CN101828134A - Resin film with adhesive and optical laminate using the same - Google Patents
Resin film with adhesive and optical laminate using the same Download PDFInfo
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- CN101828134A CN101828134A CN200880105125A CN200880105125A CN101828134A CN 101828134 A CN101828134 A CN 101828134A CN 200880105125 A CN200880105125 A CN 200880105125A CN 200880105125 A CN200880105125 A CN 200880105125A CN 101828134 A CN101828134 A CN 101828134A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—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
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- 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
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- 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
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polarising Elements (AREA)
Abstract
Disclosed is a resin film with adhesive, which is obtained by forming an adhesive layer on the surface of a resin film. The adhesive layer is excellent in durability and provided with high antistatic properties which hardly change over time. Specifically disclosed is a resin film with adhesive, which is obtained by forming an adhesive layer on at least one side of a resin film such as an optical film or a surface protection film. The adhesive layer is made from a composition containing 0.2-8 parts by weight of an ionic compound (B) having an organic cation, which is in a solid state at room temperature, per 100 parts by weight of an acrylic resin (A) mainly composed of a structural unit derived from a (meth)acrylate represented by the following formula (I). In the formula (I), R1 represents a hydrogen atom or a methyl group; and R2 represents an alkyl or aralkyl group having 1-14 carbon atoms which may be substituted by an alkoxy group having 1-10 carbon atoms.
Description
Technical field
The present invention relates to a kind of resin molding that is formed with adhesive phase.As the resin molding that is set at object among the present invention, can enumerate the blooming that for example contains polarizing coating and/or phase retardation film and the adhesive phase that is pasted on this blooming is in the face of opposition side and its surperficial surface protection film of protection in use.The invention still further relates to a kind of use and be formed with the liquid crystal display optical laminate of the resin molding of this adhesive phase.
Background technology
Polarizing coating often is installed on the liquid crystal indicator and is widely used, and it is with in the stacked transparent protective film in the two sides of polaroid, the state circulation that forms adhesive phase on the surface of at least one diaphragm, paste stripping film on described adhesive phase.In addition, be pasted with stacked phase retardation film on the polarizing coating of state of diaphragm on the two sides of polaroid sometimes, make the elliptic polarization film, and, paste adhesive phase and stripping film with the order of adhesive phase/stripping film in this phase retardation film side.And then, sometimes on the surface of phase retardation film, paste adhesive phase and stripping film with the order of adhesive phase/stripping film.Before being pasted on liquid crystal cells, peel stripping film from these polarizing coatings, elliptic polarization film, phase retardation film etc., be pasted on liquid crystal cells via the adhesive phase that exposes.Produce static when this polarizing coating, elliptic polarization film or phase retardation film are pasted on liquid crystal cells peeling off stripping film, therefore, urgent expectation is developed it and is prevented countermeasure.
As one of its countermeasure; in No. 3012860 communique of patent, a kind of polarizing coating has been proposed; described polarizing coating is at the surperficial stacked diaphragm of polarizer membrane, be provided with adhesive phase on the surface of diaphragm; wherein; as bonding agent, use ionic conductivity composition that constitutes by electrolytic salt and organopolysiloxane and the composition that contains acrylic acid series copolymer.By using this bonding agent, though manifest antistatic behaviour, may not we can say that its performance is abundant, in addition, the sufficient performance of aspect adhesion durability, can not saying so.
Therefore, in Japanese Unexamined Patent Application Publication 2004-536940 communique (WO2003/011958), disclose the antistatic agent that in pressure adhesive (bonding agent), cooperates organic salt, thereby give antistatic behaviour this bonding agent.In addition, in TOHKEMY 2004-114665 communique, record to make and contain the salt that quaternary ammonium cation and contain fluorine atoms negative ion by total carbon number 4~20 constitute in bonding agent etc., thereby give its antistatic behaviour.And then, in TOHKEMY 2006-307238 communique, record make contain in the bonding agent in room temperature (25 ℃) down antistatic to seek for the ionic liquid of liquid.But long-time the placement when being coated with the polarizing coating of bonding agent causes the antistatic behaviour variation because of timeliness changes sometimes.The circulation of general polarizing coating and storage time begin to be to the maximum about 6 months from making, therefore, require to keep antistatic property during using until client.
In addition, the blooming of aforesaid band bonding agent is pasted in the liquid crystal cell with its adhesive phase side and makes liquid crystal indicator, under this state, place under high temperature or the hot and humid condition or when carrying out heating and cooling repeatedly, follow the change in size of blooming, sometimes adhesive phase produce to bubble or floats or peel off etc. producing between blooming and the adhesive phase or between adhesive phase and liquid crystal cells glass, therefore, also require not produce such unfavorable condition and excellent in te pins of durability.And then, be exposed to high temperature following time, act on the skewness of the residual stress of blooming, peripheral part generation stress at blooming is concentrated, the whiting that is called as that peripheral part turns white takes place, or produces color spot in its result sometimes when black the demonstration, therefore, also require to suppress this whiting or color spot.And then, when the blooming of being with bonding agent is pasted on liquid crystal cells, under situation defective, need peel this blooming off and then paste new film again, but when this is peeled off, adhesive phase is followed blooming and is peeled, and therefore, also requires on unit glass (Cell glass) not residual adhesive, does not produce so-called re-workabilities such as fuzzy.
On the other hand, surface protection film generally is pasted on as the blooming of protected body etc. via the bonding agent that is formed at its one side, is used to prevent to process or the damage that produces when carrying protected body or pollution etc.For example, be applied to bloomings such as the polarizing coating of liquid crystal indicator or phase retardation film in order to prevent damage or pollution etc., to be pasted with the state circulation of described surface protection film at the face that is in opposition side with the above-mentioned adhesive phase that is used to be pasted on liquid crystal cells.This surface protection film is stripped from after blooming is pasted on liquid crystal cells and is removed; when peeling off, it produces static; when under the state of residual this static, liquid crystal cells being applied voltage; there is the orientation of infringement liquid crystal molecule or produces the damaged problem of panel; therefore, surface protection film is implemented various antistatic treatment.
Problem of the present invention is, a kind of resin molding with bonding agent is provided, and the resin molding of described band bonding agent is provided with on the surface of resin molding and has been endowed high antistatic behaviour, this antistatic behaviour is difficult to change along with the time and permanance is also excellent simultaneously adhesive phase.The inventor etc. concentrate on studies in order to solve above-mentioned problem, found that, by the surface at resin molding be provided with relatively be with the acryl resin bonding agent of principal ingredient be combined with room temperature (25 ℃) down for the composition of the specific ionic compound of solid as adhesive phase, the timeliness that can obtain antistatic behaviour, antistatic behaviour changes and the resin molding of the band bonding agent of excellent in te pins of durability, finishes the present invention thus.
Summary of the invention
The inventor etc. concentrate on studies to achieve these goals, found that, by being arranged on the surface of blooming by the adhesive phase that adhesive composition forms, can obtain excellent result, wherein, in described adhesive composition, constitute the acryl resin of the principal ingredient that becomes bonding agent by material with specific molecular weight and molecular weight distribution, cooperate 2 kinds of specific materials as crosslinking chemical simultaneously, and and then cooperate and to have the oligomer of specific functional group as silane compound.
