WO2015098727A1 - 光学用粘着剤、光学用粘着テープ及び積層体 - Google Patents
光学用粘着剤、光学用粘着テープ及び積層体 Download PDFInfo
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- WO2015098727A1 WO2015098727A1 PCT/JP2014/083660 JP2014083660W WO2015098727A1 WO 2015098727 A1 WO2015098727 A1 WO 2015098727A1 JP 2014083660 W JP2014083660 W JP 2014083660W WO 2015098727 A1 WO2015098727 A1 WO 2015098727A1
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- C09J133/10—Homopolymers or copolymers of methacrylic acid 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
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2405/00—Adhesive articles, e.g. adhesive tapes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/208—Touch screens
Definitions
- the present invention relates to an optical pressure-sensitive adhesive that does not become cloudy even after being exposed to high temperature and high humidity, has excellent foam resistance and workability, and does not deteriorate a transparent electrode made of ITO or the like. Moreover, this invention relates to the optical adhesive tape and laminated body which were manufactured using this optical adhesive.
- the adhesive used for optical applications is used, for example, when a display, a touch panel, or the like is bonded to a module housing in a portable information terminal. Since the display screen is required to be clear, an adhesive that does not cloud even after being exposed to high temperature and high humidity is desired.
- outgas is generated from the adherend when exposed to high temperature and high humidity, and bubbles may be formed on the adhesion surface with the adherend. Since such bubbles cause a deterioration in the clarity of the display screen, it is also desired that the adhesive has excellent foam resistance.
- Patent Document 1 describes an adhesive tape mainly composed of a polyacrylate ester obtained by polymerizing a polymerizable monomer containing an acrylic monomer having a bicyclo ring by a free radical polymerization method. It is described that it is not easily clouded even after being exposed to moisture, is easy to process, and exhibits an excellent effect of suppressing bubbles on the adhesive surface.
- a transparent electrode made of tin-doped indium oxide (ITO) or the like may be deteriorated.
- the pressure-sensitive adhesive having further excellent performance, in particular, it is not cloudy even after being exposed to high temperature and high humidity even when used for a thin pressure-sensitive adhesive tape as recently requested, and has excellent foam resistance.
- a pressure-sensitive adhesive suitable for optical applications having excellent processability is desired.
- the present invention provides an optical pressure-sensitive adhesive that does not become cloudy even after being exposed to high temperature and high humidity, has excellent foam resistance and workability, and does not deteriorate a transparent electrode made of ITO or the like. Objective. Moreover, an object of this invention is to provide the optical adhesive tape and laminated body which were manufactured using this optical adhesive.
- the present invention includes a) 60 to 95 parts by weight of an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms, b) 0.1 to 1 part by weight of a carboxyl group-containing monomer, and c) a hydroxyl group and an amino group.
- a (meth) acrylic polymer having a molecular weight distribution (Mw / Mn) of 1.05 to 2.5 obtained by copolymerizing a monomer mixture containing 10 to 30 parts by weight of an amide group-containing monomer by living radical polymerization, and a crosslinking agent A) an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms is an optical pressure-sensitive adhesive containing a (meth) acrylate having a bicyclo ring structure.
- polymers obtained by polymerizing radically polymerizable monomers such as (meth) acrylic monomers by “free radical polymerization” are generally used.
- free radical polymerization cannot sufficiently control the molecular weight, molecular weight distribution, copolymer composition, etc., and has the disadvantage that a low molecular weight component is produced or a homopolymer is produced even in the case of copolymerization. is there.
- the present inventors have found that such a low molecular weight component or homopolymer causes the pressure-sensitive adhesive to become cloudy after being exposed to high temperature and high humidity, causes bubbles on the adhesive surface, and deteriorates workability. I thought.
- Living radical polymerization is a polymerization in which a molecular chain grows without being hindered by a side reaction such as a termination reaction or a chain transfer reaction, so that it is easy to control the molecular weight and molecular weight distribution, copolymer composition, etc. Generation of a low molecular weight component and formation of a homopolymer that occurs without copolymerization can be suppressed. Furthermore, by adopting living radical polymerization, a sufficient cohesive force can be secured even if the amount of the carboxyl group-containing monomer is reduced, and the polymer chain containing the free carboxyl group-containing monomer can be reduced. Can be prevented.
- the present inventors specified a specific blending ratio of a) an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms, b) a carboxyl group-containing monomer, and c) a hydroxyl group, amino group or amide group-containing monomer. Containing a (meth) acrylic polymer having a molecular weight distribution (Mw / Mn) in a specific range and a cross-linking agent obtained by copolymerizing a monomer mixture containing the above by living radical polymerization, and a) an alkyl having 1 to 14 carbon atoms.
- Mw / Mn molecular weight distribution
- the alkyl (meth) acrylate having a group is an optical pressure-sensitive adhesive containing a (meth) acrylate having a bicyclo ring structure, it is not cloudy even after being exposed to high temperature and high humidity, and has excellent foam resistance and processability. And it discovered that the transparent electrode which consists of ITO etc. was not deteriorated, and came to complete this invention.
- the optical pressure-sensitive adhesive of the present invention comprises a) 60 to 95 parts by weight of an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms, b) 0.1 to 1 part by weight of a carboxyl group-containing monomer, and c).
- (Meth) acrylic having a molecular weight distribution (Mw / Mn) of 1.05 to 2.5 obtained by copolymerizing a monomer mixture containing 10 to 30 parts by weight of a hydroxyl group, amino group or amide group-containing monomer by living radical polymerization Contains polymer.
- (meth) acrylate means an acrylate and a methacrylate.
- the monomer mixture contains 60 to 95 parts by weight of a) an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms
- the cohesive force, initial adhesiveness, adhesion, etc. of the optical pressure-sensitive adhesive are improved.
- the preferable lower limit of the content of the a) alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms in the monomer mixture is 70 parts by weight, and the preferable upper limit is 90 parts by weight.
- the a) alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms includes (meth) acrylate having a bicyclo ring structure.
- the bicyclo ring structure is not particularly limited, and examples of the functional group having the bicyclo ring structure include a bicyclo [1.1.0] butyl group, a bicyclo [1.1.1] pentyl group, and a bicyclo [2.1.
- a functional group having a structure substituted with a group may be one place and may be multiple places.
- a norbornyl group and an isobornyl group are preferable, and an isobornyl group is particularly preferable. That is, the (meth) acrylate having the bicyclo ring structure is particularly preferably isobornyl (meth) acrylate having an isobornyl group and a (meth) acryloyl group.
- the (meth) acrylate having the bicyclo ring structure is preferably 5 to 55 parts by weight.
- the blending ratio of the (meth) acrylate having a bicyclo ring structure is more preferably 7 to 40 parts by weight.
- alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms other than the (meth) acrylate having the bicyclo ring structure the alkyl group having 1 to 14 carbon atoms may be a long chain or a branched chain. Or it may be annular.
- alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl.
- the (meth) acrylate which has cyclic alkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, is also mentioned.
- an optical pressure-sensitive adhesive having a low low-temperature elastic modulus and high initial wettability is obtained, it is selected from the group consisting of 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate and butyl (meth) acrylate. At least one of these is preferred.
- the b) carboxyl group-containing monomer is contained in the monomer mixture, whereby the cohesive force and the like of the optical pressure-sensitive adhesive are improved.
- Examples of the b) carboxyl group-containing monomer include (meth) acrylic acid, phthalic acid, terephthalic acid, pyromellitic acid, and the like. Of these, acrylic acid is preferred.
- the blending ratio of the above b) carboxyl group-containing monomer in the monomer mixture is less than 0.1 parts by weight, the cohesive force of the optical pressure-sensitive adhesive is easy to peel off, and air bubbles are easily generated on the adhesive surface. The processability of the pressure-sensitive adhesive tape produced using the optical pressure-sensitive adhesive is also lowered.
