionic solid 4:1-methyl-3-ethyl imidazol(e) hexafluorophosphoric acid ester (there is the structure of following formula, fusing point 62 DEG C)
Ionic solid 5: TBuA hexafluorophosphoric acid ester (there is the structure of following formula, fusing point 78 DEG C)
Ionic liquid 1:N-hexyl-4-picoline hexafluorophosphoric acid ester (there is the structure of following formula, fusing point 18 DEG C)
In addition, as crosslinking chemical and silane compound, use following compound (being all trade name).
(crosslinking chemical)
タ ケ ネ mono-ト D160N: the ethyl acetate solution (solid component concentration 75%) of the trimethylolpropane adduct of hexamethylene diisocyanate, to obtain from Mitsui Chemical Polyurethane Co., Ltd.
コ ロ ネ mono-ト L: the ethyl acetate solution (solid component concentration 75%) of the trimethylolpropane adduct of tolylene diisocyanate, to obtain from Japanese polyurethane Co., Ltd..
(silane compound)
KBE-402: glycidoxypropyl group diethoxymethylsilane (liquid), to obtain from Shin-Etsu Chemial Co., Ltd.
KBM-403: glycidoxypropyltrime,hoxysilane (liquid), to obtain from Shin-Etsu Chemial Co., Ltd.
[embodiment 1 ~ 5 and comparative example 1 ~ 3]
The manufacture of (a) bonding agent
The solid constituent 100 parts of the acryl resin A1 relatively obtained by polymerization example 1, to crosslinking chemical " タ ケ ネ mono-ト D160N ", the silane compound " KBE-402 " 0.5 part of 0.8 part be counted by solid constituent and mix with the ionic compound shown in the table 1 of the amount shown in table 1 respectively, the mode being 13% with solid component concentration further adds ethyl acetate, makes adhesive composition.
[table 1]
The making of the resin molding of (b) band bonding agent
(trade name " PET 3811 ", to obtain from リ ンテツク Co., Ltd. at the poly terephthalic acid 7 diol ester film of demoulding process; Be called spacer) demoulding treated side, use applicator to apply above-mentioned each adhesive composition in the mode that dried thickness is 15 μm, at 90 DEG C, make its dry 1 minute, obtain the bonding agent of sheet.Then; utilize stacked machine make to be in the spacer of sheet bonding agent obtained above opposition side face (bonding agent face), adsorb iodine and the one side of the polarizing coating of the 3-tier architecture on the two sides of the polyvinyl alcohol polarization sheet of orientation is pasted with clamping with the diaphragm be made up of Triafol T; then; slaking 7 days under the condition of temperature 23 DEG C, relative humidity 65%, obtains the resin molding being with bonding agent.About each adhesive phase after slaking, measure gel fraction by the method described above, the results are shown in table 2.
The antistatic behaviour evaluation of the resin molding of (c) band bonding agent
When peeling off the spacer of band bonding agent polarizing coating of gained, measure the sheet resistance value of bonding agent with surperficial intrinsic resistance determinator [" Hirest-up MCP-HT450 " (trade name) of Mitsubishi chemical Co., Ltd], evaluate antistatic behaviour.If sheet resistance value is 10 11Ω/ level or its below, then can obtain good antistatic behaviour.The evaluation of antistatic behaviour is directly carried out after the slaking of the polarizing coating of band bonding agent terminates.In addition, in order to observe timeliness change during long-time preservation, polarizing coating keeping in the baking oven of temperature 60 C, relative humidity 70% of the band bonding agent after slaking being terminated, after 6 days, peels off spacer as described above, measures the sheet resistance value of bonding agent.At this, when temperature 60 C, relative humidity 70% time keeping 6 days, the effect roughly the same with at room temperature taking care of 6 months can be obtained.Table 2 will be the results are summarized in.
The making of (d) optical laminate and evaluation
After peeling spacer from the polarizing coating of the band bonding agent be made up of above-mentioned (b), its bonding agent face is pasted on the one side of liquid crystal cells glass substrate [" 1737 " (trade name) of コ mono-ニ Application グ society], makes optical laminate.About optical laminate, respectively to carry out under the drying condition of temperature 80 DEG C the keeping heat resistant test of 300 hours situation, carry out temperature 60 C, relative humidity 90% time keeping hot resistance test of 300 hours situation and-30 DEG C will be cooled to from the state being heated to 70 DEG C, then be warming up to the process of 70 DEG C as 1 circulation (1 hour), the situation carrying out being repeated the heatproof impact test that 100 circulate, visualization test after optical laminate.The following benchmark of result is classified, is summarized in table 2.