That is, according to the present invention, provide a kind of resin molding with bonding agent, its one side at least at resin molding is formed with adhesive phase, and this adhesive phase is by containing following composition (A) and composition (B) forms.
(A) with from following formula (I)
(in the formula, R
1Expression hydrogen atom or methyl, R
2The alkyl or the aralkyl of expression carbon number 1~14 are perhaps respectively by the alkyl or the aralkyl of the carbon number 1~14 of the alkoxy of carbon number 1~10 replacement.) structural unit of (methyl) acrylate of expression is acryl resin 100 weight portions of principal ingredient and (B) has an organic cation and at room temperature be ionic compound 0.2~8 weight portion of solid.
Thus, the present invention finds, for the acryl resin (A) that constitutes bonding agent, give the adhesive phase that forms by this bonding agent with antistatic behaviour, simultaneously, the antistatic agent of the inhibition that changes as the timeliness that is used to realize antistatic behaviour is effective especially for the ionic compound of solid (B) down in room temperature (25 ℃).
The resin molding that forms this adhesive phase can be the blooming that contains polarizing coating and/or phase retardation film.In addition, also can be pasted on this blooming with adhesive phase be in opposition side face, when using till its surperficial surface protection film of protection.
When resin molding is blooming, can be laminated in glass substrate, make the liquid crystal display optical laminate with its adhesive phase side.Therefore, according to the present invention, also provide a kind of optical laminate, it is to be laminated in glass substrate at the blooming that blooming is formed with the band bonding agent of above-mentioned adhesive phase with its adhesive phase side to form.
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 in the one side at least of resin molding, and this adhesive phase is by containing
(A) acryl resin reaches
(B) has organic cation and at room temperature forming for the composition of the ionic compound of solid.At first, each composition that constitutes adhesive composition is described.
[acryl resin (A)]
In the resin molding of band bonding agent of the present invention, the acryl resin (A) that is used for adhesive phase is a principal ingredient with the structural unit from (methyl) acrylate of above-mentioned formula (I) expression, particularly, on basis, can also contain 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 from the structural unit of described (methyl) acrylate.At this, so-called (methyl) acrylic acid is meant to be in the acrylic or methacrylic acid any, and " methyl " when in addition, being called (methyl) acrylate etc. also is the same meaning.
In the above-mentioned formula (I) of main composition unit that is acryl resin (A), R
1Be hydrogen atom or methyl, R
2Alkyl or aralkyl for carbon number 1~14 are preferably alkyl.R
2Hydrogen atom in the alkyl of expression or each group of aralkyl can be replaced by the alkoxy of carbon number 1~10.
As (methyl) acrylate of formula (I) expression, particular instantiation: the alkyl acrylate of the straight chain shape of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, acrylic acid n-octyl, lauryl acrylate and so on; The alkyl acrylate of a chain of isobutyl acrylate, 2-EHA, Isooctyl acrylate monomer and so on; The alkyl methacrylate of the straight chain shape of methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, n octyl methacrylate, lauryl methacrylate and so on; The alkyl methacrylate of a chain of isobutyl methacrylate, methacrylic acid 2-Octyl Nitrite, EHMA and so on etc.
As R
2During the alkyl that replaces for alkoxy, R
2(methyl) acrylate of formula during for alkoxyalkyl (I) expression, particular instantiation acrylic acid 2-methoxyl ethyl ester, acrylic acid ethoxy methyl esters, methacrylic acid 2-methoxyl ethyl ester, methacrylic acid ethoxy methyl esters etc.As R
2(methyl) acrylate of formula during for aralkyl (I) expression, particular instantiation benzyl acrylate and benzyl methacrylate etc.
These (methyl) acrylate can be distinguished use separately, in addition, can use different multiple (methyl) acrylate to make its copolymerization.
As the example of monomer, can enumerate: the monomer with free carboxy of acrylic acid, methacrylic acid, propenoic acid beta-carboxylic ethyl ester and so on polar functional group; The monomer with hydroxyl of (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 2-or 3-chloro-2-hydroxy propyl ester, diethylene glycol one (methyl) acrylate and so on; Acryloyl morpholine, caprolactam, N-vinyl-2-Pyrrolidone, (methyl) acrylic acid tetrahydrofuran ester, caprolactone modification tetrahydrofuran acrylate, 3,4-epoxy radicals cyclohexyl methyl (methyl) acrylate, (methyl) glycidyl acrylate, 2, the monomer with heterocyclic radical of 5-dihydrofuran and so on; N, the monomer with amino different of N-dimethyl aminoethyl (methyl) acrylate and so on etc. with heterocycle.Monomer with these polar functional groups can be distinguished use separately, also can use different multiple monomers.
Wherein, the monomer that preferably will have a hydroxyl contains one of polar functional group monomer as what constitute acryl resin (A).In addition, on the basis of the monomer with hydroxyl, and the monomer that with the monomer with other polar functional group, for example has a free carboxy also is effective.
The acryl resin (A) that is used for adhesive phase is its nonvolatile component 100 weight portions relatively, the structural unit that contains (methyl) acrylate of representing from above-mentioned formula (I) with the ratio of common 60~99.9 weight portions, preferred 80~99.6 weight portions, in addition, contain structural unit with the ratio of common 0.1~20 weight portion, preferred 0.4~10 weight portion from monomer with polar functional group.
Be used for the structural unit that acryl resin of the present invention (A) can contain (methyl) acrylate of the formula (I) from above explanation and have the monomer monomer in addition of polar functional group.As these examples, can enumerate structural unit, from the structural unit of styrene monomer, from the structural unit of vinyl monomer, from structural unit of the monomer that has a plurality of (methyl) acryloyl group in the molecule etc. from (methyl) acrylate that has the ester ring type structure in the molecule.
So-called ester ring type structure,, preferred about 5~7 cycloolefin structure common more than 5 for carbon number.Concrete example as acrylate with ester ring type structure, can enumerate: isobornyl acrylate, cyclohexyl acrylate, acrylic acid dicyclo pentyl ester, acrylic acid cyclo-dodecyl ester, acrylic acid methyl cyclohexane ester, acrylic acid 3-methyl cyclohexanol ester, acrylic acid tert-butyl group cyclohexyl, α-ethoxy-c olefin(e) acid cyclohexyl, acrylic acid cyclohexyl phenyl ester etc., as the concrete example of methacrylate, can enumerate: isobornyl methacrylate with ester ring type structure, cyclohexyl methacrylate, methacrylic acid dicyclo pentyl ester, methacrylic acid cyclo-dodecyl ester, methyl methacrylate base cyclohexyl, methacrylic acid 3-methyl cyclohexanol ester, methacrylic acid tert-butyl group cyclohexyl, methacrylic acid cyclohexyl phenyl ester etc.
Example as styrene monomer, except that styrene, can enumerate: the ring-alkylated styrenes of methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, diethylbenzene ethene, triethylbenzene ethene, propylstyrene, butylstyrene, hexyl benzene ethene, heptyl benzene ethene, octyl group 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.