- the blending ratio of the above b) carboxyl group-containing monomer exceeds 1 part by weight, a transparent electrode made of ITO or the like may be deteriorated when used for an electronic component.
- the gel fraction of the optical pressure-sensitive adhesive becomes too high, and is easily peeled off after being exposed to high temperature and high humidity. Air bubbles are likely to be generated at the adhesive interface, and the foam resistance is likely to be lowered.
- the c) hydroxyl group, amino group or amide group-containing monomer is contained in the monomer mixture, so that the optical pressure-sensitive adhesive can be prevented from being clouded after being exposed to high temperature and high humidity.
- examples of the hydroxyl group-containing monomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, one terminal And polyethylene glycol modified with an acryloyl group, and polypropylene glycol modified at one end with an acryloyl group. Of these, hydroxyethyl acrylate is preferred.
- Examples of the amino group-containing monomer include dimethylamino (meth) acrylate, diethylamino (meth) acrylate, aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and the like. Of these, dimethylaminoethyl (meth) acrylate is preferred.
- Examples of the amide group-containing monomer include diacetone acrylamide (diacetone acrylamide), N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N-hydroxyethylacrylamide, acrylamide, and methacrylamide. Can be mentioned. Of these, diacetone acrylamide is preferable.
- hydroxyl group, amino group or amide group-containing monomer may be used alone or in combination of two or more. When using 2 or more types together, it is preferable to use combining a hydroxyl group containing monomer and an amino group or an amide group containing monomer.
- the optical pressure-sensitive adhesive tends to become cloudy after being exposed to high temperature and high humidity.
- the mixing ratio of the above-mentioned c) hydroxyl group, amino group or amide group-containing monomer exceeds 30 parts by weight, the viscosity at the time of coating becomes too high to be coated, and the thickness unevenness of the coated optical pressure-sensitive adhesive May occur.
- the monomer mixture includes, in addition to a) an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms, b) a carboxyl group-containing monomer, and c) a hydroxyl group, amino group or amide group-containing monomer. You may contain the monomer copolymerizable with these.
- the copolymerizable monomer is not particularly limited, and examples thereof include (meth) acrylic acid esters and vinyl compounds.
- the (meth) acrylic acid ester is not particularly limited, and is a (meth) acrylic acid alkyl ester such as isomyristyl (meth) acrylate or stearyl (meth) acrylate, benzyl (meth) acrylate, or 2-butoxyethyl (meth) acrylate. 2-phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, polypropylene glycol mono (meth) acrylate and the like. These (meth) acrylic acid esters may be used alone or in combination of two or more.
- the vinyl compound is not particularly limited, and examples thereof include N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylacetamide, N-acryloylmorpholine, acrylonitrile, styrene, vinyl acetate and the like. These vinyl compounds may be used alone or in combination of two or more.
- the (meth) acrylic polymer is a (meth) acrylic polymer obtained by copolymerizing the monomer mixture by living radical polymerization, preferably living radical polymerization using an organic tellurium polymerization initiator.
- Living radical polymerization is a polymerization in which a molecular chain grows without being hindered by a side reaction such as a termination reaction or a chain transfer reaction, so that it is easy to control the molecular weight and molecular weight distribution, copolymer composition, etc. Generation of a low molecular weight component and formation of a homopolymer that occurs without copolymerization can be suppressed.
- the optical pressure-sensitive adhesive of the present invention does not cloud even after being exposed to high temperature and high humidity, and has excellent foam resistance and processability. It will be.
- living radical polymerization it is possible to secure a sufficient cohesion even if the amount of the carboxyl group-containing monomer is reduced, and it is possible to reduce the polymer chain containing the carboxyl group-containing monomer in a free state. Deterioration of the electrode can be prevented.
- FIG. 1 shows a schematic diagram for explaining living radical polymerization.
- Living radical polymerization is polymerization in which molecular chains grow without the polymerization reaction being hindered by side reactions such as termination reactions or chain transfer reactions.
- the reaction proceeds without the growth terminal radicals being deactivated and without generating new radical species during the reaction.
- all polymer chains are polymerized while uniformly reacting with the monomer, and the composition of all polymers approaches uniform. Therefore, the hydroxyl group, amino group or amide group-containing monomer 12 containing a crosslinkable functional group, and the carboxyl group-containing monomer 13 are included in all the polymers of the (meth) acrylic polymer 1 subjected to living radical polymerization.
- FIG. 3 is a schematic diagram for explaining free radical polymerization.
- free radical polymerization radical species are continuously generated during the reaction and added to the monomer, and the polymerization proceeds. Therefore, in the free radical polymerization, a polymer 24 in which the growing terminal radical is deactivated during the reaction and a polymer 25 grown by the radical species newly generated during the reaction are generated. Therefore, when a (meth) acrylic polymer is produced by free radical polymerization, a relatively low molecular weight polymer that does not contain the hydroxyl group, amino group, or amide group-containing monomer 22 containing a crosslinkable functional group is generated.
- FIG. 4 shows a schematic diagram for explaining a case where a free-radically polymerized (meth) acrylic polymer is cross-linked.
- the composition of the polymer is heterogeneous, and it contains a relatively low molecular weight polymer that does not contain a hydroxyl group, amino group, or amide group-containing monomer, and therefore cannot participate in crosslinking.
- a chain is present (in FIG.
- a hydroxyl group is shown as an example of a crosslinkable functional group).
- polymer chains containing free carboxyl group-containing monomers When a free-radically polymerized (meth) acrylic polymer is used, bubbles are formed on the adhesive surface or workability is deteriorated due to a relatively low molecular weight component that is not crosslinked. Moreover, in order to ensure cohesive force, it is necessary to mix
- the living radical polymerization using the organic tellurium polymerization initiator is different from other living radical polymerizations such as carboxyl group, hydroxyl group, epoxy group, amino group, isocyanate group, amide group, nitrile group, etc. Without protecting any monomer having a functional group, a polymer having a uniform molecular weight and composition can be obtained by polymerization with the same initiator. For this reason, the monomer which has such a functional group can be copolymerized easily.
- the organic tellurium polymerization initiator is not particularly limited as long as it is generally used for living radical polymerization, and examples thereof include organic tellurium compounds and organic telluride compounds.
- examples of the organic tellurium compounds include (methylterranyl-methyl) benzene, (1-methylterranyl-ethyl) benzene, (2-methylterranyl-propyl) benzene, 1-chloro-4- (methylterranyl-methyl) benzene, 1-hydroxy- 4- (methylterranyl-methyl) benzene, 1-methoxy-4- (methylterranyl-methyl) benzene, 1-amino-4- (methylterranyl-methyl) benzene, 1-nitro-4- (methylterranyl-methyl) benzene, 1- Cyano-4- (methylterranyl-methyl) benzene, 1-methylcarbonyl-4- (methylterranyl-methyl) benzene, 1-phenylcarbonyl-4- (methylterran
- the methyl terranyl group in these organic tellurium compounds may be an ethyl terranyl group, n-propyl terranyl group, isopropyl terranyl group, n-butyl terranyl group, isobutyl terranyl group, t-butyl terranyl group, phenyl terranyl group, etc.
- These organic tellurium compounds may be used alone or in combination of two or more.
- organic telluride compound examples include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, di-n-butyl ditelluride, di-sec-butyl ditelluride.
- These organic telluride compounds may be used alone or in combination of two or more. Of these, dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, di-n-butyl ditelluride and diphenyl ditelluride are preferable.
- an azo compound as a polymerization initiator for the purpose of acceleration
- the azo compound is not particularly limited as long as it is generally used for radical polymerization.
- 2,2′-azobis isobutyronitrile
- the living radical polymerization method conventionally known methods are used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like.
- solution polymerization boiling point polymerization or constant temperature polymerization
- emulsion polymerization emulsion polymerization
- suspension polymerization bulk polymerization and the like.