(metewand to the permanance of hot, damp and hot and thermal shock (being denoted as in table 2 " HS "))
◎: do not see completely float, peel off, the cosmetic variation such as foaming.
Zero: almost do not see float, peel off, the cosmetic variation such as foaming.
△: float, peel off, the cosmetic variation such as foaming is remarkable a little.
×: see significantly float, peel off, the cosmetic variation such as foaming.
[embodiment 6]
The solid constituent 100 parts of the acryl resin A2 relatively obtained by polymerization example 2, crosslinking chemical " コ ロ ネ mono-ト L ", silane compound " KBM-403 " 0.5 part and the 7.5 parts of ionic solids 3 of counting 0.5 part by solid constituent are mixed, the mode being 13% with solid component concentration further adds ethyl acetate, makes adhesive composition.Use this adhesive composition to carry out the evaluation same with embodiment 1 ~ 5, will table 2 be the results are summarized in.
[table 2]
State during 25 DEG C of the ionic compound * used
Learnt by table 1 and table 2, relative acryl resin 100 parts, coordinate in the present invention the ionic solid 1 part that specifies and form the embodiment 1 ~ 5 of bonding agent and coordinate ionic solid 7.5 parts and form the embodiment 6 of bonding agent, compared with the comparative example 1 being combined with ionic liquid, equal antistatic behaviour is manifested at the making initial stage, simultaneously, even if place for a long time, antistatic behaviour also changes hardly, in addition, in thermotolerance, humidity resistance and resistance to sudden heating, the result that also can be roughly satisfied with.
Relative to this, be engaged in the comparative example 1 forming bonding agent at 25 DEG C for N-hexyl-4-picoline hexafluorophosphoric acid ester (ionic liquid 1) of liquid, although manifest good antistatic behaviour at the making initial stage, but, when promoting temperature 60 C, relative humidity 70% time keeping 6 days of test as heating, sheet resistance value after spacer stripping and the value at initial stage are in a ratio of more than 10 times, see the tendency that antistatic behaviour weakens because taking care of for a long time.By cooperation identical ionic solid 3 but it measures the result of altered embodiment 3, comparative example 2 and comparative example 3, if be 0.1 part relative to the use level of the ionic solid of acryl resin 100 parts, the effect of then giving antistatic behaviour is insufficient, in addition, when its amount is 10 parts, the result that display permanance is insufficient.
Utilizability in industry
The resin molding of band bonding agent of the present invention can suppress the charged of optical component effectively.And then, even if long-time keeping after making, the antistatic behaviour at initial stage also can be kept.
The resin molding of this band bonding agent, by such as forming resin molding by blooming and being laminated in the glass substrate of liquid crystal cells, provides liquid crystal display optical laminate.The stress that the change in size that the adhesive phase of this optical laminate absorbs under wet heat condition, relax blooming and glass substrate causes, therefore, the stress that can alleviate local is concentrated, and suppresses the floating or peel off of adhesive phase relative to glass substrate.In addition, the optical defect that uneven stress distribution causes can be prevented, therefore, whiting can be suppressed.And then, once after the resin molding of band bonding agent is laminated in glass substrate, when exist any bad, even if this resin molding is peeled off from glass substrate together with bonding agent, also the surface generation paste of little glass substrate after stripping is residual or fuzzy, again can be used as glass substrate, be the film of re-workability excellence.
In addition, the resin molding of this band bonding agent also can be pasted on the surface of blooming, makes until protect the surface protection film on its surface when using.Now, also give excellent antistatic effect, such as, after can making that blooming is pasted on liquid crystal cells via the adhesive phase being in opposition side with surface protection film, the electrostatic produced when peeling this surface protection film diminishes.
The resin molding of band bonding agent of the present invention has been endowed high antistatic behaviour, and meanwhile, can keep this antistatic behaviour for a long time, in addition, permanance is also excellent.The resin molding of this band bonding agent forms resin molding by blooming, can be preferred for liquid crystal indicator.In addition, the resin molding of this band bonding agent is also preferably used as the surface protection film on the surface of protection blooming.