Example as the monomer that has a plurality of (methyl) acryloyl group in the molecule, can enumerate: 1,4-butylene glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1 has the monomer of 2 (methyl) acryloyl groups in the molecule of 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; Has the monomer of 3 (methyl) acryloyl groups etc. in the molecule of trimethylolpropane tris (methyl) acrylate and so on.
(methyl) acrylate of formula (I) and the monomer that has beyond the monomer of polar functional group can be used singly or two or more kinds in combination respectively.Be used for the acryl resin of bonding agent (A), relative nonvolatile component 100 weight portions of this resin contain from (methyl) acrylate of formula (I) and have the structural unit of the monomer beyond the monomer of polar functional group with the ratio of common 0~20 weight portion, preferred 0~10 weight portion.
The effective constituent of bonding agent is principal ingredient with the structural unit of aforesaid (methyl) acrylate from formula (I) expression, can comprise the acryl resin that contains more than 2 kinds from the structural unit of the monomer with polar functional group.And then, can in the aforesaid propylene acid resin, mix the acryl resin different, concrete example as having from the structural unit of (methyl) acrylate of formula (I) and not containing acryl resin of polar functional group etc. with it.Be principal ingredient, contain acryl resin from the structural unit of monomer in acryl resin is overall with structural unit with polar functional group from (methyl) acrylate of formula (I), be preferably set to more than the 60 weight %, more preferably more than the 80 weight %.
Be principal ingredient, contain acryl resin from the structural unit of monomer and preferably utilize weight-average molecular weight (Mw) that the polystyrene standard of gel permeation chromatography (GPC) converts with structural unit 1 with polar functional group from (methyl) acrylate of formula (I), 000,000~2,000,000 scope.The weight-average molecular weight that polystyrene standard converts is 1,000,000 when above, cementability under hot and humid improves, and between glass substrate and adhesive phase, produce the possibility of floating or peeling off and tend to step-down, and, re-workability tends to improve, and is therefore preferred.In addition, this weight-average molecular weight is 2,000,000 when following, changes even be pasted on the size of the blooming of this adhesive phase, and adhesive phase also follows this change in size and changes, therefore, do not have difference between the bright degree of the periphery of liquid crystal cells and the bright degree of central part, have the tendency that suppresses whiting or color spot, therefore preferred.With the molecular weight distribution of the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) the expression scope about 2~10 usually.
This acryl resin also can be only be made of the acryl resin of aforesaid higher molecular weight, also can be on the basis of described acryl resin by constituting with the potpourri of the acryl resin different with it.As the acryl resin that can mix use, for example can enumerate with the structural unit from (methyl) acrylate of above-mentioned formula (I) expression be principal ingredient, weight-average molecular weight 50,000~300, the acryl resin of 000 scope.
Acryl resin (situation of combination more than 2 kinds is both potpourris) preferably makes it be dissolved in ethyl acetate and the solution that is adjusted into nonvolatile component concentration 20 weight % shows below the 20Pas down at 25 ℃, further be the viscosity of 0.1~7Pas.The viscosity of this moment is 20Pas when following, and hot and humid cementability down improves, between glass substrate and adhesive phase, produce the possibility of floating or peeling off and tend to step-down, and re-workability tends to improve, so preferably.Viscosity can utilize rich reining in to fly viscosity meter and measure.
The acryl resin that constitutes adhesive phase for example can utilize known the whole bag of tricks such as solution polymerization process, emulsion polymerization, mass polymerization, suspension polymerization to make.In the manufacturing of this acryl resin, use polymerization initiator usually.Polymerization initiator is used for total 100 weight portions of whole monomers of the manufacturing of acryl resin relatively, uses about 0.001~5 weight portion.
As polymerization initiator, use thermal polymerization or Photoepolymerizationinitiater initiater etc.As Photoepolymerizationinitiater initiater, can enumerate for example 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone etc.As thermal polymerization, for example can enumerate 2,2 '-azoisobutyronitrile, 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (cyclohexane-1-nitrile), 2,2 '-azo two (2, the 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-methylol propionitrile) 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 of potassium persulfate, ammonium persulfate, hydrogen peroxide and so on etc.Also can be used as polymerization initiator in addition, and with redox system initiating agent of superoxide and reductive agent etc.
As the manufacture method of acryl resin, in the method shown in above, the preferred solution polymerization.When the concrete example of enumerating solution polymerization process describes, can enumerate target monomer and organic solvent are mixed, under nitrogen atmosphere, add thermal polymerization, about 40~90 ℃, preferred about 60~80 ℃ stir method about 3~10 hours etc.In addition,, can in polymerization, add monomer or thermal polymerization continuously or off and on, or add being dissolved under the state of organic solvent in order to control reaction.At this,, can use the aromatic hydrocarbon based of for example toluene, dimethylbenzene and so on as organic solvent; The ester class of ethyl acetate, butyl acetate and so on; The aliphatics alcohols of propyl alcohol, isopropyl alcohol and so on; The ketone of acetone, methyl ethyl ketone, methylisobutylketone and so on etc.
[ionic compound (B)]
In the present invention, on the basis of aforesaid acryl resin (A),, use at the following ionic compound (B) of room temperature (25 ℃) as solid as antistatic agent.This ionic compound (B) has organic cation.In the present invention, at room temperature be called ionic solid for the ionic compound of solid with described sometimes.
Constitute the cation constituent of ionic compound (B) so long as satisfy the organic kation that becomes ionic solid and get final product, except that being not particularly limited it.For example can enumerate: glyoxaline cation, pyridylium, ammonium cation, sulfonium cation, phosphonium cation etc., the situation that is used for the adhesive phase of resin molding, consider preferred pyridylium or glyoxaline cation from when peeling thereon stripping film of setting, being difficult to charged viewpoint.
On the other hand, in ionic compound (B), for the anion component of the counterion of above-mentioned cation constituent so long as satisfy the negative ion that becomes ionic solid and get final product, be not particularly limited, both can be inorganic negative ion, also organic negative ion can be, for example following negative ion can be enumerated.
Chloride anion [Cl
-],
Bromide negative ion [Br
-],
Iodide anion [I
-],
Tetrachloro 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 -],
Acetate negative ion [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 negative ion [(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 phosphinate negative ion [(CH
3)
2POO
-],
(gathering) hydrogen fluorine fluoride anion [F (HF)
n -] (n is about 1~3),
Dicyan amido 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) (trifluoromethyl carbonyl) imines negative ion [(CF
3SO
2) (CF
3CO) N
-] etc.
Wherein, consider the preferred especially anion component that contains fluorine atom that uses, especially preferred hexafluorophosphoric acid salt anionic from the ionic solid aspect of giving excellent antistatic property.
The concrete example that is used for ionic solid of the present invention can suitably 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-octyl group pyridine 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,
The TBuA hexafluorophosphate,
The TBuA tosilate,
(2-hydroxyethyl) trimethyl ammonium dimethyl phosphinate etc.
This ionic solid can be used singly or two or more kinds in combination respectively.The example of ionic solid is not limited to the above material of enumerating.