- the polymerization solvent is not particularly limited.
- a nonpolar solvent such as hexane, cyclohexane, octane, toluene, xylene, water, methanol, ethanol, propanol, butanol, acetone, Highly polar solvents such as methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, N, N-dimethylformamide can be used. These polymerization solvents may be used alone or in combination of two or more.
- the polymerization temperature is preferably 0 to 110 ° C. from the viewpoint of the polymerization rate.
- the (meth) acrylic polymer has a molecular weight distribution (Mw / Mn) of 1.05 to 2.5.
- Mw / Mn molecular weight distribution
- the molecular weight distribution exceeds 2.5 the low molecular weight components generated in the living radical polymerization increase, so that the optical pressure-sensitive adhesive tends to become cloudy after being exposed to high temperature and high humidity, or bubbles are formed on the adhesive surface.
- a preferable upper limit of the molecular weight distribution is 2.0, and a more preferable upper limit is 1.8.
- the said (meth) acrylic polymer has a preferable lower limit of 100,000 and a preferable upper limit of 2 million of a weight average molecular weight (Mw).
- Mw weight average molecular weight
- the more preferable lower limit of the weight average molecular weight is 200,000.
- the molecular weight distribution (Mw / Mn) is a ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
- a weight average molecular weight (Mw) and a number average molecular weight (Mn) are measured as a polystyrene conversion molecular weight by the gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were obtained by filtering a diluted solution obtained by diluting a (meth) acrylic polymer with tetrahydrofuran (THF) 50 times through a filter. It is measured as polystyrene-reduced molecular weight by the GPC method using the filtrate. In the GPC method, for example, 2690 Separations Model (manufactured by Waters) or the like can be used.
- a preferable lower limit of the content of the (meth) acrylic polymer in the optical pressure-sensitive adhesive of the present invention is 50% by weight, a more preferable lower limit is 70% by weight, and a still more preferable lower limit is 90% by weight.
- the optical pressure-sensitive adhesive of the present invention contains a crosslinking agent.
- a crosslinking agent By appropriately adjusting the type or amount of the crosslinking agent, the gel fraction of the obtained optical pressure-sensitive adhesive can be adjusted.
- the living radical polymerized (meth) acrylic polymer has a uniform composition of all polymers contained and has crosslinkable functional groups such as hydroxyl groups, so that all polymers can participate in crosslinking between polymer chains. . For this reason, excellent foam resistance and workability can be exhibited, and the deterioration of the transparent electrode can be prevented.
- the crosslinking agent is not particularly limited.
- an isocyanate-based crosslinking agent, an aziridine-based crosslinking agent, an epoxy-based crosslinking agent, or a metal chelate-type crosslinking agent is used depending on the type of the crosslinking functional group of the (meth) acrylic polymer. Select and use.
- the (meth) acrylic polymer has a hydroxyl group as a crosslinkable functional group
- the (meth) acrylic polymer can be crosslinked by using, for example, an isocyanate-based crosslinking agent as a crosslinking agent.
- Examples of the isocyanate-based crosslinking agent include Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.), Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd.), and Mytec NY260A (manufactured by Mitsubishi Chemical Corporation).
- the amount of the crosslinking agent is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. Within this range, the gel fraction of the pressure-sensitive adhesive layer can be adjusted to an appropriate range.
- the optical pressure-sensitive adhesive of the present invention may further contain a tackifier resin as long as the transparency is not impaired.
- a tackifier resin examples include a hydrogenated rosin ester resin and a hydrogenated terpene phenol resin.
- optical pressure-sensitive adhesive is, as necessary, within the range not impairing transparency, plasticizer, emulsifier, softener, fine particles, filler, pigment, dye, silane coupling agent, antioxidant, interface. You may contain well-known additives, such as an activator and a wax.
- An optical pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer formed from the optical pressure-sensitive adhesive of the present invention is also one aspect of the present invention.
- the pressure-sensitive adhesive layer preferably has a gel fraction of 70 to 95% by weight.
- the gel fraction is less than 70% by weight, the pressure-sensitive adhesive layer becomes too soft and foaming may occur. If the gel fraction exceeds 95% by weight, the adhesive strength may be insufficient.
- a more preferable lower limit of the gel fraction is 80% by weight, and a more preferable upper limit is 93% by weight.
- the gel fraction is measured as follows. First, an optical pressure-sensitive adhesive tape was cut into a flat rectangular shape of 50 mm ⁇ 100 mm to prepare a test piece. The test piece was immersed in ethyl acetate at 23 ° C. for 24 hours, then taken out from ethyl acetate, Dry under conditions for 1 hour.
- the optical pressure-sensitive adhesive tape of the present invention is not easily peeled even when it is a thin pressure-sensitive adhesive tape, the pressure-sensitive adhesive layer and the substrate described later can be made thin according to the application.
- the thickness of the pressure-sensitive adhesive layer is not particularly limited because it is set depending on the application, but a preferred lower limit is 1 ⁇ m and a preferred upper limit is 100 ⁇ m. When the thickness is less than 1 ⁇ m, the optical pressure-sensitive adhesive tape is likely to be peeled off, and bubbles may be easily generated on the adhesive surface. When the said thickness exceeds 100 micrometers, a thin adhesive tape may not be obtained.
- the more preferable lower limit of the thickness is 25 ⁇ m, and the more preferable upper limit is 75 ⁇ m.
- the optical pressure-sensitive adhesive tape of the present invention may be a support type having a base material or a non-support type having no base material.
- the pressure-sensitive adhesive layer may be formed on one side of the substrate, or the pressure-sensitive adhesive layer may be formed on both sides.
- the base material is not particularly limited as long as it is a transparent base material.
- acrylic resin polyolefin resin, polycarbonate, polyvinyl chloride, acrylonitrile butadiene styrene (ABS) resin, polyethylene terephthalate (PET), polyethylene naphthalate.
- ABS acrylonitrile butadiene styrene
- PET polyethylene terephthalate
- PEN phthalate
- nylon polyurethane
- polyimide polyimide
- the thickness of the substrate is not particularly limited because it is set depending on the use, but for example, in the case of a film substrate, it is preferably 1 to 100 ⁇ m, more preferably 5 to 75 ⁇ m. When the thickness of the substrate is less than 1 ⁇ m, the mechanical strength of the optical pressure-sensitive adhesive tape may be lowered. If the thickness of the substrate exceeds 100 ⁇ m, the optical adhesive tape becomes too stiff and it may be difficult to adhere and adhere together along the shape of the adherend.
- the method for producing the optical pressure-sensitive adhesive tape of the present invention is not particularly limited.
- the (meth) acrylic polymer is mixed with other compounding components such as the tackifying resin and the crosslinking agent as necessary and stirred.
- the pressure-sensitive adhesive solution is prepared, and this pressure-sensitive adhesive solution is applied to a release-treated PET film and dried to form a pressure-sensitive adhesive layer.
- the resulting pressure-sensitive adhesive layer is transferred to one or both sides of the substrate.
- the method of making it adhere, the method of coating and drying directly on a base material, etc. are mentioned.
- a pressure-sensitive adhesive layer formed by applying and drying a pressure-sensitive adhesive solution to a release-treated PET film may be directly used as a non-support type optical pressure-sensitive adhesive tape without a substrate.
- optical pressure-sensitive adhesive of the present invention and the optical pressure-sensitive adhesive tape of the present invention is not particularly limited as long as it is an optical use, but an electronic device (for example, a mobile phone or a portable information terminal) equipped with an image display device or an input device Etc.) and the like.
- the optical pressure-sensitive adhesive of the present invention is used for bonding a surface protection plate and a display when manufacturing an image display device such as a portable information terminal, or manufacturing an input device such as a portable information terminal. It can be used to bond the touch panel and the display together.