Claims (3)

1. an optical laminate, it is the optical laminate being with the blooming of bonding agent to be laminated in glass substrate in its adhesive phase side, wherein, the blooming of described band bonding agent is formed with adhesive phase in the one side being selected from the blooming in polarizing coating and phase retardation film, and described blooming is resin molding
This adhesive phase is formed by following composition, described composition contain (A) be acryl resin 100 weight portion of principal ingredient from the structural unit of (methyl) acrylate shown in following formula (I), (B) have pyridylium or glyoxaline cation and at room temperature for ionic compound 0.2 ~ 3 weight portion of solid, (C) crosslinking chemical 0.01 ~ 10 weight portion and (D) silane compound 0.01 ~ 10 weight portion, gel fraction is in the scope of 50 ~ 99 % by weight
In formula, R 1represent hydrogen atom or methyl, R2 represents alkyl or the aralkyl of carbon number 1 ~ 14, or respectively by the alkyl of the carbon number 1 ~ 14 of the alkoxy of carbon number 1 ~ 10 replacement or aralkyl.
2. optical laminate according to claim 1, wherein,
Ionic compound (B) has the anion component containing fluorine atom.
3. optical laminate according to claim 2, wherein,
Anion component is hexafluorophosphoric acid salt anionic.
CN200880105125.3A 2007-09-03 2008-08-27 Resin film with adhesive and optical laminate using the same Active CN101828134B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2007-227447 2007-09-03
JP2007227447 2007-09-03
PCT/JP2008/065791 WO2009031548A1 (en) 2007-09-03 2008-08-27 Resin film with adhesive and optical laminate using the same

Publications (2)

Publication Number Publication Date
CN101828134A CN101828134A (en) 2010-09-08
CN101828134B true CN101828134B (en) 2015-03-18

Family

ID=40428862

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200880105125.3A Active CN101828134B (en) 2007-09-03 2008-08-27 Resin film with adhesive and optical laminate using the same

Country Status (5)

Country Link
JP (1) JP5332315B2 (en)
KR (1) KR101532104B1 (en)
CN (1) CN101828134B (en)
TW (1) TWI529230B (en)
WO (1) WO2009031548A1 (en)