As mentioned above, at room temperature giving antistatic behaviour for the ionic compound of solid (B) to the adhesive phase that is formed by the composition that contains acryl resin (A), simultaneously, is effective keeping aspect the various rerum naturas of bonding agent.Particularly compare, can keep antistatic property for a long time with using under the normal temperature ionic compound as liquid.When the viewpoint of the long-time stability of this antistatic behaviour was considered, ionic compound (B) preferably had more than 30 ℃, further fusing point more than 35 ℃.On the other hand, poor when its fusing point is too high with the compatibility of acryl resin (A), therefore, preferably have below 90 ℃, further fusing point below 80 ℃.
Nonvolatile component 100 weight portions of aforesaid propylene acid resin (A) (using the situation more than 2 kinds to amount to weight for it) contain ionic compound (B) with the ratio of 0.2~8 weight portion relatively.Relative nonvolatile component 100 weight portions of acryl resin (A), when containing the above ionic compound of 0.2 weight portion (B), antistatic property improves, and is therefore preferred, and in addition, its amount is 8 weight portions when following, keeps permanance easily, so preferably.The amount of the ionic compound (B) of nonvolatile component 100 weight portions of acryl resin (A) also can be set at the scope of 0.2~5 weight portion relatively, is preferably more than 0.5 weight portion, below other 3 weight portions.
[constituting other composition of bonding agent]
In aforesaid acryl resin (A) and ionic compound (B), further cooperate crosslinking chemical (C) usually, make adhesive composition.Crosslinking chemical (C) for have in the molecule at least 2 can with the compound from the crosslinked functional group of the structural unit that particularly contains the polar functional group monomer in the acryl resin (A), particular instantiation isocyanate ester compound, epoxy compounds, metallo-chelate compounds, aziridines compound etc.
Isocyanate ester compound is to have at least 2 isocyanos in the molecule (compound NCO) for example can be enumerated: benzal diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenation of benzene dimethyl diisocyanate, methyl diphenylene diisocyanate, hydrogenated diphenyl methane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate etc.In addition, make the adduct that polyol reactions such as these isocyanate compounds and glycerine or trimethylolpropane generate or make isocyanate compound form dipolymer, trimer etc. and material also can become the crosslinking chemical that is used for bonding agent.Also can be mixed with two or more isocyanate ester compound.
Epoxy compounds is the compound that has at least 2 epoxy radicals in the molecule, for example can enumerate: 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, two (N, N '-diglycidyl amino methyl) cyclohexanes of 3-etc.Also can be mixed with two or more epoxy compounds.
As metallo-chelate, for example can enumerate: coordination has the compound of diacetone or ethyl acetoacetate etc. in polyvalent metals such as aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium.
Aziridines compound is to have at least 2 in the molecule to be called as the compounds that second is embraced 3 yuan of ring skeletons that are made of 1 nitrogen-atoms and 2 carbon atoms of imines, for example can enumerate: diphenyl methane-4,4 '-two (1-aziridine carboxylic acid amides), Toluene-2,4-diisocyanate, 4-two (1-aziridine carboxylic acid amides), triethylene melamines, isophthaloyl be two-1-(2-methylaziridine), three-1-aziridinyl phosphine oxide, hexa-methylene-1, and 6-two (1-aziridine carboxylic acid amides), trimethylolpropanes-three-β-aziridine propionate, tetramethylol methane-three-β-aziridine propionate etc.
In these crosslinking chemicals, preferably use isocyanate ester compound, especially xylylene diisocyanate, benzal diisocyanate or hexamethylene diisocyanate or make these isocyanate compounds and polyol reaction such as glycerine or trimethylolpropane and the adduct that generates or make isocyanate compound form dipolymer, trimer etc. and material potpourri, with the composite material of these isocyanate compounds etc.As preferred isocyanate ester compound, can enumerate: the benzal diisocyanate, make benzal diisocyanate and polyol reaction and the trimer or the hexamethylene diisocyanate of the dipolymer of the adduct that generates, benzal diisocyanate and benzal diisocyanate, make hexamethylene diisocyanate and polyol reaction and the adduct that generates, the dipolymer of hexamethylene diisocyanate and the trimer of hexamethylene diisocyanate.
Acryl resin (A) 100 weight portions (using the situation more than 2 kinds to amount to weight for it) cooperate crosslinking chemical (C) with the ratio about common 0.01~10 weight portion, about preferred 0.1~5 weight portion relatively.With respect to the amount of acryl resin (A) 100 parts by weight of cross-linking agent (C) is that 0.01 weight portion is when above, the permanance of adhesive phase is tended to improve, therefore preferred, in addition, when it is that 10 weight portions are when following, whiting when the blooming of being with bonding agent is applied to liquid crystal indicator becomes not obvious, and is therefore preferred.
When the resin molding of band bonding agent of the present invention is pasted on glass substrate with its adhesive phase side, for the adaptation that makes adhesive phase and glass substrate improves, preferably in being used to form the bonding agent of this adhesive phase, contain silane compound, especially preferably contain silane compound in the acryl resin before cooperating crosslinking chemical.
As silane compound, can enumerate: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, the 3-mercaptopropyl trimethoxysilane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group dimethoxy-methyl silane, 3-glycidoxy propyl group ethoxy dimethylsilane etc.Can use silane compound more than 2 kinds.
Silane compound can be the silane compound of silicone oligomeric.When representing the silicone oligomer, can enumerate for example following material with the form of (monomer) oligomer.
3-mercaptopropyl trimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-mercaptopropyl trimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-mercaptopropyltriethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer that contains the 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 that contains 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 triethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-methacryloxypropyl triethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-methacryloxypropyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-methacryloxypropyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-methacryloxypropyl methyldiethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer that contains methacryloxypropyl of 3-methacryloxypropyl methyldiethoxysilane-tetraethoxy-silicane alkyl copolymer and so on;
3-acryloxy propyl trimethoxy silicane-tetramethoxy-silicane alkyl copolymer,
3-acryloxy propyl trimethoxy silicane-tetraethoxy-silicane alkyl copolymer,
3-acryloxy propyl-triethoxysilicane-tetramethoxy-silicane alkyl copolymer,
3-acryloxy propyl-triethoxysilicane-tetraethoxy-silicane alkyl copolymer,
3-acryloxy propyl group methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-acryloxy propyl group methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-acryloxy propyl group methyldiethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer that contains the acryloxy propyl group of 3-acryloxy propyl group methyldiethoxysilane-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 methyldiethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer that contains vinyl of vinyl methyldiethoxysilane-tetraethoxy-silicane alkyl copolymer and so on;
3-TSL 8330-tetramethoxy-silicane alkyl copolymer,
3-TSL 8330-tetraethoxy-silicane alkyl copolymer,
3-aminopropyltriethoxywerene werene-tetramethoxy-silicane alkyl copolymer,
3-aminopropyltriethoxywerene werene-tetraethoxy-silicane alkyl copolymer,
3-aminopropyl methyl dimethoxysilane-tetramethoxy-silicane alkyl copolymer,
3-aminopropyl methyl dimethoxysilane-tetraethoxy-silicane alkyl copolymer,
3-aminopropyl methyldiethoxysilane-tetramethoxy-silicane alkyl copolymer,
The multipolymer that contains amino of 3-aminopropyl methyldiethoxysilane-tetraethoxy-silicane alkyl copolymer and so on etc.