- the laminated body in which the said adhesive layer is formed from the optical adhesive of this invention is also one of this invention.
- an optical pressure-sensitive adhesive that does not become cloudy even after being exposed to high temperature and high humidity, has excellent foam resistance and workability, and does not deteriorate a transparent electrode made of ITO or the like. be able to.
- the optical adhesive tape and laminated body manufactured using this optical adhesive can be provided.
- the filtrate was supplied to a gel permeation chromatograph (manufactured by Waters, 2690 Separations Model), GPC measurement was performed under the conditions of a sample flow rate of 1 ml / min, and a column temperature of 40 ° C., and the polystyrene equivalent molecular weight of the polymer was measured. Molecular weight distribution (Mw / Mn) was determined. GPC KF-806L (manufactured by Showa Denko) was used as the column, and a differential refractometer was used as the detector.
- Example 4 In the same manner as in Example 1, after preparing a living radical polymerization polymer (LRP) -containing solution, Maitec NY260A (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 1.5, which is a crosslinking agent, with respect to 100 parts by weight of the solid content of the copolymer After adding parts by weight and stirring, it was coated on a release-treated surface of a release polyethylene terephthalate (PET) film, and dried at 110 ° C. for 10 minutes to remove ethyl acetate, and a 50 ⁇ m thick adhesive A layer was formed. In addition, the release film for protecting an adhesive layer was laminated
- LRP living radical polymerization polymer
- Maitec NY260A manufactured by Mitsubishi Gas Chemical Co., Ltd.
- Comparative Example 5 A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Comparative Example 4 except that the monomers shown in Table 1 were used in the synthesis of the free radical polymerization polymer (FRP).
- FRP free radical polymerization polymer
- the transparent double-sided pressure-sensitive adhesive tape after being exposed to high temperature and high humidity was cut so as to have a planar shape of 45 mm ⁇ 60 mm. Remove one release polyethylene terephthalate film of the cut double-sided adhesive tape, paste a transparent polyethylene terephthalate film to the exposed adhesive layer, then peel the other release polyethylene terephthalate film, and expose the adhesive
- the agent layer was bonded to a slide glass (trade name “S-1214” manufactured by MATSUNAMI) to prepare a test piece having a layer structure of polyethylene terephthalate film / double-sided adhesive tape / slide glass.
- the haze value (%) immediately after preparation of the test piece was measured according to JIS K 7105 using a haze meter, and the test piece was left in a constant temperature and humidity chamber with a temperature of 85 ° C. and a humidity of 85 RH% for 24 hours. The haze value was measured immediately after taking out.
- the ⁇ haze value was calculated by the following formula (2).
- ⁇ Haze value (%) ⁇ Haze value of test piece after standing for 24 hours (%) ⁇ ⁇ ⁇ Haze value immediately after preparation of test piece (%) ⁇ (2) Transparency was evaluated as “transparent” when the ⁇ haze value was 0.3 or less and “white turbidity” when the haze value exceeded 0.3.
- Bubble generation state (foam resistance test)
- the double-sided adhesive tape was cut so as to have a planar shape of 45 mm ⁇ 60 mm.
- One release polyethylene terephthalate film of the cut double-sided pressure-sensitive adhesive tape was peeled off to expose the pressure-sensitive adhesive layer.
- the exposed surface of the double-sided pressure-sensitive adhesive tape was bonded onto the ITO film surface of the ITO-attached film having a thickness of 0.18 mm.
- the other release polyethylene terephthalate film of the double-sided pressure-sensitive adhesive tape is peeled off, the pressure-sensitive adhesive layer is exposed, and the surface of the double-sided pressure-sensitive adhesive tape exposed on a polycarbonate plate (PC board) having a planar shape with a thickness of 2.0 mm was laminated to obtain a laminate in which a double-sided adhesive tape and a film with ITO were laminated in this order on a polycarbonate plate (PC plate).
- the obtained laminate was treated in an autoclave at 23 ° C. and 0.5 MPa for 15 minutes, and then allowed to stand for 500 hours at a temperature of 85 ° C. and a relative humidity (RH) of 85% to obtain a test sample. It was.
- the bubble generation state in the adhesion interface of the obtained test sample was visually observed. “ ⁇ ” indicates that no bubbles of a size of 0.01 mm or more were observed at all, and “x” indicates that 1 to 5 bubbles of a size of 0.01 mm or more were observed per test sample. The bubble generation state was evaluated.
- the double-sided pressure-sensitive adhesive tape was cut so as to have a planar shape of length 40 mm x width 60 mm. Further, two corners adjacent in the width direction were cut into a planar shape having a length of 10 mm from the corner and a size of 10 mm from the corner to obtain a convex tape.
- One release polyethylene terephthalate film of the convex tape was peeled off, and the exposed surface of the convex tape was stuck on polyethylene terephthalate.
- the other release polyethylene terephthalate film of the convex tape was peeled off, and the exposed surface of the convex tape was bonded to the ITO film surface of the ITO film having a planar shape of 40 mm ⁇ width 60 mm.
- membrane surface of an ITO film was obtained.
- the initial resistance value of the obtained conductive film laminate was measured.
- the conductive film laminate was then allowed to stand for 360 hours under high temperature and high humidity at 60 ° C. and a relative humidity of 90 RH%, and then left standing under high temperature and high humidity using an amorphous ITO film (manufactured by Oike Kogyo Co., Ltd.).
- the resistance value of the conductive film laminate was measured.
- the resistance value was measured by placing the terminal of the two-terminal resistance value measuring device on the exposed surface of the ITO film having a size of 10 mm ⁇ 10 mm. From the obtained initial resistance value and the resistance value after standing under high temperature and high humidity, the resistance value change rate (%) was calculated by the following formula.
- Resistance value change rate (%) (resistance value after standing under high temperature and high humidity ⁇ initial resistance value) / initial resistance value ⁇ 100
- an optical pressure-sensitive adhesive that does not become cloudy even after being exposed to high temperature and high humidity, has excellent foam resistance and workability, and does not deteriorate a transparent electrode made of ITO or the like. be able to.
- the optical adhesive tape and laminated body manufactured using this optical adhesive can be provided.