Families Citing this family (70)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4963485B2 (en) * 2008-04-07 2012-06-27 綜研化学株式会社 Adhesive composition for polarizing plate and method for producing the same
JP5322280B2 (en) * 2009-03-27 2013-10-23 サイデン化学株式会社 Optical pressure-sensitive adhesive composition
JP2011006595A (en) * 2009-06-26 2011-01-13 Tokyo Ohka Kogyo Co Ltd Adhesive composition and adhesive film
JP5549357B2 (en) * 2009-10-07 2014-07-16 住友化学株式会社 LCD panel
JP5540863B2 (en) * 2010-04-22 2014-07-02 住友化学株式会社 RESIN FILM WITH ADHESIVE AND OPTICAL LAMINATE USING THE SAME
US9429685B2 (en) 2010-05-25 2016-08-30 Sharp Kabushiki Kaisha Laminate
JP5968587B2 (en) 2010-10-21 2016-08-10 日東電工株式会社 Optical adhesive sheet, optical film and display device
KR101784825B1 (en) * 2011-04-21 2017-10-13 동우 화인켐 주식회사 Adhesive composition, polarizing plate and liquid crystal display device comprising the same
JP5921641B2 (en) * 2011-05-26 2016-05-24 日東電工株式会社 Polarizing film with adhesive layer and image display device
JP2013008019A (en) 2011-05-26 2013-01-10 Nitto Denko Corp Polarization film having adhesive layer and image display unit
JP5734754B2 (en) * 2011-06-10 2015-06-17 藤森工業株式会社 Adhesive composition containing antistatic agent and adhesive film
TW201336954A (en) * 2012-02-10 2013-09-16 Sumitomo Chemical Co Adhesive sheet, optical film with adhesive, optical laminate, and method for producing adhesive sheet
JP5882774B2 (en) * 2012-02-13 2016-03-09 藤森工業株式会社 Adhesive composition, adhesive film and surface protective film
JP2013163783A (en) * 2012-02-13 2013-08-22 Fujimori Kogyo Co Ltd Adhesive composition, adhesive film and surface-protecting film
JP6268407B2 (en) * 2012-07-27 2018-01-31 藤森工業株式会社 Adhesive composition and surface protective film
KR101887570B1 (en) * 2012-09-04 2018-08-10 동우 화인켐 주식회사 Adhesive composition
JP6187896B2 (en) * 2012-11-16 2017-08-30 藤森工業株式会社 Adhesive layer, adhesive film and surface protective film
JP6393920B2 (en) * 2012-11-20 2018-09-26 藤森工業株式会社 Adhesive composition, adhesive film and surface protective film
JP6292808B2 (en) * 2013-09-13 2018-03-14 デクセリアルズ株式会社 Adhesive and light emitting device
KR102262160B1 (en) * 2013-12-24 2021-06-08 동우 화인켐 주식회사 Polarizing Plate and Liquid Crystal Display Comprising the Same
TWI645010B (en) * 2014-03-17 2018-12-21 日商住友化學股份有限公司 Resin film with adhesive and optical laminate using the same
JP2015200698A (en) * 2014-04-04 2015-11-12 日東電工株式会社 Transparent resin layer, polarizing film with adhesive layer, and image display device
JP2015091988A (en) * 2015-01-09 2015-05-14 藤森工業株式会社 Adhesive agent composition and surface protective film
JP6339515B2 (en) * 2015-03-26 2018-06-06 藤森工業株式会社 Surface protective film and optical component on which it is bonded
JP6550250B2 (en) * 2015-03-27 2019-07-24 リンテック株式会社 Adhesive film with optical film
KR20160117289A (en) * 2015-03-31 2016-10-10 스미또모 가가꾸 가부시키가이샤 Optical laminate and liquid crystal display device
WO2016163287A1 (en) 2015-04-10 2016-10-13 日本合成化学工業株式会社 Adhesive composition, adhesive obtained using same, and adhesive for polarizing plates
JP2015165027A (en) * 2015-04-15 2015-09-17 藤森工業株式会社 Adhesive composition containing antistatic agent, and adhesive film
JP6320358B2 (en) * 2015-09-29 2018-05-09 日東電工株式会社 Liquid crystal panel with touch sensing function and liquid crystal display device
CN106566445A (en) * 2015-10-07 2017-04-19 住友化学株式会社 Adhesive composition, adhesive layer, and optical member with adhesive layer
JP7158126B2 (en) 2015-11-17 2022-10-21 住友化学株式会社 Resin film with adhesive and optical laminate containing the same
JP6043445B2 (en) * 2016-01-29 2016-12-14 藤森工業株式会社 Adhesive composition and surface protective film