These silane compounds in most cases are liquid.Nonvolatile component 100 weight portions of the relative acryl resin of the use level of the silane compound in the bonding agent (A) (using the situation more than 2 kinds to amount to weight for it) are generally about 0.01~10 weight portion, preferably use with the ratio of 0.05~5 weight portion.With respect to the amount of the silane compound of nonvolatile component 100 weight portions of acryl resin is 0.01 weight portion when above, and the adaptation of adhesive phase and glass substrate improves, and is therefore preferred.In addition, its amount is 10 weight portions when following, has and suppresses the tendency that silane compound oozes out from adhesive phase, and is therefore preferred.
In the bonding agent of above explanation, can also further cooperate crosslinking catalyst, weather-proof stabilizing agent, bonding agent, plastifier, softening agent, dyestuff, pigment, inorganic filler, acryl resin (A) resin in addition etc.In addition, in bonding agent, cooperate ultra-violet solidified compound, to form the back irradiation ultraviolet radiation and it is solidified, form harder adhesive phase at adhesive phase also be useful.Wherein, if in bonding agent, cooperate crosslinking catalyst with crosslinking chemical, then can prepare adhesive phase by the slaking of short time, and between resin molding and adhesive phase, produce in the resin molding of the band bonding agent that can suppress to obtain to float or peel off or in adhesive phase, produce and bubble, in addition, re-workability is also better sometimes.As crosslinking catalyst, for example can enumerate: the aminated compounds of hexamethylene diamine, ethylenediamine, polyethylene imine based, hexamethylene tetramine, diethylene triamine, trien, isophorone diamine, trimethylene diamines, poly-amino resins, melamine resin and so on etc.When in bonding agent, cooperating the aminated compounds as crosslinking chemical, as crosslinking chemical, the preferred isocyanate compounds.
Constitute under the state of these each compositions in being dissolved in solvent of bonding agent and make adhesive composition, be coated on the suitable base material and make its drying, make adhesive phase.
In the resin molding of band bonding agent of the present invention, the gel fraction that preferably makes adhesive phase is the scope of 50~99 weight %.At this, gel fraction is the value of measuring according to following (I)~(IV).
(I) paste the adhesive phase of about 8cm * about 8cm area and by the metallic screen (its weight is set at Wm) of the SUS304 formation of about 10cm * about 10cm.
(II) weight of the paste that obtained by above-mentioned (I) of weighing is set at Ws with this weight, then, in folding 4 times of the mode that wraps into adhesive phase, after fixing together with stapler (staple gun), carries out weighing, and this weight is set at Wb.
(III) in glass container, put into the sieve that above-mentioned (II) gets up with stapler nail, after adding ethyl acetate 60ml floods, this glass container was at room temperature taken care of 3 days.
(IV) take out sieve from glass container, after under 120 ℃ dry 24 hours, carry out weighing, this weight is set at Wa, divide rate based on the following formula calculated for gel.
Gel fraction (weight %)=[Wa-(Wb-Ws)-Wm}/(Ws-Wm)] * 100
The gel fraction of adhesive phase is 50 weight % when above, and the permanance of adhesive phase is tended to improve, and is therefore preferred, and in addition, its gel fraction is 99 weight % when following, makes easily, therefore preferably.
When the gel fraction of adhesive phase is adjusted into 50~99 weight %, also because of the kind as the acryl resin of the effective constituent of adhesive phase is different, if increase the amount of crosslinking chemical, then gel fraction raises, therefore, adjusting gel fraction according to the amount of crosslinking chemical gets final product.Particularly, scope from about 0.01~10 weight portion suitably selects the use level of the crosslinking chemical of nonvolatile component 100 weight portions (using the situation more than 2 kinds is its total metering) with respect to the acryl resin that constitutes adhesive phase to get final product according to the kind of acryl resin.The gel fraction that more preferably makes adhesive phase be 65 weight % above, more preferably more than the 75 weight %, be below the 95 weight % in addition.
[resin molding of band bonding agent]
The resin molding of band bonding agent of the present invention is provided with the adhesive phase that is formed by aforesaid adhesive composition in the one side at least of resin molding.Resin molding used herein can enumerate contain the blooming that is selected from the film in polarizing coating and the phase retardation film or, be pasted on as the blooming of protected body etc. and to protect its surface to avoid to damage or surface protection film that purpose such as pollution is used etc.
So-called polarizing coating is for having the blooming of the function that penetrates polarized light to incident lights such as natural lights.Polarizing coating has: have the character of rectilinearly polarized light that absorbs vibration plane and the rectilinearly polarized light that transmission has perpendicular vibration plane with certain direction the straight line polarizing coating, have reflection have the character of the rectilinearly polarized light of vibration plane of certain direction and the rectilinearly polarized light that transmission has perpendicular vibration plane polarized light separation membrane, be laminated with the elliptic polarization film of polarizing coating and phase retardation film described later etc.As the preferred concrete example of polarizing coating, particularly straight line polarizing coating (being sometimes referred to as polaroid or polarizer membrane), can be set forth in the polarizing coating of dichromatism pigments such as absorption iodine or dichroic dye in the polyvinyl alcohol resin film that uniaxial tension becomes and orientation.
So-called phase retardation film, be the anisotropic blooming of display optical, can enumerate for example by being stretched to stretched film that obtains about 1.01~6 times etc. by the polymeric membrane that 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. constitute.Wherein, the polymeric membrane of preferred uniaxial tension or biaxial stretch-formed polycarbonate membrane or cyclic polyolefin hydro carbons film.The film that is called as single shaft phase retardation film, wide viewing angle phase retardation film, low light elastic modulus phase retardation film etc. is arranged, and any can be suitable for.
In addition, the coating by liquid crystal compounds, orientation manifest optically anisotropic film or the coating by inorganic layered compounds and manifest optically anisotropic film and also can be used as phase retardation film.This phase retardation film has: the film that is called as the temperature compensating type phase retardation film, or by the film of Shin Nihon Oil Co., Ltd with the rod shaped liquid crystal twisted-oriented one-tenth of the trade name sale of " LC film ", equally by the film of Shin Nihon Oil Co., Ltd with the rod shaped liquid crystal tilted alignment one-tenth of the trade name sale of " NH film ", the film that the discoid liquid crystal tilted alignment of being sold with the trade name of " WV film " by Fuji Photo Film Co., Ltd. becomes, by the film of Sumitomo Chemical Co with the complete biaxial orienting type of the trade name sale of " VAC film ", the film of the biaxial orienting type of selling with the trade name of " new VAC film " by Sumitomo Chemical Co etc. equally.