Abstract
Description
以下、本発明を詳述する。
しかしながら、フリーラジカル重合は、分子量及び分子量分布、共重合体組成等を充分に制御できず、低分子量成分が生成したり、共重合の場合であってもホモポリマーが生成したりするという欠点がある。本発明者らは、このような低分子量成分又はホモポリマーが、高温高湿下に晒された後に粘着剤が曇りやすくなったり、接着面に気泡が生じたり、加工性が悪化したりする原因となっていると考えた。また、粘着剤に用いられるポリマーには、粘着剤に凝集力を付与する目的で、(メタ)アクリル酸等のカルボキシル基含有モノマーを配合することが一般的である。本発明者らは、フリーラジカル重合により得られたポリマーでは、カルボキシル基含有モノマーを含むポリマー鎖が遊離した状態で含まれ、これが透明電極を劣化させる原因となっているものと考えた。透明電極の劣化を防止するためには、カルボキシル基含有モノマーの配合量を減らすことが考えられるが、カルボキシル基含有モノマーの配合量を減らすと得られる粘着剤の凝集力を確保できない。
リビングラジカル重合は、重合反応が停止反応又は連鎖移動反応等の副反応で妨げられることなく分子鎖が生長していく重合であるため、分子量及び分子量分布、共重合体組成等を制御しやすく、低分子量成分の生成及び共重合せずに生じるホモポリマーの生成を抑えることができる。更に、リビングラジカル重合を採用することにより、カルボキシル基含有モノマーの配合量を減らしても充分な凝集力を確保できるとともに、遊離状態のカルボキシル基含有モノマー含むポリマー鎖を減らすことができることから、透明電極の劣化を防止することができる。
なお、(メタ)アクリレートとは、アクリレート及びメタクリレートを意味する。
上記ビシクロ環構造は特に限定されず、上記ビシクロ環構造を有する官能基として、例えば、ビシクロ[1.1.0]ブチル基、ビシクロ[1.1.1]ペンチル基、ビシクロ[2.1.0]ペンチル基、ビシクロ[3.1.0]ヘキシル基、ビシクロ[2.1.1]ヘキシル基、ビシクロ[2.2.0]ヘキシル基、ビシクロ[2.2.1]ヘプチル基、ビシクロ[3.1.1]ヘプチル基、ビシクロ[3.2.0]ヘプチル基、ビシクロ[4.1.0]ヘプチル基、ビシクロ[2.2.2]オクチル基、ビシクロ[3.2.1]オクチル基、ビシクロ[3.3.0]オクチル基、ビシクロ[4.1.1]オクチル基、ビシクロ[4.2.0]オクチル基、ビシクロ[5.1.0]オクチル基、ビシクロ[3.2.2]ノニル基、ビシクロ[3.3.1]ノニル基、ビシクロ[4.2.1]ノニル基、ビシクロ[4.3.0]ノニル基、ビシクロ[5.1.1]ノニル基、ビシクロ[5.2.0]ノニル基、ビシクロ[6.1.0]ノニル基、ビシクロ[4.3.1]デシル基、及び、これらのビシクロ環構造を有する官能基の水素原子の一部を鎖状アルキル基又は環状アルキル基で置換した構造を有する官能基等が挙げられる。なお、上記置換は1箇所であってもよく、複数箇所であってもよい。なかでも、ノルボルニル基、イソボルニル基が好ましく、イソボルニル基が特に好ましい。即ち、上記ビシクロ環構造を有する(メタ)アクリレートとしては、イソボルニル基と(メタ)アクリロイル基とを有するイソボルニル(メタ)アクリレートが特に好ましい。
上記b)カルボキシル基含有モノマーとしては、例えば、(メタ)アクリル酸、フタル酸、テレフタル酸、ピロメリット酸等が挙げられる。なかでも、アクリル酸が好ましい。
上記c)ヒドロキシル基、アミノ基又はアミド基含有モノマーのうち、ヒドロキシル基含有モノマーとしては、例えば、ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、片末端をアクリロイル基で変性したポリエチレングリコール、片末端をアクリロイル基で変性したポリプロピレングリコール等が挙げられる。なかでも、ヒドロキシエチルアクリレートが好ましい。
上記アミノ基含有モノマーとしては、例えば、ジメチルアミノ(メタ)アクリレート、ジエチルアミノ(メタ)アクリレート、アミノメチル(メタ)アクリレート、アミノエチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート等が挙げられる。なかでも、ジメチルアミノエチル(メタ)アクリレートが好ましい。
上記アミド基含有モノマーとしては、例えば、ジアセトンアクリルアミド(ダイアセトンアクリルアミド)、N,N-ジメチルアクリルアミド、N,N-ジエチルアクリルアミド、N-イソプロピルアクリルアミド、N-ヒドロキシエチルアクリルアミド、アクリルアミド、メタクリルアミド等が挙げられる。なかでも、ジアセトンアクリルアミドが好ましい。
上記(メタ)アクリル酸エステルは特に限定されず、イソミリスチル(メタ)アクリレート、ステアリル(メタ)アクリレート等の(メタ)アクリル酸アルキルエステルや、ベンジル(メタ)アクリレート、2-ブトキシエチル(メタ)アクリレート、2-フェノキシエチル(メタ)アクリレート、グリシジル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート等が挙げられる。これらの(メタ)アクリル酸エステルは、単独で用いてもよく、2種以上を併用してもよい。
リビングラジカル重合は、重合反応が停止反応又は連鎖移動反応等の副反応で妨げられることなく分子鎖が生長していく重合であるため、分子量及び分子量分布、共重合体組成等を制御しやすく、低分子量成分の生成及び共重合せずに生じるホモポリマーの生成を抑えることができる。このため、上記(メタ)アクリルポリマーを含有することにより、本発明の光学用粘着剤は、高温高湿下に晒された後でも曇らず、耐発泡性に優れ、かつ、加工性にも優れたものとなる。また、リビングラジカル重合を採用することにより、カルボキシル基含有モノマーの配合量を減らしても充分な凝集力を確保できるとともに、遊離状態のカルボキシル基含有モノマーを含むポリマー鎖を減らすことができることから、透明電極の劣化を防止することができる。
リビングラジカル重合は、重合反応が停止反応又は連鎖移動反応等の副反応で妨げられることなく分子鎖が生長していく重合である。リビングラジカル重合では、生長末端ラジカルが失活することなく、また反応中に新しくラジカル種が発生することもなく、反応が進行する。その反応途中では、全てのポリマー鎖が均一にモノマーと反応しながら重合し、全てのポリマーの組成は均一に近づく。そのため、架橋性官能基を含むヒドロキシル基、アミノ基又はアミド基含有モノマー12や、カルボキシル基含有モノマー13は、リビングラジカル重合された(メタ)アクリルポリマー1の全てのポリマーに含まれる。このようなリビングラジカル重合された(メタ)アクリルポリマー1を、架橋剤を用いて架橋すると、ほとんど全てのポリマーがポリマー鎖間の架橋に関与することができる。
図2に、リビングラジカル重合により得られた(メタ)アクリルポリマーを架橋した場合を説明する模式図を示した。リビングラジカル重合により得られた(メタ)アクリルポリマーでは、全てのポリマーの組成は均一であり、架橋性官能基を含むヒドロキシル基、アミノ基又はアミド基含有モノマーを含むことから、すべてのポリマー鎖が架橋に関与している(なお、図2では架橋性官能基の例として水酸基を記載した。)。このように、ほとんど全てのポリマーがポリマー鎖間の架橋に関与することができることから、低分子量成分の生成及び共重合せずに生じるホモポリマーの生成を抑えて、優れた耐発泡性や加工性を発揮することができる。更に、カルボキシル基含有モノマーの配合量を減らしても充分な凝集力を確保できるとともに、遊離状態のカルボキシル基含有モノマーを含むポリマー鎖がほとんど含まれないことから、透明電極の劣化を防止することができる。
図3にフリーラジカル重合を説明する模式図を示した。
フリーラジカル重合では、反応中に連続的にラジカル種が発生してモノマーに付加し、重合が進行する。そのためフリーラジカル重合では、反応の途中で生長末端ラジカルが失活したポリマー24や、反応中に新しく発生したラジカル種により生長したポリマー25が生成する。そのため、(メタ)アクリルポリマーをフリーラジカル重合で製造すると、架橋性官能基を含むヒドロキシル基、アミノ基又はアミド基含有モノマー22を含まない、比較的低分子量のポリマーが生成してしまう。このようなフリーラジカル重合された(メタ)アクリルポリマー2を、架橋剤を用いて架橋しても、ヒドロキシル基、アミノ基又はアミド基含有モノマーを含まないポリマーは、ポリマー鎖間での架橋に関与することができない。