JP6039118B2 (en) * 2016-01-29 2016-12-07 藤森工業株式会社 Adhesive composition and surface protective film
JP6364644B2 (en) * 2016-02-04 2018-08-01 藤森工業株式会社 Surface protective film for optical film and optical film on which it is bonded
JP6131351B2 (en) * 2016-02-15 2017-05-17 藤森工業株式会社 Adhesive layer, adhesive film and surface protective film
JP6316875B2 (en) * 2016-06-10 2018-04-25 藤森工業株式会社 Adhesive composition and surface protective film
JP6288866B2 (en) * 2016-06-10 2018-03-07 藤森工業株式会社 Surface protection film
JP6240275B2 (en) * 2016-08-09 2017-11-29 藤森工業株式会社 Surface protection film
JP6243491B2 (en) * 2016-08-19 2017-12-06 藤森工業株式会社 Adhesive composition for surface protective film and surface protective film
JP2018090725A (en) * 2016-12-06 2018-06-14 Dic株式会社 Adhesive film and information display device using the same
JP6334018B2 (en) * 2017-01-25 2018-05-30 藤森工業株式会社 Adhesive composition and surface protective film
JP6293947B2 (en) * 2017-03-13 2018-03-14 藤森工業株式会社 Surface protection film
US20210108109A1 (en) * 2017-03-28 2021-04-15 Nitto Denko Corporation Polarizing film with added adhesive layer, polarizing film with added adhesive layer for in-cell liquid crystal panel, in-cell liquid crystal panel, and liquid crystal display device
JP6737735B2 (en) * 2017-04-14 2020-08-12 藤森工業株式会社 Surface protection film
JP6408653B2 (en) * 2017-05-30 2018-10-17 藤森工業株式会社 Surface protection film
JP6363262B2 (en) * 2017-06-12 2018-07-25 藤森工業株式会社 Surface protective film and optical film on which it is bonded
JP6796035B2 (en) * 2017-06-29 2020-12-02 藤森工業株式会社 Adhesive composition and adhesive film
JP6483764B2 (en) * 2017-07-21 2019-03-13 藤森工業株式会社 Surface protection film
JP6676593B2 (en) * 2017-09-08 2020-04-08 リンテック株式会社 Resin sheet and semiconductor device
JP6525355B2 (en) * 2017-11-01 2019-06-05 藤森工業株式会社 Surface protection film
JP6635611B2 (en) * 2018-02-02 2020-01-29 藤森工業株式会社 Surface protection film
JP6559283B2 (en) * 2018-03-27 2019-08-14 藤森工業株式会社 Adhesive composition and surface protective film
JP6558816B2 (en) * 2018-04-24 2019-08-14 藤森工業株式会社 Adhesive composition and surface protective film
JP6529203B2 (en) * 2018-05-10 2019-06-12 藤森工業株式会社 Release film for antistatic surface protection film
JP6970169B2 (en) * 2018-06-26 2021-11-24 藤森工業株式会社 Surface protective film for optical film
JP6635613B2 (en) * 2018-06-26 2020-01-29 藤森工業株式会社 Surface protection film
JP2020012098A (en) * 2018-07-10 2020-01-23 三菱ケミカル株式会社 Adhesive composition, and adhesive including the same, adhesive for polarizing plate, and image display device
KR102152295B1 (en) * 2018-09-04 2020-09-04 (주)이녹스첨단소재 Adhesive sheet for display and display comprising the same
JP6734335B2 (en) * 2018-09-20 2020-08-05 藤森工業株式会社 Surface protection film
JP6864031B2 (en) * 2019-04-26 2021-04-21 藤森工業株式会社 Surface protective film
JP6876751B2 (en) * 2019-07-10 2021-05-26 藤森工業株式会社 Surface protective film
KR20210098188A (en) * 2020-01-31 2021-08-10 (주)이녹스첨단소재 Adhesive Sheet for protect display
JP6871450B2 (en) * 2020-03-12 2021-05-12 藤森工業株式会社 Adhesive composition and surface protective film
JP7227340B2 (en) * 2020-04-14 2023-02-21 藤森工業株式会社 surface protection film
JP6999735B2 (en) * 2020-04-14 2022-02-10 藤森工業株式会社 Surface protective film
CN115485346A (en) * 2020-07-15 2022-12-16 惠和株式会社 Protective sheet body and laminate
JP7014879B2 (en) * 2020-11-12 2022-02-01 藤森工業株式会社 Adhesive composition and adhesive film
CN113980171B (en) * 2021-12-01 2022-10-11 香港中文大学（深圳） Polymer material hardened in wet and preparation method and application thereof
JP2023146370A (en) * 2022-03-29 2023-10-12 日東電工株式会社 Optical pressure sensitive adhesive sheet
JP2023146369A (en) * 2022-03-29 2023-10-12 日東電工株式会社 Optical pressure sensitive adhesive sheet