And then the film that is pasted with diaphragm on these bloomings also can be used as blooming.As diaphragm; use transparent resin molding; as this transparent resin, for example can enumerate with Triafol T or cellulose diacetate and be the cellulose acetate resinoid of representative, be methacrylic resin, vibrin, polyolefin resin, polycarbonate resin, polyether-ether-ketone resin, polysulfone resin of representative etc. with the polymethylmethacrylate.Can in the resin that constitutes diaphragm, cooperate ultraviolet light absorbers such as bigcatkin willow acid esters compound, benzophenone compound, benzotriazole compound, compound in triazine class, cyanoacrylate compound, nickel complex salt compounds.As diaphragm, preferably use cellulose acetate resin films such as three cellulose acetate membrane.
In the blooming of above explanation, the straight line polarizing coating is many to be used with the state of pasting diaphragm at the one or both sides of the polaroid that constitutes it, the polarizer membrane that for example is made of polyvinyl alcohol resin.In addition, above-mentioned elliptic polarization film is the film that is laminated with straight line polarizing coating and phase retardation film, and this polarizing coating also uses with the state of pasting diaphragm at the one or both sides of polarizer membrane mostly.When on this elliptic polarization film, forming adhesive phase of the present invention, form adhesive phase in its phase retardation film side usually.
So-called surface protection film; for avoiding damaging or pollute as the surface of the blooming of protected body etc. with protection is the film that purpose is used; polarizing coating, phase retardation film, the light that for example is used for the production of liquid crystal indicator expands penetrates various bloomings such as sheet, reflector plate usually (to have the situation of adhesive phase in one side on its surface; for being in the face of opposition side with this adhesive phase) the state circulation of adhesive surface diaphragm; after making it be pasted on liquid crystal cells etc., peel off and remove this surface protection film.As the base material of surface protection film, for example can enumerate: the polyolefin resin of tygon, polypropylene, polymethylpentene and so on; The fluorinated polyolefin resinoid of polyvinyl fluoride base, Kynoar, polyvinyl fluoride and so on; The polyester based resin of PEN, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate/m-phthalic acid ester copolymer 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 till its adhesive layer surface stickup stripping film is when using, carry out temporary protection.Stripping film used herein can be for for example being set at base material by the film that various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate constitute and the film that gets that the demoulding of silicone-treated and so on handles etc. being implemented on composition surface this base material and adhesive phase.
The resin molding of band bonding agent can utilize for example following method manufacturing, that is, the adhesive composition that coating illustrates previously on aforesaid stripping film forms adhesive phase, the method for further laminated resin film on the adhesive phase that obtains; Applying adhesive composition on resin molding forms adhesive phase, pastes stripping film and protect on this bonding agent face, makes the method for the resin molding of being with bonding agent etc.
The thickness of adhesive phase is not particularly limited, and preferably is generally below the 30 μ m, in addition, is preferably more than the 10 μ m, more preferably 10~20 μ m.The thickness of adhesive phase is that 30 μ m are when following, cementability under hot and humid improves, between glass substrate and adhesive phase, produce the possibility of floating or peeling off and tend to step-down, and, re-workability tends to improve, therefore preferred, in addition, its thickness is 10 μ m when above, changes even paste the size of blooming thereon, and bonding coat also follows this change in size and changes, therefore, do not have difference between the bright degree of the periphery of liquid crystal cells and the bright degree of central part, have the tendency that suppresses whiting or color spot, therefore preferred.At present, the thickness that is pasted on the adhesive phase of liquid crystal cells glass is standard with 25 μ m generally, in the present invention, even be below the 20 μ m with this thickness setting, also brings into 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, there being any unfavorable condition with this resin molding when glass substrate is peeled off, adhesive phase is followed resin molding and is stripped from, produce fuzzy hardly on the surface of the glass substrate that contacts with adhesive phase or paste residual etc., therefore, paste the resin molding of being with bonding agent more again on the glass substrate after peeling off easily.That is so-called re-workability excellence.
[optical laminate]
The resin molding of band bonding agent of the present invention can be the resin molding that comprises blooming, is laminated in glass substrate with its adhesive phase, makes optical laminate.In order to make optical laminate in glass substrate with the resin molding of bonding agent is stacked, for example, peel stripping film from the resin molding of the band bonding agent that obtains as described above, the surface that the adhesive phase that will expose is pasted on glass substrate gets final product.At this,, for example can enumerate as glass substrate: the glass substrate of liquid crystal cells, anti-dazzle with glass, sunglasses with glass etc.Wherein, the optical laminate that the blooming (following polarizing coating) of stacked other band bonding agent forms on the blooming (going up polarizing coating) of stacked band bonding agent on the glass substrate of the front face side (identification side) of liquid crystal cells, glass substrate in the rear side of liquid crystal cells can be used as liquid crystal indicator, therefore preferably.As the material of glass substrate, for example can enumerate: soda-lime glass, glass with lower alkali content, alkali-free glass etc.
Optical laminate of the present invention can be as the liquid crystal cells of liquid crystal indicator.
The notebook computer that the liquid crystal indicator that is formed by optical laminate of the present invention can be used to comprise notebook type for example, desk-top, PDA (Personal Digital Assistance) etc. with LCD, televisor, vehicle with display, e-dictionary, digital camera, digital camera, electronic desktop computer, clock and watch etc.
Below, enumerate embodiment and further specifically describe the present invention, but the present invention is not limited by these examples.In the example, expression use amount or content " part " reaches " % ", unless otherwise specified, is weight basis just.
In following example, nonvolatile component is to use the value of measuring according to the method for JIS K 5407.Particularly, put into binder solution to water glass with cover, be shown in the residual nonvolatile component weight after making its dry 2 hours under 115 ℃ in the explosion-proof baking oven with schedule of proportion with the weight of the solution of initial measurement with any weight.In addition, the mensuration of weight-average molecular weight is following carries out, promptly, " the TSK gel GMHHR-H (S) " of configuration 2 Gen East ソ one system that is connected in series in the GPC device is as chromatographic column, use tetrahydrofuran as dissolution fluid, under sample solution concentration 5mg/ml, sample import volume 100 μ l, 40 ℃ of temperature, flow velocity 1ml/ minute condition, convert by polystyrene standard and to carry out.
At first, the Production Example of illustration acryl resin.
[polymerization example 1]
Take into account the mixed solution that adds 0.4 part in 81.8 parts of ethyl acetates, 98.6 parts of butyl acrylates, 1.0 parts of acrylic acid 2-hydroxyl ethyl esters and acrylic acid in the reaction vessel of stirring machine having cooling tube, nitrogen ingress pipe, temperature, one side is with the air in the nitrogen replaceable equipment and be set at oxygen-free, on one side internal temperature is risen to 55 ℃.Thereafter, total amount is added the solution that makes 0.14 part of azoisobutyronitrile (polymerization initiator) be dissolved in 10 parts of ethyl acetates and form.After initiating agent adds 1 hour, be that 35% mode adds ethyl acetate continuously with 17.3 parts/hr of interpolation speed in reaction vessel on one side with the concentration of the acryl resin of removing monomer, be incubated 12 hours down for 54~56 ℃ at internal temperature on one side, at last, add ethyl acetate and regulate, so that the concentration of acryl resin is 20%.It is 1,230,000 that the acryl resin that obtains utilizes the weight-average molecular weight Mw of the polystyrene conversion of GPC, and Mw/Mn is 3.9.Be set and be acryl resin A1.The structural unit from as the acrylic acid 2-hydroxyl ethyl ester of hydroxyl monomer among the acryl resin A1 is 1%, in addition, and from being 0.4% as the acrylic acid structural unit that contains carboxylic monomer.
[polymerization example 2]
Monomer formed change to 0.4 part in 81.8 parts of ethyl acetates, 78.6 parts of butyl acrylates, 20.0 parts of methyl acrylates, 1.0 parts of acrylic acid 2-hydroxyl ethyl esters and acrylic acid, in addition, similarly operate the manufacturing acryl resin with polymerization example 1.It is 1,648,000 that the acryl resin that obtains utilizes the weight-average molecular weight Mw of the polystyrene conversion of GPC, and Mw/Mn is 4.1.Be set and be acryl resin A2.Among the acryl resin A2, be 1%, from being 0.4% as the ratio that contains acrylic acid structural unit of carboxylic monomer from ratio as the structural unit of the acrylic acid 2-hydroxyl ethyl ester of hydroxyl monomer.
The acryl resin of making more than then illustration is used prepares bonding agent and is applied to the embodiment and the comparative example of blooming.In following example, use following compound as ionic compound.The mark of each compound is the mark additional in order to be used for reference in the back, and the compound that is called ionic solid 1~ionic solid 5 is solid under 25 ℃ room temperature, and the compound that is called ionic solid 1 is liquid under 25 ℃ room temperature.
Ionic solid 1:N-butyl-4-picoline hexafluorophosphoric acid ester (structure with following formula, 48 ℃ of fusing points)
Ionic solid 2:N-hexyl pyridine hexafluorophosphoric acid ester (structure with following formula, 45 ℃ of fusing points)
Ionic solid 3:N-octyl group-4-picoline hexafluorophosphoric acid ester (structure with following formula, 44 ℃ of fusing points)
Ionic solid 4:1-methyl-3-ethyl imidazol(e) hexafluorophosphoric acid ester (structure with following formula, 62 ℃ of fusing points)
Ionic solid 5: TBuA hexafluorophosphoric acid ester (structure with following formula, 78 ℃ of fusing points)
Ionic liquid 1:N-hexyl-4-picoline hexafluorophosphoric acid ester (structure with following formula, 18 ℃ of fusing points)
In addition, as crosslinking chemical and silane compound, use following compound (all being trade name).
(crosslinking chemical)
タ ケ ネ one ト D160N: the ethyl acetate solution of the trimethylolpropane adduct of hexamethylene diisocyanate (solid component concentration 75%), obtain from Mitsui Chemical Polyurethane Co., Ltd.
コ ロ ネ one ト L: the ethyl acetate solution of the trimethylolpropane adduct of benzal diisocyanate (solid component concentration 75%), obtain from Japanese polyurethane Co., Ltd..
(silane compound)
KBE-402: glycidoxy propyl group diethoxymethyl silane (liquid), obtain from Shin-Etsu Chemial Co., Ltd.
KBM-403: glycidoxypropyltrime,hoxysilane (liquid), obtain from Shin-Etsu Chemial Co., Ltd.
[embodiment 1~5 and comparative example 1~3]
(a) manufacturing of bonding agent
Relatively the solid constituent of the acryl resin A1 that is obtained by polymerization example 1 is 100 parts, to count 0.8 part crosslinking chemical " タ ケ ネ one ト D160N ", 0.5 part of silane compound " KBE-402 " and mix with the ionic compound shown in the table 1 of the amount shown in the table 1 respectively by solid constituent, be that 13% mode is added ethyl acetate further, make adhesive composition with solid component concentration.
[table 1]
(b) making of the resin molding of band bonding agent
The polyethylene terephthalate film of handling in the demoulding (trade name " PET 3811 ", obtains from リ Application テ Star Network Co., Ltd.; Be called spacer) demoulding treated side, using applicator is that the mode of 15 μ m applies above-mentioned each adhesive composition with dried thickness, makes its dry 1 minute under 90 ℃, obtains the bonding agent of sheet.Then; utilize stacked machine make with the spacer of the sheet bonding agent that obtains above be in opposition side face (bonding agent face), paste with the one side of the polarizing coating of the 3-tier architecture on the two sides of the polyvinyl alcohol (PVA) polaroid of using the diaphragm clamping absorption iodine that constitutes by Triafol T and orientation; then; slaking is 7 days under the condition of 23 ℃ of temperature, relative humidity 65%, obtains the resin molding with bonding agent.About each adhesive phase after the slaking, measure gel fraction with the method for narrating previously, it be the results are shown in table 2.
(c) the antistatic behaviour evaluation of the resin molding of band bonding agent
When the spacer of the band bonding agent polarizing coating of peeling off gained,, estimate antistatic behaviour with the sheet resistance value of surperficial intrinsic resistance determinator [" Hirest-up MCP-HT450 " (trade name) of Mitsubishi chemical Co., Ltd's system] mensuration bonding agent.If sheet resistance value is 10
11Ω/ level or below it 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 finishes.In addition, the timeliness when observing long-time preserve changes, and the keeping in the baking oven of 60 ℃ of temperature, relative humidity 70% of the polarizing coating of the band bonding agent after slaking is finished with the above-mentioned spacer of similarly peeling off, was measured the sheet resistance value of bonding agent after 6 days.At this, in the time of 6 days, can obtain and at room temperature take care of 6 months roughly the same effects in 60 ℃ of temperature, 70% time keeping of relative humidity.To the results are summarized in table 2.
(d) making of optical laminate and evaluation
After peeling spacer from the polarizing coating of the band bonding agent made by above-mentioned (b), its bonding agent face is pasted on the one side of liquid crystal cells with glass substrate [" 1737 " (trade name) of コ one ニ Application グ society system], makes optical laminate.About optical laminate, respectively to the situation of carrying out under the drying condition of 80 ℃ of temperature 300 hours heat resistant test of keeping, carry out the situation of 60 ℃ of temperature, 300 hours hot resistance test of 90% time keeping of relative humidity and will be cooled to from the state that is heated to 70 ℃-30 ℃, then be warming up to 70 ℃ process as 1 circulation (1 hour), carry out it is repeated the situation of 100 round-robin heatproof impact tests, the optical laminate after visualization is tested.The result is classified with following benchmark, be summarized in table 2.
(to the Evaluation of Durability benchmark of hot, damp and hot and thermal shock (note is made " HS " in table 2))
◎: do not see fully float, peel off, appearance change such as foaming.
Zero: almost do not see float, peel off, appearance change such as foaming.
△: float, peel off, appearance change such as foaming is remarkable a little.
*: see significantly float, peel off, appearance change such as foaming.
[embodiment 6]
Relatively the solid constituent of the acryl resin A2 that is obtained by polymerization example 2 is 100 parts, to count 0.5 part and 7.5 parts ionic solids 3 mixing of crosslinking chemical " コ ロ ネ one ト L ", silane compound " KBM-403 " of 0.5 part by solid constituent, be that 13% mode is added ethyl acetate further, make adhesive composition with solid component concentration.Use this adhesive composition to carry out the evaluation same, will the results are summarized in table 2 with embodiment 1~5.
[table 2]
* the state 25 of the ionic compound of Shi Yonging ℃ the time
Learn by table 1 and table 2, acryl resin is 100 parts relatively, cooperate 1 part of the ionic solid of stipulating among the present invention and constitute the embodiment 1~5 of bonding agent and cooperate 7.5 parts of ionic solids and constitute the embodiment 6 of bonding agent, compare with the comparative example 1 that is combined with ionic liquid, manifest equal antistatic behaviour at the making initial stage, simultaneously, even long-time the placement, antistatic behaviour also changes hardly, in addition, aspect thermotolerance, humidity resistance and resistance to sudden heating, also can obtain roughly satisfied result.
With respect to this, N-hexyl-4-picoline hexafluorophosphoric acid ester (ionic liquid 1) for liquid under being engaged in 25 ℃ constitutes the comparative example 1 of bonding agent, though manifest good antistatic behaviour at the making initial stage, but, promoting 70% time keeping of 60 ℃ of temperature, relative humidity of test in the time of 6 days as heating, the sheet resistance value after spacer is peeled off and the value at initial stage are in a ratio of more than 10 times, see the tendency that antistatic behaviour weakens because of long-term keeping.By cooperating identical ionic solid 3 but it measures the result of altered embodiment 3, comparative example 2 and comparative example 3, if the use level with respect to the ionic solid of 100 parts of acryl resins is 0.1 part, the effect of then giving antistatic behaviour is insufficient, in addition, when its amount is 10 parts, show the inadequate result of permanance.
Utilizability on the industry
Resin molding with adhesive of the present invention can suppress the charged of optical component effectively. And then, even long-time keeping after making also can keep the antistatic behaviour at initial stage.
This provides the liquid crystal display optical laminate with the glass substrate of resin molding by for example being consisted of resin molding and be laminated in liquid crystal cells by blooming of adhesive. The adhesive phase of this optical laminate absorbs, relaxes the stress that the change in size of blooming and glass substrate causes under wet heat condition, therefore, can alleviate local stress and concentrate, and suppresses floating or peel off etc. with respect to the adhesive phase of glass substrate. In addition, the optical defect that inhomogeneous stress distribution causes can be prevented, therefore, whiting can be suppressed. And then, in case will be stacked behind glass substrate with the resin molding of adhesive, exist in any bad situation, even this resin molding is peeled off from glass substrate with adhesive, also seldom generation paste in the surface of the glass substrate after peeling off is residual or fuzzy, can again be used as glass substrate, be the film of re-workability excellence.
In addition, this also can be pasted on the surface of blooming with the resin molding of adhesive, makes until its surperficial surface protection film of protection when using. At this moment, also given excellent antistatic effect, for example, can make blooming is pasted on liquid crystal cells via the adhesive phase that is in opposition side with surface protection film after, the static that produces when peeling this surface protection film diminishes.
Resin molding with adhesive of the present invention has been endowed high antistatic behaviour, simultaneously, can keep for a long time this antistatic behaviour, and in addition, durability is also excellent. This resin molding with adhesive consists of resin molding by blooming, can be preferred for liquid crystal indicator. In addition, this resin molding with adhesive also is preferably used as the surface protection film on the surface of protection blooming.
Claims (6)
1. resin molding with bonding agent, wherein,
The resin molding of described band bonding agent is formed with adhesive phase in the one side at least of resin molding, this adhesive phase is formed by following composition, described composition contains (A) to be acryl resin 100 weight portions of principal ingredient with the structural unit from (methyl) acrylate shown in the following formula (I) and (B) to have an organic cation and at room temperature be ionic compound 0.2~8 weight portion of solid
In the formula, R
1Expression hydrogen atom or methyl, R
2The alkyl or the aralkyl of expression carbon number 1~14 are perhaps respectively by the alkyl or the aralkyl of the carbon number 1~14 of the alkoxy of carbon number 1~10 replacement.
2. the resin molding of band bonding agent according to claim 1, wherein,
With respect to acryl resin (A) 100 weight portions, ionic compound (B) exists with the ratio of 0.2~3 weight portion.
3. the resin molding of band bonding agent according to claim 1 and 2, wherein,
Resin molding is to contain the blooming that is selected from the film in polarizing coating and the phase retardation film.
4. the resin molding of band bonding agent according to claim 1 and 2, wherein,
Resin molding is a surface protection film.
5. the resin molding of band bonding agent according to claim 1, wherein,
Surface at adhesive phase is pasted with stripping film.
6. an optical laminate is characterized in that,
The resin molding of the described band bonding agent of claim 3 is laminated in glass substrate in its adhesive phase side and forms.
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PCT/JP2008/065791 WO2009031548A1 (en) | 2007-09-03 | 2008-08-27 | Resin film with adhesive and optical laminate using the same |
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JP2023146370A (en) * | 2022-03-29 | 2023-10-12 | 日東電工株式会社 | Optical pressure sensitive adhesive sheet |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1727426A (en) * | 2004-07-26 | 2006-02-01 | 日东电工株式会社 | Adhesive composition, adhesive sheets, and surface protecting film |
WO2006137559A1 (en) * | 2005-06-24 | 2006-12-28 | Toyo Ink Manufacturing Co., Ltd. | Antistatic acrylic pressure-sensitive adhesive |
Family Cites Families (5)
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 |
TW200420703A (en) * | 2002-11-25 | 2004-10-16 | Sumitomo Chemical Co | Acrylic resin composition, adhesive comprising the composition, and optical laminate comprising the adhesive |
JP5030251B2 (en) * | 2004-07-26 | 2012-09-19 | 日東電工株式会社 | Adhesive composition, adhesive sheet and surface protective film |
WO2006043794A1 (en) * | 2004-10-21 | 2006-04-27 | Lg Chem, Ltd. | Acrylic pressure sensitive adhesive with good antistatic property |
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 |
-
2008
- 2008-05-30 JP JP2008142377A patent/JP5332315B2/en active Active
- 2008-08-27 WO PCT/JP2008/065791 patent/WO2009031548A1/en active Application Filing
- 2008-08-27 KR KR1020107006679A patent/KR101532104B1/en active IP Right Grant
- 2008-08-27 CN CN200880105125.3A patent/CN101828134B/en active Active
- 2008-08-29 TW TW097133062A patent/TWI529230B/en active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1727426A (en) * | 2004-07-26 | 2006-02-01 | 日东电工株式会社 | Adhesive composition, adhesive sheets, and surface protecting film |
WO2006137559A1 (en) * | 2005-06-24 | 2006-12-28 | Toyo Ink Manufacturing Co., Ltd. | Antistatic acrylic pressure-sensitive adhesive |
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Also Published As
Publication number | Publication date |
---|---|
CN101828134B (en) | 2015-03-18 |
TW200920811A (en) | 2009-05-16 |
KR20100070336A (en) | 2010-06-25 |
KR101532104B1 (en) | 2015-06-26 |
JP2009079205A (en) | 2009-04-16 |
TWI529230B (en) | 2016-04-11 |
WO2009031548A1 (en) | 2009-03-12 |
JP5332315B2 (en) | 2013-11-06 |
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