図4に、フリーラジカル重合された(メタ)アクリルポリマーを架橋した場合を説明する模式図を示した。フリーラジカル重合された(メタ)アクリルポリマーでは、ポリマーの組成が不均一であり、ヒドロキシル基、アミノ基又はアミド基含有モノマーを含まない比較的低分子量のポリマーを含むことから、架橋に関与できないポリマー鎖が存在している(なお、図4では架橋性官能基の例として水酸基を記載した。)。また、遊離状態のカルボキシル基含有モノマーを含むポリマー鎖も含まれる。フリーラジカル重合された(メタ)アクリルポリマーを用いた場合には、架橋されない比較的低分子量の成分により、接着面に気泡が生じたり、加工性が悪化したりする。また、凝集力を確保するためには比較的多量のカルボキシル基含有モノマーを配合する必要があり、透明電極の劣化を防止することができない。更に、遊離状態のカルボキシル基含有モノマーを含むポリマー鎖も透明電極の劣化の原因となる。
上記有機テルル化合物として、例えば、(メチルテラニル-メチル)ベンゼン、(1-メチルテラニル-エチル)ベンゼン、(2-メチルテラニル-プロピル)ベンゼン、1-クロロ-4-(メチルテラニル-メチル)ベンゼン、1-ヒドロキシ-4-(メチルテラニル-メチル)ベンゼン、1-メトキシ-4-(メチルテラニル-メチル)ベンゼン、1-アミノ-4-(メチルテラニル-メチル)ベンゼン、1-ニトロ-4-(メチルテラニル-メチル)ベンゼン、1-シアノ-4-(メチルテラニル-メチル)ベンゼン、1-メチルカルボニル-4-(メチルテラニル-メチル)ベンゼン、1-フェニルカルボニル-4-(メチルテラニル-メチル)ベンゼン、1-メトキシカルボニル-4-(メチルテラニル-メチル)ベンゼン、1-フェノキシカルボニル-4-(メチルテラニル-メチル)ベンゼン、1-スルホニル-4-(メチルテラニル-メチル)ベンゼン、1-トリフルオロメチル-4-(メチルテラニル-メチル)ベンゼン、1-クロロ-4-(1-メチルテラニル-エチル)ベンゼン、1-ヒドロキシ-4-(1-メチルテラニル-エチル)ベンゼン、1-メトキシ-4-(1-メチルテラニル-エチル)ベンゼン、1-アミノ-4-(1-メチルテラニル-エチル)ベンゼン、1-ニトロ-4-(1-メチルテラニル-エチル)ベンゼン、1-シアノ-4-(1-メチルテラニル-エチル)ベンゼン、1-メチルカルボニル-4-(1-メチルテラニル-エチル)ベンゼン、1-フェニルカルボニル-4-(1-メチルテラニル-エチル)ベンゼン、1-メトキシカルボニル-4-(1-メチルテラニル-エチル)ベンゼン、1-フェノキシカルボニル-4-(1-メチルテラニル-エチル)ベンゼン、1-スルホニル-4-(1-メチルテラニル-エチル)ベンゼン、1-トリフルオロメチル-4-(1-メチルテラニル-エチル)ベンゼン、1-クロロ-4-(2-メチルテラニル-プロピル)ベンゼン、1-ヒドロキシ-4-(2-メチルテラニル-プロピル)ベンゼン、1-メトキシ-4-(2-メチルテラニル-プロピル)ベンゼン、1-アミノ-4-(2-メチルテラニル-プロピル)ベンゼン、1-ニトロ-4-(2-メチルテラニル-プロピル)ベンゼン、1-シアノ-4-(2-メチルテラニル-プロピル)ベンゼン、1-メチルカルボニル-4-(2-メチルテラニル-プロピル)ベンゼン、1-フェニルカルボニル-4-(2-メチルテラニル-プロピル)ベンゼン、1-メトキシカルボニル-4-(2-メチルテラニル-プロピル)ベンゼン、1-フェノキシカルボニル-4-(2-メチルテラニル-プロピル)ベンゼン、1-スルホニル-4-(2-メチルテラニル-プロピル)ベンゼン、1-トリフルオロメチル-4-(2-メチルテラニル-プロピル)ベンゼン、2-(メチルテラニル-メチル)ピリジン、2-(1-メチルテラニル-エチル)ピリジン、2-(2-メチルテラニル-プロピル)ピリジン、2-メチルテラニル-エタン酸メチル、2-メチルテラニル-プロピオン酸メチル、2-メチルテラニル-2-メチルプロピオン酸メチル、2-メチルテラニル-エタン酸エチル、2-メチルテラニル-プロピオン酸エチル、2-メチルテラニル-2-メチルプロピオン酸エチル、2-メチルテラニルアセトニトリル、2-メチルテラニルプロピオニトリル、2-メチル-2-メチルテラニルプロピオニトリル等が挙げられる。これらの有機テルル化合物中のメチルテラニル基は、エチルテラニル基、n-プロピルテラニル基、イソプロピルテラニル基、n-ブチルテラニル基、イソブチルテラニル基、t-ブチルテラニル基、フェニルテラニル基等であってもよく、また、これらの有機テルル化合物は、単独で用いてもよく、2種以上を併用してもよい。
上記アゾ化合物は、ラジカル重合に一般的に用いられるものであれば特に限定されず、例えば、2,2’-アゾビス(イソブチロニトリル)、2,2’-アゾビス(2-メチルブチロニトリル)、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、1,1-アゾビス(シクロヘキサン-1-カルボニトリル)、1-[(1-シアノ-1-メチルエチル)アゾ]ホルムアミド、4,4’-アゾビス(4-シアノバレリアン酸)、ジメチル-2,2’-アゾビス(2-メチルプロピオネート)、ジメチル-1,1’-アゾビス(1-シクロヘキサンカルボキシレート)、2,2’-アゾビス{2-メチル-N-[1,1’-ビス(ヒドロキシメチル)-2-ヒドロキシエチル]プロピオンアミド}、2,2’-アゾビス[2-メチル-N-(2-ヒドロキシエチル)プロピオンアミド]、2,2’-アゾビス[N-(2-プロペニル)-2-メチルプロピオンアミド]、2,2’-アゾビス(N-ブチル-2-メチルプロピオンアミド)、2,2’-アゾビス(N-シクロヘキシル-2-メチルプロピオンアミド)、2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]二塩酸塩、2,2’-アゾビス{2-[1-(2-ヒドロキシエチル)-2-イミダゾリン-2-イル]プロパン}二塩酸塩、2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]、2,2’-アゾビス(2-アミジノプロパン)二塩酸塩、2,2’-アゾビス[N-(2-カルボキシエチル)-2-メチルプロピオンアミジン]四水和物、2,2’-アゾビス(1-イミノ-1-ピロリジノ-2-メチルプロパン)二塩酸塩、2,2’-アゾビス(2,4,4-トリメチルペンタン)等が挙げられる。これらのアゾ化合物は、単独で用いてもよく、2種以上を併用してもよい。
上記リビングラジカル重合において重合溶媒を用いる場合、該重合溶媒は特に限定されず、例えば、ヘキサン、シクロヘキサン、オクタン、トルエン、キシレン等の非極性溶媒や、水、メタノール、エタノール、プロパノール、ブタノール、アセトン、メチルエチルケトン、メチルイソブチルケトン、テトラヒドロフラン、ジオキサン、N,N-ジメチルホルムアミド等の高極性溶媒を用いることができる。これらの重合溶媒は、単独で用いてもよく、2種以上を併用してもよい。
また、重合温度は、重合速度の観点から0~110℃が好ましい。
上記分子量分布が2.5を超えると、上記リビングラジカル重合において生成した低分子量成分等が増えるため、高温高湿下に晒された後に光学用粘着剤が曇りやすくなるか、接着面に気泡が発生しやすくなるか、光学用粘着剤を用いて製造した粘着テープの加工性が低下するかのいずれかの問題が生じる。上記分子量分布の好ましい上限は2.0であり、より好ましい上限は1.8である。
重量平均分子量(Mw)及び数平均分子量(Mn)は、ゲルパミエーションクロマトグラフィ(GPC)法によりポリスチレン換算分子量として測定される。具体的には、重量平均分子量(Mw)及び数平均分子量(Mn)は、(メタ)アクリルポリマーをテトラヒドロフラン(THF)によって50倍希釈して得られた希釈液をフィルターで濾過し、得られた濾液を用いてGPC法によりポリスチレン換算分子量として測定される。GPC法では、例えば、2690 Separations Model(Waters社製)等を使用できる。
例えば、上記(メタ)アクリルポリマーが架橋性官能基として水酸基を有する場合、架橋剤として例えばイソシアネート系架橋剤を用いることにより、上記(メタ)アクリルポリマーを架橋させることができる。
上記イソシアネート系架橋剤として、例えば、コロネートHX(日本ポリウレタン工業社製)、コロネートL(日本ポリウレタン工業社製)、マイテックNY260A(三菱化学社製)等が挙げられる。
上記粘着付与樹脂としては、例えば、水添ロジンエステル樹脂、水添テルペンフェノール樹脂等が挙げられる。
なお、ゲル分率は、次のようにして測定される。まず、光学用粘着テープを50mm×100mmの平面長方形状に裁断して試験片を作製し、試験片を酢酸エチル中に23℃にて24時間浸漬した後、酢酸エチルから取り出して、110℃の条件下で1時間乾燥させる。乾燥後の試験片の重量を測定し、下記式(1)を用いてゲル分率を算出する。なお、試験片には、粘着剤層を保護するための離型フィルムは積層されていないものとする。
ゲル分率(重量%)=100×(W2-W0)/(W1-W0) (1)
(W0:基材の重量、W1:浸漬前の試験片の重量、W2:浸漬、乾燥後の試験片の重量)
上記粘着剤層の厚みは用途によって設定されるので特に限定されないが、好ましい下限が1μm、好ましい上限が100μmである。上記厚みが1μm未満であると、光学用粘着テープが剥がれやすくなり、接着面に気泡が発生しやすくなることがある。上記厚みが100μmを超えると、薄い粘着テープが得られないことがある。上記厚みのより好ましい下限は25μm、より好ましい上限は75μmである。
少なくとも2つの被着体(例えば、上記電子機器を構成する部材等)の間に粘着剤層を配した積層体であって、上記被着体のうち少なくとも1つが透明な被着体であり、上記粘着剤層が本発明の光学用粘着剤から形成されている積層体もまた、本発明の1つである。
(1)リビングラジカル重合ポリマー(LRP)の合成
Tellurium(40メッシュ、金属テルル、アルドリッチ社製)6.38g(50mmol)をテトラヒドロフラン(THF)50mLに懸濁させ、これに1.6mol/Lのn-ブチルリチウム/ヘキサン溶液(アルドリッチ社製)34.4mL(55mmol)を、室温でゆっくり滴下した。この反応溶液を金属テルルが完全に消失するまで攪拌した。この反応溶液に、エチル-2-ブロモ-イソブチレート10.7g(55mmol)を室温で加え、2時間攪拌した。反応終了後、減圧下で溶媒を濃縮し、続いて減圧蒸留して、黄色油状物の2-メチル-2-n-ブチルテラニル-プロピオン酸エチルを得た。
得られたリビングラジカル重合ポリマー(LRP)をテトラヒドロフラン(THF)によって50倍希釈して得られた希釈液をフィルター(材質:ポリテトラフルオロエチレン、ポア径:0.2μm)で濾過し、得られた濾液をゲルパミエーションクロマトグラフ(Waters社製、2690 Separations Model)に供給して、サンプル流量1ミリリットル/min、カラム温度40℃の条件でGPC測定を行い、ポリマーのポリスチレン換算分子量を測定して、分子量分布(Mw/Mn)を求めた。カラムとしてはGPC KF-806L(昭和電工社製)を用い、検出器としては示差屈折計を用いた。
上記で得られたリビングラジカル重合ポリマー(LRP)含有溶液に、共重合体固形分100重量部に対して、架橋剤であるマイテックNY260A(三菱ガス化学社製)0.2重量部を添加し、攪拌した後、離型ポリエチレンテレフタレート(PET)フィルムの離型処理面上に塗工し、110℃で10分間乾燥することにより酢酸エチルを除去して、厚み50μmの粘着剤層を形成した。なお、粘着剤層の両側の表面には、粘着剤層を保護するために厚み50μmの離型処理したPETフィルムを積層した。
実施例1と同様に、リビングラジカル重合ポリマー(LRP)含有溶液を作製した後、共重合体固形分100重量部に対して、架橋剤であるマイテックNY260A(三菱ガス化学社製)1.5重量部を添加し、攪拌した後、離型ポリエチレンテレフタレート(PET)フィルムの離型処理面上に塗工し、110℃で10分間乾燥することにより酢酸エチルを除去して、厚み50μmの粘着剤層を形成した。なお、粘着剤層の両側の表面には、粘着剤層を保護するための離型フィルムを積層した。
(1)フリーラジカル重合ポリマー(FRP)の合成
反応容器内に、重合溶媒として酢酸エチル50gを加え、窒素でバブリングした後、窒素を流入しながら反応容器を加熱して還流を開始した。続いて、重合開始剤としてV-60(2,2’-アゾビスイソブチロニトリル、和光純薬工業社製)0.15gを酢酸エチルで10倍希釈した重合開始剤溶液を反応容器内に投入し、表1に示すモノマーの合計100gを2時間かけて滴下添加した。滴下終了後、重合開始剤としてV-60(2,2’-アゾビスイソブチロニトリル、和光純薬工業社製)0.15gを酢酸エチルで10倍希釈した重合開始剤溶液を反応容器内に再度投入し、4時間重合反応を行い、フリーラジカル重合ポリマー(FRP)含有溶液を得た。リビングラジカル重合ポリマー(LRP)の場合と同様にして、分子量分布(Mw/Mn)を求めた。
リビングラジカル重合ポリマー(LRP)の場合と同様にして、両面粘着テープを得た。
フリーラジカル重合ポリマー(FRP)の合成において表1に示すモノマーを用いた以外は比較例4と同様にして、両面粘着テープを得た。
実施例、比較例で得られた両面粘着テープについて、下記の評価を行った。結果を表1に示した。
両面粘着テープについて、カッター刃を用いて打ち抜き作業を40回行い、カッター刃に粘着剤が付着することにより発生する刃汚れ、及び、打ち抜き作業時における粘着剤の糸引き現象を目視により観察した。
粘着剤が付着することにより発生する刃汚れが見られず、粘着剤の糸引き現象も見られない場合を「○」、刃汚れは多少見られるが、糸引き現象は見られない場合を「△」、刃汚れが見られ、かつ、糸引き現象も見られる場合を「×」として切断加工性を評価した。
両面粘着テープを45mm×60mmの平面形状を有するように裁断した。裁断された両面粘着テープの一方の離型ポリエチレンテレフタレートフィルムを剥離し、露出した粘着剤層に透明なポリエチレンテレフタレートフィルムを貼り付け、次いで、もう一方の離型ポリエチレンテレフタレートフィルムを剥離し、露出した粘着剤層をスライドガラス(商品名「S-1214」MATSUNAMI社製)に貼り合わせて、ポリエチレンテレフタレートフィルム/両面粘着テープ/スライドガラスの層構造を有する試験片を作製した。試験片作製直後のヘイズ値(%)を、ヘイズメータを用いてJIS K 7105に従って測定し、更に、この試験片を温度85℃、湿度85RH%の恒温恒湿器に24時間放置した後、試験片を取り出してただちにヘイズ値を測定した。下記式(2)によりΔヘイズ値を算出した。
Δヘイズ値(%)={24時間放置した後の試験片のヘイズ値(%)}-{試験片作製直後のヘイズ値(%)}(2)
Δヘイズ値が0.3以下である場合を「透明」、ヘイズ値が0.3を超える場合を「白濁」として透明性を評価した。
両面粘着テープを45mm×60mmの平面形状を有するように裁断した。裁断された両面粘着テープの一方の離型ポリエチレンテレフタレートフィルムを剥離し、粘着剤層を露出させた。次いで、厚みが0.18mmのITO付フィルムのITO膜面上に、両面粘着テープの露出した面を貼り合わせた。更に、両面粘着テープのもう一方の離型ポリエチレンテレフタレートフィルムを剥離し、粘着剤層を露出させ、厚みが2.0mmの平面形状を有するポリカーボネート板(PC板)上に両面粘着テープの露出した面を貼り合わせることにより、ポリカーボネート板(PC板)上に、両面粘着テープとITO付フィルムとがこの順で積層されている積層体を得た。その後、得られた積層体を23℃、0.5MPaのオートクレーブにて15分間処理を行った後、温度85℃、相対湿度(RH)85%の条件で500時間静置し、試験サンプルを得た。得られた試験サンプルの接着界面における気泡発生状態を目視により観察した。
0.01mm以上の大きさの気泡が全く観察されなかった場合を「〇」と、0.01mm以上の大きさの気泡が1つの試験サンプル当たり1~5個観察された場合を「×」として、気泡発生状態を評価した。
両面粘着テープを長さ40mm×幅60mmの平面形状を有するように裁断した。更に、幅方向で隣り合う2つの角を、それぞれ角からの長さが10mm、角から幅の10mmのサイズの平面形状で切断し、凸状のテープを得た。
凸状のテープの一方の離型ポリエチレンテレフタレートフィルムを剥離し、凸状のテープの露出した面をポリエチレンテレフタレート上に貼り付けた。更に、凸状のテープのもう一方の離型ポリエチレンテレフタレートフィルムを剥離し、凸状のテープの露出した面を40mm×幅60mmの平面形状を有するITOフィルムのITO膜面上に貼り合わせた。これにより、ITOフィルムのITO膜面上に、両面粘着テープとポリエチレンテレフタレートとがこの順で積層されている導電性フィルム積層体を得た。
得られた初期抵抗値及び高温高湿下放置後の抵抗値より、下記式により抵抗値変化率(%)を算出した。得られた抵抗値変化率(%)が3未満であった場合を「○」と、3以上、10未満であった場合を「△」と、10以上であった場合を「×」と評価した。
抵抗値変化率(%)=(高温高湿下放置後の抵抗値-初期抵抗値)/初期抵抗値×100
11 炭素数1~14のアルキル基を有するアルキル(メタ)アクリレート
12 ヒドロキシル基、アミノ基又はアミド基含有モノマー
13 カルボキシル基含有モノマー
2 フリーラジカル重合された(メタ)アクリルポリマー
21 炭素数1~14のアルキル基を有するアルキル(メタ)アクリレート
22 ヒドロキシル基、アミノ基又はアミド基含有モノマー
23 カルボキシル基含有モノマー
24 反応の途中で生長末端ラジカルが失活したポリマー
25 反応中に新しく発生したラジカル種により生長したポリマー
Claims (3)
- a)炭素数1~14のアルキル基を有するアルキル(メタ)アクリレート60~95重量部、b)カルボキシル基含有モノマー0.1~1重量部、及び、c)ヒドロキシル基、アミノ基又はアミド基含有モノマー10~30重量部を含むモノマー混合物をリビングラジカル重合により共重合させて得られた分子量分布(Mw/Mn)1.05~2.5の(メタ)アクリルポリマーと、架橋剤とを含有し、
前記a)炭素数1~14のアルキル基を有するアルキル(メタ)アクリレートは、ビシクロ環構造を有する(メタ)アクリレートを含むことを特徴とする光学用粘着剤。 - 請求項1記載の光学用粘着剤から形成されている粘着剤層を有することを特徴とする光学用粘着テープ。
- 少なくとも2つの被着体の間に粘着剤層を配した積層体であって、前記被着体のうち少なくとも1つが透明な被着体であり、前記粘着剤層が請求項1記載の光学用粘着剤から形成されていることを特徴とする積層体。
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CN201480059825.9A CN105683324B (zh) | 2013-12-27 | 2014-12-19 | 光学用粘合剂、光学用粘合带及层叠体 |
JP2015505358A JP5860566B2 (ja) | 2013-12-27 | 2014-12-19 | 光学用粘着剤、光学用粘着テープ及び積層体 |
KR1020167007184A KR20160104613A (ko) | 2013-12-27 | 2014-12-19 | 광학용 점착제, 광학용 점착 테이프 및 적층체 |
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WO2018117038A1 (ja) * | 2016-12-22 | 2018-06-28 | 日本ゼオン株式会社 | 末端変性アクリルゴム、アクリルゴム組成物、アクリルゴム架橋物、及び末端変性アクリルゴムの製造方法 |
CN108047965A (zh) * | 2017-12-26 | 2018-05-18 | 苏州凡赛特材料科技有限公司 | 一种光学胶、液体光学胶黏剂及曲面屏光学胶带的制备方法 |
KR20210015747A (ko) * | 2018-06-01 | 2021-02-10 | 세키스이가가쿠 고교가부시키가이샤 | 점착 시트 |
WO2019244595A1 (ja) * | 2018-06-19 | 2019-12-26 | 積水化学工業株式会社 | 粘着剤、粘着テープ、及び、電子機器部品又は車載部品を固定する方法 |
JP7220633B2 (ja) * | 2019-07-19 | 2023-02-10 | 株式会社日本触媒 | 粘着剤組成物及びその利用 |
JPWO2021200647A1 (ja) * | 2020-03-31 | 2021-10-07 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007119884A1 (ja) * | 2006-04-14 | 2007-10-25 | Otsuka Chemical Co., Ltd. | 樹脂組成物および耐熱性粘着剤 |
WO2011007861A1 (ja) * | 2009-07-16 | 2011-01-20 | 積水化学工業株式会社 | 粘着テープ、積層体及び画像表示装置 |
JP2011074380A (ja) * | 2009-09-07 | 2011-04-14 | Lintec Corp | 保護フィルム及び保護フィルムの製造方法 |
WO2012132115A1 (ja) * | 2011-03-31 | 2012-10-04 | 株式会社クラレ | 透明両面粘着シートおよびタッチパネル付き画像表示装置 |
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DE10234246A1 (de) * | 2002-07-27 | 2004-02-05 | Tesa Ag | Haftklebemassen mit hohem Brechungsindex auf Basis von Acrylatblockcopolymeren |
KR101938894B1 (ko) * | 2010-03-18 | 2019-01-15 | 세키스이가가쿠 고교가부시키가이샤 | 광학 부재용 점착제 조성물 및 광학 부재용 점착 테이프 |
JP5614328B2 (ja) * | 2011-02-25 | 2014-10-29 | 藤倉化成株式会社 | 粘着剤組成物、粘着フィルム、および光学部品 |
JP2012237965A (ja) * | 2011-04-27 | 2012-12-06 | Nitto Denko Corp | 粘着剤層、光学フィルムおよび画像表示装置 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007119884A1 (ja) * | 2006-04-14 | 2007-10-25 | Otsuka Chemical Co., Ltd. | 樹脂組成物および耐熱性粘着剤 |
WO2011007861A1 (ja) * | 2009-07-16 | 2011-01-20 | 積水化学工業株式会社 | 粘着テープ、積層体及び画像表示装置 |
JP2011074380A (ja) * | 2009-09-07 | 2011-04-14 | Lintec Corp | 保護フィルム及び保護フィルムの製造方法 |
WO2012132115A1 (ja) * | 2011-03-31 | 2012-10-04 | 株式会社クラレ | 透明両面粘着シートおよびタッチパネル付き画像表示装置 |
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JP2016094616A (ja) | 2016-05-26 |
TWI649386B (zh) | 2019-02-01 |
CN105683324A (zh) | 2016-06-15 |
JP6457922B2 (ja) | 2019-01-23 |
CN105683324B (zh) | 2018-06-22 |
JP5860566B2 (ja) | 2016-02-16 |
KR20160104613A (ko) | 2016-09-05 |
JPWO2015098727A1 (ja) | 2017-03-23 |
TW201533191A (zh) | 2015-09-01 |
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