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1508184A (en) * 2002-11-25 2004-06-30 ס�ѻ�ѧ��ҵ��ʽ���� Proenoic-acid resin composition, adhesive comprising same and optical laminated product containing said adhesive
CN1727426A (en) * 2004-07-26 2006-02-01 日东电工株式会社 Adhesive composition, adhesive sheets, and surface protecting film

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4370888B2 (en) * 2002-11-25 2009-11-25 住友化学株式会社 Optical film with adhesive and optical laminate using the same
JP5030251B2 (en) * 2004-07-26 2012-09-19 日東電工株式会社 Adhesive composition, adhesive sheet and surface protective film
US7750075B2 (en) * 2004-10-21 2010-07-06 Lg Chem, Ltd. Acrylic pressure sensitive adhesive with good antistatic property
KR101198531B1 (en) * 2005-06-24 2012-11-06 토요잉크Sc홀딩스주식회사 Antistatic acrylic pressure-sensitive adhesive
JP5452850B2 (en) * 2007-07-13 2014-03-26 チェイル インダストリーズ インコーポレイテッド Surface protection sheet for optical members

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1508184A (en) * 2002-11-25 2004-06-30 ס�ѻ�ѧ��ҵ��ʽ���� Proenoic-acid resin composition, adhesive comprising same and optical laminated product containing said adhesive
CN1727426A (en) * 2004-07-26 2006-02-01 日东电工株式会社 Adhesive composition, adhesive sheets, and surface protecting film

Also Published As

Publication number Publication date
KR20100070336A (en) 2010-06-25
TWI529230B (en) 2016-04-11
CN101828134A (en) 2010-09-08
JP5332315B2 (en) 2013-11-06
KR101532104B1 (en) 2015-06-26
JP2009079205A (en) 2009-04-16
TW200920811A (en) 2009-05-16
WO2009031548A1 (en) 2009-03-12

Similar Documents

Publication Publication Date Title
CN101828134B (en) Resin film with adhesive and optical laminate using the same
CN102119348B (en) Optical film with adhesive and optical laminate using same
CN102119349B (en) Optical film with adhesive and optical laminate using same
CN103403117B (en) Optical film having adhesive agent, and optical laminated body in which same is used
CN102721992B (en) Be coated with the blooming of bonding agent
CN104105769B (en) The manufacture method of the blooming of adhesive sheet, band tackiness agent, optical laminate and adhesive sheet
CN102033355B (en) Liquid crystal panel
CN101796439A (en) Optical film with adhesive and optical laminate
CN108291126A (en) Adhesive composition, adhesive sheet and the optical film with adhesive
TWI675081B (en) Optical film with adhesive agent and optical laminate
CN104927691A (en) Resin film with adhesive and optical laminated body using the same
CN103562759A (en) Polarizing film with adhesive layer and image display apparatus
KR102473610B1 (en) Adhesive composition, adhesive layer and optical member with adhesive layer
JP2011100095A (en) Liquid crystal panel
CN101490587A (en) Polarizing film with adhesive, optical laminate, and set of polarizing films
JP2008095081A (en) Optical film with pressure-sensitive adhesive
CN106566445A (en) Adhesive composition, adhesive layer, and optical member with adhesive layer
JP2017125105A (en) Adhesive composition
CN105585979B (en) Adhesive composition, adhesive phase and the optical component with adhesive phase
JP2019174814A (en) Optical film with adhesive and optical laminate
CN108350325A (en) Resin film with adhesive and the optical laminate comprising it
JP2011154079A (en) Liquid crystal panel

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant