WO2012020764A1 - 粘着剤組成物、粘着剤層、および粘着剤シート - Google Patents
粘着剤組成物、粘着剤層、および粘着剤シート Download PDFInfo
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- WO2012020764A1 WO2012020764A1 PCT/JP2011/068173 JP2011068173W WO2012020764A1 WO 2012020764 A1 WO2012020764 A1 WO 2012020764A1 JP 2011068173 W JP2011068173 W JP 2011068173W WO 2012020764 A1 WO2012020764 A1 WO 2012020764A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
- C09J125/06—Polystyrene
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- 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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- 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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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- 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
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- 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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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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
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- C09J2425/00—Presence of styrenic polymer
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2433/00—Presence of (meth)acrylic polymer
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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
- C09J2451/00—Presence of graft polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/14—Layer or component removable to expose adhesive
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
Definitions
- the present invention can be applied to various pressure-sensitive adhesive compositions containing titanium nanoparticles, a pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition, and a pressure-sensitive adhesive having such a pressure-sensitive adhesive layer on at least one side of a support.
- the agent sheet can be applied to various pressure-sensitive adhesive compositions containing titanium nanoparticles, a pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition, and a pressure-sensitive adhesive having such a pressure-sensitive adhesive layer on at least one side of a support.
- an adhesive composition made of an acrylic polymer has been used as an adhesive used when bonding various optical films such as an antireflection film and a conductive film to a display panel such as a liquid crystal display device.
- the refractive index of materials used for optical films and optical members is, for example, about 1.52 for glass, about 1.51 for methacrylic resin, and about 1.5 for polycarbonate. , About 1.60.
- the conventional pressure-sensitive adhesive composition has a refractive index of about 1.47 after drying or curing. For this reason, a difference in refractive index occurs at the interface between the optical film or optical member and the pressure-sensitive adhesive layer, and total reflection occurs with light at a shallow angle, which may reduce the light extraction efficiency.
- the refractive index is higher than that of a conventional acrylic pressure-sensitive adhesive composition, It is not the desired balance with other properties.
- Patent Document 1 For example, adding various silane coupling agents to colloidal silica gel of 30 nm or less to modify the silica surface and mixing with a polymer solution to create an adhesive, reducing the volume shrinkage due to the presence of fine particles Therefore, expression of the effect of increasing the adhesive strength itself is expected (Patent Document 1).
- Patent Document 2 proposes nanoparticles as a diffusion adhesive to increase the contrast and the viewing angle, but the specific stable dispersion method here is not clear (Patent Document 2).
- Patent Document 3 a method of preparing an adhesive syrup by treating a metal oxide particle of 200 nm or less with a long-chain aliphatic acid or an organosilane as a surface modifier and dispersing it in a monomer or the like is also disclosed.
- an ultraviolet shielding adhesive in which an organic polymer that does not generate an acidic functional group is mixed with an acrylic polymer copolymerized with a monomer having a hydroxyl group and zinc oxide fine particles of 0.2 ⁇ m or less are mixed and applied (patent) Reference 4).
- the fine particles prepared using the surface treatment method are dispersed in various compositions, depending on the type of polymer, the fine particles may aggregate and the composite may become cloudy and haze may occur.
- the type of solvent, the surface modifier, or the type of coupling agent in a timely manner.
- an object of the present invention is to provide a pressure-sensitive adhesive composition in which titanium-based nanoparticles are stably dispersed and desired physical properties can be obtained without going through complicated steps.
- Another object of the present invention is to provide a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer.
- (Meth) acrylate represented by the formula (A) represents 50% by weight or more, and contains substantially no acid component having a weight average molecular weight of 500,000 to 3,000,000 by gel permeation chromatography (meth).
- Acrylic polymer It is composed of 120 to 400 parts by weight of an aromatic ring-containing monomer having a polymerizable functional group having an unsaturated double bond and having an aromatic ring with respect to 100 parts by weight of the (meth) acrylic polymer.
- An aromatic polymer having a weight average molecular weight of 200 to 900 by gel permeation chromatography; and 150 to 600 parts by weight of an average particle size of 100 nm or less with respect to 100 parts by weight of the (meth) acrylic polymer.
- the present invention relates to a pressure-sensitive adhesive composition comprising titanium-based nanoparticles.
- the (meth) acrylic polymer may further contain CH 2 ⁇ C (R 1 ) COOC n H 2n OH (where R 1 is hydrogen or a methyl group, n is 1 It is preferably a copolymer containing 0.05 to 10% by weight of a hydroxyl group-containing (meth) acrylate represented by (representing an integer from 1 to 10).
- the pressure-sensitive adhesive composition it is preferable to contain 0.02 to 2 parts by weight of a crosslinking agent with respect to 100 parts by weight of the (meth) acrylic polymer.
- the (meth) acrylic polymer may be a graft polymer having a side chain having a composition different from the main chain constituting the trunk.
- the present invention also relates to a pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition as described above.
- the pressure-sensitive adhesive layer preferably has a gel fraction of 40 to 90% by weight.
- the pressure-sensitive adhesive layer preferably has a haze value of 20% or less.
- the present invention also relates to an adhesive sheet, wherein any one of the above-mentioned adhesive layers is formed on at least one side of a support.
- the pressure-sensitive adhesive composition of the present invention can be used in a wide range of applications because a large amount of titanium-based nanoparticles are stably dispersed, the mechanical properties are further enhanced, and the refractive index and adhesive strength are also excellent. it can.
- the pressure-sensitive adhesive composition for an optical member of the present invention has, as monomer units, CH 2 ⁇ C (R 1 ) COOR 2 (where R 1 is hydrogen or a methyl group, R 2 is a non-carbon group having 1 to 20 carbon atoms).
- R 1 is hydrogen or a methyl group
- R 2 is a non-carbon group having 1 to 20 carbon atoms.
- a (meth) acrylic polymer containing no components is included as a base polymer.
- the unsubstituted alkyl group having 1 to 20 carbon atoms or the substituted alkyl group as R 2 refers to a linear or branched alkyl group or a cyclic cycloalkane.
- the substituent is preferably an aryl group having 3 to 8 carbon atoms or an aryloxy group having 3 to 8 carbon atoms.
- the aryl group is not limited, but is preferably a phenyl group.
- Examples of such a monomer represented by CH 2 ⁇ C (R 1 ) COOR 2 include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and s-butyl (meth) acrylate.
- T-butyl (meth) acrylate isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, isoamyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n- Dodecyl (Meth) acrylate, isomyristyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (
- the monomer represented by CH 2 ⁇ C (R 1 ) COOR 2 is 50% by weight or more and 50 to 98% by weight with respect to the total monomer components of the (meth) acrylic polymer. It is preferable.
- butyl (meth) acrylate is preferably 50% by weight or more, and more preferably 60 to 99.5% by weight from the viewpoints of polymerizability and dispersion stability of titanium-based nanoparticles.
- the (meth) acrylic polymer of the present invention may further contain a hydroxyl group-containing monomer represented by CH 2 ⁇ C (R 1 ) COOC n H 2n OH. That is, this monomer is a monomer containing a hydroxyalkyl group having 1 or more carbon atoms and one hydroxyl group.
- Examples of such monomers include 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meta ) Acrylates, hydroxyalkyl (meth) acrylates such as 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, etc .; hydroxyalkylcycloalkanes (meth) such as 4-hydroxymethylcyclohexyl (meth) acrylate An acrylate is mentioned.
- the hydroxyl group-containing monomer When included, the hydroxyl group-containing monomer is used in a proportion of 0.05 to 10% by weight with respect to the total amount of monomer components forming the (meth) acrylic polymer.
- the proportion of the hydroxyl group-containing monomer is preferably 0.05 to 5% by weight, more preferably 0.1 to 1% by weight.
- the (meth) acrylic polymer As the monomer component forming the (meth) acrylic polymer, other copolymerization monomers may be used alone or in combination as long as the object of the present invention is not impaired. However, in the present invention, the (meth) acrylic polymer contains substantially no acid component.
- substantially does not contain an acid component means that it is not contained at all in the whole polymer or less than 0.1% by weight even if it is contained.
- an acid component is not limited, For example, a carboxylic acid containing monomer, acrylic acid, etc. are pointed out.
- vinyl monomers such as vinyl acetate, vinyl propionate, styrene, ⁇ -methylstyrene, N-vinylcaprolactam; glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 3, Epoxy group-containing monomers such as 4-epoxycyclohexylmethyl (meth) acrylate; (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) acrylic acid methoxypolypropylene glycol Glycol acrylic ester monomers such as tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate and 2-methoxyethyl acrylate Acrylic acid ester monomer; amide group-containing monomers, amino group-containing monomers, imide group-containing monomer, N
- silane type monomer containing a silicon atom etc. are mention
- examples of the silane monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyltrimethoxysilane.
- 8-vinyloctyltriethoxysilane 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, 10-acryloyloxydecyltriethoxysilane, and the like.
- the weight average molecular weight of the (meth) acrylic polymer of the present invention needs to be 500,000 or more, preferably 600,000 or more.
- the weight average molecular weight is less than 500,000, the durability of the pressure-sensitive adhesive layer becomes poor, or the cohesive force of the pressure-sensitive adhesive layer becomes small and adhesive residue tends to occur.
- the weight average molecular weight is more than 3 million, the bonding property and the adhesive strength are lowered, which is not preferable.
- the pressure-sensitive adhesive composition may become too viscous in a solution system, and coating may be difficult.
- the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
- the production of such a (meth) acrylic polymer can be appropriately selected from known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations. Further, the (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
- solution polymerization for example, ethyl acetate, toluene or the like is used as a polymerization solvent.
- the reaction is carried out under an inert gas stream such as nitrogen and a polymerization initiator is added, usually at about 50 to 70 ° C. under reaction conditions for about 5 to 30 hours.
- the polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used.
- the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator and a chain transfer agent, and reaction conditions, The usage-amount is suitably adjusted according to these kinds.
- polymerization initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2 -Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), 2,2 Azo initiators such as' -azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057, manufactured by Wako Pure Chemical Industries, Ltd.), persulfates such as potassium persulfate and ammonium persulfate , Di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di-sec-butyl Peroxydicarbonate, t
- the polymerization initiator may be used singly or as a mixture of two or more, but the total content is 0.005 to 1 part by weight with respect to 100 parts by weight of the monomer. Is preferably about 0.02 to 0.5 parts by weight.
- the amount of the polymerization initiator used is a monomer.
- the amount is preferably about 0.06 to 0.2 parts by weight, more preferably about 0.08 to 0.175 parts by weight with respect to 100 parts by weight of the total amount of the components.
- chain transfer agent examples include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
- the chain transfer agent may be used alone or in combination of two or more, but the total content is 0.1 parts by weight with respect to 100 parts by weight of the total amount of monomer components. Less than or equal to
- emulsifier used in emulsion polymerization examples include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, and polyoxy Nonionic emulsifiers such as ethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene-polyoxypropylene block polymer are listed. These emulsifiers may be used alone or in combination of two or more.
- reactive emulsifiers emulsifiers into which radical polymerizable functional groups such as propenyl groups and allyl ether groups are introduced, specifically, for example, Aqualon HS-10, HS-20, KH-10, BC-05 BC-10, BC-20 (all of which are manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria soap SE10N (manufactured by ADEKA), and the like.
- Reactive emulsifiers are preferable because they are incorporated into the polymer chain after polymerization and thus have improved water resistance.
- the amount of the emulsifier used is preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomer components, and more preferably 0.5 to 1 part by weight from the viewpoint of polymerization stability and mechanical stability.
- the monomer having a different composition is not particularly limited, and may be various (meth) acrylic monomers, preferably a monomer that is contained only in 10% by weight or less in the polymer composition of the trunk; styrene derivatives such as ⁇ styrene; derivatives such as vinyl toluene and ⁇ vinyl toluene;
- the method of graft polymerization is not particularly limited as long as it is a method known to those skilled in the art.
- the monomer to be graft polymerized and the viscosity adjustment to the acrylic polymer solution after the reaction for the structure of the trunk After adding the solvent for the above, purging with nitrogen, adding 0.02 to 5 parts by weight of peroxide and heating at 50 to 80 ° C. for 4 to 15 hours.
- acrylic polymer particles are prepared by adding water for adjusting the solid content to an aqueous dispersion of acrylic polymer constituting the trunk, adding necessary monomers, and substituting with nitrogen while stirring. Further, after absorbing the monomer for graft polymerization, a water-soluble aqueous peroxide solution is added, and the reaction is terminated by heating at 50 to 80 ° C. for 4 to 15 hours.
- a homopolymer by this monomer is also produced, but graft polymerization also occurs.
- the homopolymer by the monomer used for graft polymerization is in a state of being uniformly present in the acrylic polymer.
- the resulting graft polymer has good heat resistance.
- a hydroxyl group-containing acrylic monomer is present in the trunk polymer, better compatibility with the compatibility of the position at which hydrogen abstraction occurs and the compatibility of the graft polymer or the resulting homopolymer is imparted.
- an acrylic polymer that is a normal polymer, or an acrylic polymer that constitutes a trunk polymer in the case of a graft polymer preferably has a glass transition temperature of 250 K or less.
- the final pressure-sensitive adhesive composition obtained has good heat resistance.
- the glass transition temperature of the site constituting the branch in the graft polymer is 300K or higher.
- the pressure-sensitive adhesive composition of the present invention is an aromatic system having a polymerization average molecular weight of 200 to 900 by gel permeation chromatography with respect to 100 parts by weight of such a (meth) acrylic polymer.
- the polymer further contains 150 to 600 parts by weight of titanium-based nanoparticles having an average particle diameter of 100 nm or less, preferably an average particle diameter of 5 to 100 nm.
- an aromatic ring-containing monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having an aromatic ring Can be given.
- aromatic ring-containing monomer examples include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, 2-naphthoethyl (meth) acrylate, 2- (4-methoxy-1- And naphthoxy) ethyl (meth) acrylate, phenoxypropyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and polystyryl (meth) acrylate.
- styrene derivatives such as styrene and ⁇ -methylstyrene, vinyl toluene, ⁇ -vinyl toluene, and the like can be given.
- the polymerization average molecular weight of the aromatic polymer is 200 or more and 900 or less, and preferably 300 or more and 800 or less. If it is greater than 900, adhesion may be lost. Moreover, when it is less than 200, the effect of dispersing and stabilizing the titanium-based nanoparticles cannot be obtained.
- a method of synthesizing a low molecular weight polymer a method of adjusting molecular weight by using a mercaptan or ⁇ -methylstyrene dimer in ordinary radical polymerization, a living using a polymerization initiator in the presence of a transition metal and a ligand Any method such as a radical polymerization method or an anionic polymerization method can be employed.
- the content of the aromatic low-molecular polymer is 120 to 400 parts by weight, preferably 150 to 350 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. If the content is less than this amount, the adhesiveness is lowered, and if it is too much, the physical properties of the acrylic polymer are changed, which is not preferable.
- the titanium-based nanoparticles contained in the pressure-sensitive adhesive composition of the present invention are nanoparticles containing titanium.
- Specific examples thereof include titanium oxide, barium titanate, zirconium titanate, strontium titanate, aluminum titanate, and titanic acid.
- Examples include potassium, lithium titanate, calcium titanate, magnesium titanate, lead titanate, titanium nitride, and combinations thereof.
- the shape of the titanium-based nanoparticles may be a bulk shape such as a spherical shape, a rectangular parallelepiped shape, or a deformed shape thereof, a needle shape, or a plate shape.
- the average particle diameter of the titanium-based nanoparticles is 5 to 100 nm, preferably 5 to 50 nm, and more preferably 5 to 20 nm.
- the maximum length is 5 to 100 nm, preferably 5 to 50 nm, and more preferably 5 to 20 nm.
- the average particle size was measured by a dynamic light scattering method using “ZetasizerNANO ZS type” manufactured by MALVERN, and displayed as a number average particle size.
- nanoparticles are not essential, but may be stabilized by treating the surface with a dispersion stabilizer such as a silane coupling agent.
- Dispersion stabilizers include octylmethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, silane coupling agents such as vinyltrimethoxysilane, lauric acid And long chain fatty acids such as oleic acid and silicone compounds modified with various organic substances.
- the dispersion stabilizer may be used alone or in combination of two or more, but the amount necessary to treat the titanium-based nanoparticles as a whole is the titanium-based nanoparticles.
- the amount is 1 to 100 parts by weight with respect to 100 parts by weight.
- the content of the titanium-based nanoparticles is 150 to 600 parts by weight, preferably 200 to 550 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer.
- the content is less than this amount, the desired refractive index cannot be achieved, and if it is too much, it is difficult to form an adhesive layer, which is not preferable.
- the ratio of the content of the titanium-based nanoparticles to the content of the aromatic-based polymer is 1.0 to 2.0, preferably 1.2 to 1. 8. If the upper limit is 2.0, the formation of the pressure-sensitive adhesive layer is smooth, and if the lower limit is 1.0, the effect of increasing the refractive index of the pressure-sensitive adhesive layer is obtained.
- the pressure-sensitive adhesive composition of the present invention further contains a crosslinking agent such as an isocyanate crosslinking agent, an epoxy crosslinking agent, an oxazoline crosslinking agent, or a peroxide.
- a crosslinking agent such as an isocyanate crosslinking agent, an epoxy crosslinking agent, an oxazoline crosslinking agent, or a peroxide.
- an isocyanate crosslinking agent or a peroxide crosslinking agent and a combination thereof are preferably used.
- the isocyanate-based crosslinking agent used as a crosslinking agent is a compound having two or more isocyanate groups (including isocyanate-regenerating functional groups in which isocyanate groups are temporarily protected by blocking agents or quantification) in one molecule.
- isocyanate-based crosslinking agent examples include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.
- lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate
- alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate
- 2,4-tolylene diisocyanate Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), tri Methylolpropane / hexamethylene diisocyanate trimer adduct (trade name Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexamethylene dii Isocyan
- the isocyanate-based crosslinking agent may be used alone or in combination of two or more, but the total content is 100 parts by weight of the (meth) acrylic polymer.
- the isocyanate compound crosslinking agent is preferably contained in an amount of 0.01 to 2 parts by weight, more preferably 0.05 to 1 part by weight. It can be appropriately contained in consideration of cohesive force and prevention of peeling in a durability test.
- the peroxide crosslinking agent can be used as appropriate as long as it generates radical active species by heating to advance the crosslinking of the base polymer of the pressure-sensitive adhesive composition, but in consideration of workability and stability. It is preferable to use a peroxide having a one-minute half-life temperature of 80 ° C. to 160 ° C., more preferably a peroxide having a 90 ° C. to 140 ° C.
- peroxides examples include di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C.), di (4-t-butylcyclohexyl) peroxydicarbonate (1 Minute half-life temperature: 92.1 ° C.), di-sec-butyl peroxydicarbonate (1 minute half-life temperature: 92.4 ° C.), t-butyl peroxyneodecanoate (1 minute half-life temperature: 103 0.5 ° C.), t-hexyl peroxypivalate (1 minute half-life temperature: 109.1 ° C.), t-butyl peroxypivalate (1 minute half-life temperature: 110.3 ° C.), dilauroyl peroxide ( 1 minute half-life temperature: 116.4 ° C.), di-n-octanoyl peroxide (1 minute half-life temperature: 117.4 ° C.), 1,1,3,3-tetramethylbutyl
- di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C.)
- dilauroyl peroxide (1 minute half-life temperature: 116. 4 ° C)
- dibenzoyl peroxide (1 minute half-life temperature: 130.0 ° C) and the like are preferably used.
- the peroxide half-life is an index representing the decomposition rate of the peroxide, and means the time until the remaining amount of peroxide is reduced to half.
- the decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer catalog, for example, “Organic peroxide catalog 9th edition by Nippon Oil & Fats Co., Ltd.” (May 2003) ".
- the peroxide may be used alone or as a mixture of two or more, but the total content is based on 100 parts by weight of the (meth) acrylic polymer.
- the peroxide is 0.02 to 2 parts by weight, preferably 0.05 to 1 part by weight. In order to adjust processability, reworkability, cross-linking stability, peelability, and the like, it is appropriately selected within this range.
- the peroxide decomposition amount remaining after the reaction treatment for example, it can be measured by HPLC (High Performance Liquid Chromatography).
- the pressure-sensitive adhesive composition after the reaction treatment is taken out, immersed in 10 ml of ethyl acetate, extracted by shaking at 25 ° C. and 120 rpm for 3 hours with a shaker, and then at room temperature. Leave for 3 days. Next, 10 ml of acetonitrile was added, shaken at 120 rpm at 25 ° C. for 30 minutes, and about 10 ⁇ l of the extract obtained by filtration through a membrane filter (0.45 ⁇ m) was injected into the HPLC for analysis. The amount of peroxide can be set. *
- an organic type crosslinking agent and a polyfunctional metal chelate as a crosslinking agent.
- the organic crosslinking agent include epoxy crosslinking agents (referring to compounds having two or more epoxy groups in one molecule).
- the epoxy-based crosslinking agent include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, terephthalic acid diglycidyl ester acrylate, spiroglycol diglycidyl ether, and the like. These may be used alone or in combination of two or more.
- the multifunctional metal chelate is a polyvalent metal having a covalent bond or a coordinate bond with an organic compound.
- polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. can give.
- the atom in the organic compound that is covalently bonded or coordinated include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound.
- the pressure-sensitive adhesive layer is formed by the cross-linking agent. In forming the pressure-sensitive adhesive layer, it is necessary to adjust the addition amount of the entire cross-linking agent and sufficiently consider the influence of the cross-linking treatment temperature and the cross-linking treatment time.
- the addition amount of the cross-linking agent so that the gel fraction of the cross-linked pressure-sensitive adhesive layer is 40 to 90% by weight, more preferably 50 to 85% by weight.
- Such a gel fraction is preferably achieved by using a peroxide, an isocyanate-based crosslinking agent, and a combination thereof.
- the crosslinking ratio is 10 to 75% when the gel fraction of the peroxide alone is measured.
- the predetermined gel fraction can be adjusted by adjusting the amount of the isocyanate-based cross-linking agent and the amount of other cross-linking agent added and taking into consideration the conditions such as the cross-linking temperature and time.
- a peroxide when used, it is a guideline to set the crosslinking treatment time and time so that the decomposition amount of the peroxide is 50% or more, preferably 60% or more. If the decomposition amount of the peroxide is small, the amount of remaining peroxide increases and a crosslinking reaction over time occurs, which is not preferable.
- the crosslinking treatment temperature is a half-life temperature of 1 minute
- the decomposition amount is 50% in 1 minute and 75% in 2 minutes, and heat treatment for 1 minute or more is required.
- the peroxide half-life time at the crosslinking treatment temperature is 30 seconds
- a crosslinking treatment of 30 seconds or more is required, and if the peroxide half-life time at the crosslinking treatment temperature is 5 minutes, 5 minutes. The above crosslinking treatment is required.
- the crosslinking treatment temperature and time are proportionally calculated and adjusted from the half-life time assuming that the peroxide is linearly proportional, but up to 170 ° C. to avoid side reactions. It is necessary to heat-process up to.
- the temperature at the time of drying may be used as it is, or it may be processed after drying.
- the processing time is set in consideration of productivity and workability, but 0.2 to 20 minutes, preferably 0.5 to 10 minutes is used.
- the pressure-sensitive adhesive thus obtained has a very small increase in adhesive strength after being applied to an adherend, and exhibits the characteristics that it can be easily re-peeled without remaining glue even after being applied for a long time.
- the pressure-sensitive adhesive layer when used for an optical member, preferably has a haze value of 20% or less. When the haze value exceeds 20%, the transmittance greatly decreases when laminated on the optical member, which is not preferable.
- the pressure-sensitive adhesive layer of the present invention is not limited, but usually has a haze value of 20% or less. A haze value of 20% or less means that although the titanium-based nanoparticles are blended, the obtained pressure-sensitive adhesive layer has no white turbidity and the titanium-based nanoparticles are uniformly dispersed. Means. Therefore, in the pressure-sensitive adhesive of the present invention, the haze value is not increased and the transmittance is hardly lowered.
- optical films and optical members having a high refractive index have been used.
- a pressure-sensitive adhesive when bonding a brightness enhancement film to polycarbonate having a refractive index of about 1.60.
- the refractive index of the pressure-sensitive adhesive layer is preferably about 1.60 or 1.60 or more, and if it is less than that, the characteristics of the member and the film may be deteriorated.
- the refractive index of the pressure-sensitive adhesive layer of the present invention is also preferably within this range.
- a silane coupling agent is used to increase the water resistance at the interface. 0.01 to 1 part by weight, preferably 0.02 to 0.6 part by weight may be blended with 100 parts by weight of the polymer. If the amount is too large, the adhesive force to the liquid crystal cell is increased and the removability is poor.
- silane coupling agents examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4 epoxy cyclohexyl).
- Epoxy group-containing silane coupling agent such as ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1 , 3-dimethylbutylidene) propylamine, amino group-containing silane coupling agents such as N-phenyl- ⁇ -aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc.
- an isocyanate group-containing silane coupling agent such as 3-isocyanatepropyltriethoxysilane.
- the pressure-sensitive adhesive composition of the present invention may contain other known additives, such as powders such as colorants and pigments, dyes, surfactants, plasticizers, tackifiers, Use surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, UV absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particles, foils, etc. It can be added appropriately depending on the application.
- the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer formed on at least one surface of a support such as an optical member using the pressure-sensitive adhesive.
- the pressure-sensitive adhesive composition is applied to a release-treated separator, and the polymerization solvent is dried and removed to form a pressure-sensitive adhesive layer, which is then transferred to an optical member. It is produced by a method or a method of applying the pressure-sensitive adhesive composition to an optical member, drying and removing a polymerization solvent and the like, and performing a crosslinking treatment to form a pressure-sensitive adhesive layer on the optical member.
- one or more solvents other than the polymerization solvent may be added as appropriate.
- a silicone release liner is preferably used as the release-treated separator.
- a method for drying the pressure-sensitive adhesive is appropriately employed depending on the purpose. obtain.
- a method of heating and drying the coating film is used.
- the heating and drying temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and particularly preferably 70 ° C to 170 ° C.
- the drying time an appropriate time can be adopted as appropriate.
- the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.
- the pressure-sensitive adhesive layer can be formed after forming an anchor layer on the surface of the optical member or performing various easy adhesion treatments such as corona treatment and plasma treatment. Moreover, you may perform an easily bonding process on the surface of an adhesive layer.
- Various methods are used as a method for forming the pressure-sensitive adhesive layer. Specifically, for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
- the thickness of the pressure-sensitive adhesive layer is not particularly limited, and is, for example, about 1 to 100 ⁇ m.
- the thickness is preferably 2 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, and still more preferably 5 to 35 ⁇ m.
- the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a peeled sheet (separator) until it is practically used.
- constituent material of the separator examples include, for example, plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
- plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films
- porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
- a thin film can be used, but a plastic film is preferably used because of its excellent surface smoothness.
- the plastic film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer.
- a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a vinyl chloride co-polymer are used.
- examples thereof include a polymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
- the thickness of the separator is usually about 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
- mold release and antifouling treatment with a silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, silica powder, etc., coating type, kneading type, vapor deposition type It is also possible to carry out antistatic treatment such as.
- a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment, the peelability from the pressure-sensitive adhesive layer can be further improved.
- seat which carried out the peeling process used in preparation of said adhesive type optical member can be used as a separator of an adhesive type optical member as it is, and can simplify in the surface of a process.
- the support such as an optical member
- those used for forming an image display device such as a liquid crystal display device are used, and the type thereof is not particularly limited.
- the optical member includes a polarizing plate.
- a polarizing plate having a transparent protective film on one or both sides of a polarizer is generally used.
- the polarizer is not particularly limited, and various types can be used.
- polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
- hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
- examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
- a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable.
- the thickness of these polarizers is not particularly limited, but is generally about 5 to 80 ⁇ m.
- a polarizer in which a polyvinyl alcohol film is dyed with iodine and uniaxially stretched can be prepared, for example, by dyeing polyvinyl alcohol in an aqueous solution of iodine and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.
- Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching.
- the film can be stretched even in an aqueous solution such as boric acid or potassium iodide or in a water bath.
- Examples of the optical member used for the adhesive optical member of the present invention include a polarizing plate.
- a polarizing plate having a transparent protective film on one or both sides of a polarizer is generally used.
- thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is used.
- thermoplastic resins include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, cyclic Examples thereof include polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.
- a transparent protective film is bonded to one side of the polarizer by an adhesive layer.
- thermosetting resin such as a system or an ultraviolet curable resin
- a thermosetting resin such as a system or an ultraviolet curable resin
- the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent.
- the content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. .
- content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.
- the transparent protective film examples include a polymer film described in JP-A-2001-343529 (WO01 / 37007), for example, (A) a thermoplastic resin having a substituted and / or unsubstituted imide group in the side chain, B) Resin compositions containing thermoplastic resins having substituted and / or unsubstituted phenyl and nitrile groups in the side chains.
- a specific example is a film of a resin composition containing an alternating copolymer of isobutylene and N-methylmaleimide and an acrylonitrile / styrene copolymer.
- As the film a film made of a mixed extruded product of the resin composition or the like can be used. Since these films have a small phase difference and a small photoelastic coefficient, problems such as unevenness due to the distortion of the polarizing plate can be eliminated, and since the moisture permeability is small, the humidification durability is excellent.
- the thickness of the transparent protective film can be appropriately determined, but is generally about 1 to 500 ⁇ m from the viewpoints of workability such as strength and handleability, and thin layer properties. 1 to 300 ⁇ m is particularly preferable, and 5 to 200 ⁇ m is more preferable. The transparent protective film is particularly suitable when the thickness is from 5 to 150 ⁇ m.
- the protective film which consists of the same polymer material may be used for the front and back, and the protective film which consists of a different polymer material etc. may be used.
- the transparent protective film of the present invention it is preferable to use at least one selected from cellulose resin, polycarbonate resin, cyclic polyolefin resin and (meth) acrylic resin.
- Cellulose resin is an ester of cellulose and fatty acid.
- Specific examples of the cellulose ester resin include triacetyl cellulose, diacetyl cellulose, tripropionyl cellulose, dipropionyl cellulose and the like. Among these, triacetyl cellulose is particularly preferable.
- Many products of triacetylcellulose are commercially available, which is advantageous in terms of availability and cost. Examples of commercially available products of triacetylcellulose include trade names “UV-50”, “UV-80”, “SH-80”, “TD-80U”, “TD-TAC”, “UZ” manufactured by Fuji Film Co., Ltd. -TAC "and” KC series "manufactured by Konica. In general, these triacetyl celluloses have an in-plane retardation (Re) of almost zero, but a thickness direction retardation (Rth) of about 60 nm.
- Re in-plane retardation
- Rth thickness direction retardation
- a cellulose resin film having a small thickness direction retardation can be obtained, for example, by treating the cellulose resin.
- a base film such as polyethylene terephthalate, polypropylene or stainless steel coated with a solvent such as cyclopentanone or methyl ethyl ketone is bonded to a general cellulose film and dried by heating (for example, at 80 to 150 ° C. for about 3 to 10 minutes) ) And then peeling the base film; a solution obtained by dissolving norbornene resin, (meth) acrylic resin, etc. in a solvent such as cyclopentanone, methyl ethyl ketone, etc. is applied to a general cellulose resin film and dried by heating ( For example, a method of peeling the coated film after 80 to 150 ° C. for about 3 to 10 minutes) is mentioned.
- a fatty acid cellulose resin film with a controlled degree of fat substitution can be used as the cellulose resin film having a small thickness direction retardation.
- triacetyl cellulose has an acetic acid substitution degree of about 2.8.
- the Rth can be reduced by controlling the acetic acid substitution degree to 1.8 to 2.7.
- a plasticizer such as dibutyl phthalate, p-toluenesulfonanilide, acetyltriethyl citrate, etc.
- Rth can be controlled to be small.
- the addition amount of the plasticizer is preferably 40 parts by weight or less, more preferably 1 to 20 parts by weight, and further preferably 1 to 15 parts by weight with respect to 100 parts by weight of the fatty acid cellulose resin.
- cyclic polyolefin resin examples are preferably norbornene resins.
- the cyclic olefin-based resin is a general term for resins that are polymerized using a cyclic olefin as a polymerization unit, and is described in, for example, JP-A-1-240517, JP-A-3-14882, JP-A-3-122137, and the like. Resin.
- cyclic olefin ring-opening (co) polymers examples include cyclic olefin addition polymers, cyclic olefins and ⁇ -olefins such as ethylene and propylene (typically random copolymers), And graft polymers obtained by modifying them with an unsaturated carboxylic acid or a derivative thereof, and hydrides thereof.
- cyclic olefin include norbornene monomers.
- Various products are commercially available as cyclic polyolefin resins.
- trade names “ZEONEX” and “ZEONOR” manufactured by ZEON CORPORATION product names “ARTON” manufactured by JSR Corporation, “TOPAS” manufactured by TICONA, and product names manufactured by Mitsui Chemicals, Inc. “APEL”.
- Tg glass transition temperature
- the polarizing plate can be excellent in durability.
- the upper limit of Tg of the (meth) acrylic resin is not particularly limited, it is preferably 170 ° C. or less from the viewpoint of moldability. From (meth) acrylic resin, a film having in-plane retardation (Re) and thickness direction retardation (Rth) of almost zero can be obtained.
- any appropriate (meth) acrylic resin can be adopted as long as the effects of the present invention are not impaired.
- poly (meth) acrylic acid ester such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester- (Meth) acrylic acid copolymer, (meth) methyl acrylate-styrene copolymer (MS resin, etc.), a polymer having an alicyclic hydrocarbon group (for example, methyl methacrylate-cyclohexyl methacrylate copolymer, Methyl methacrylate- (meth) acrylate norbornyl copolymer, etc.).
- Preferable examples include C1-6 alkyl poly (meth) acrylates such as polymethyl (meth) acrylate. More preferred is a methyl methacrylate resin containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight).
- the (meth) acrylic resin examples include, for example, (Meth) acrylic resin having a ring structure in the molecule described in Acrypet VH and Acrypet VRL20A manufactured by Mitsubishi Rayon Co., Ltd., and JP-A-2004-70296. And a high Tg (meth) acrylic resin system obtained by intramolecular crosslinking or intramolecular cyclization reaction.
- (Meth) acrylic resin having a lactone ring structure can also be used as the (meth) acrylic resin. It is because it has high mechanical strength by high heat resistance, high transparency, and biaxial stretching.
- Examples of the (meth) acrylic resin having a lactone ring structure include JP 2000-230016, JP 2001-151814, JP 2002-120326, JP 2002-254544, and JP 2005. Examples thereof include (meth) acrylic resins having a lactone ring structure described in Japanese Patent No. 146084.
- the (meth) acrylic resin having a lactone ring structure preferably has a ring pseudo structure represented by the following general formula (Formula 1).
- R 1 , R 2 and R 3 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
- the organic residue may contain an oxygen atom.
- the content of the lactone ring structure represented by the general formula (Formula 1) in the structure of the (meth) acrylic resin having a lactone ring structure is preferably 5 to 90% by weight, more preferably 10 to 70% by weight, More preferably, it is 10 to 60% by weight, and particularly preferably 10 to 50% by weight.
- the content of the lactone ring structure represented by the general formula (Chemical Formula 1) in the structure of the (meth) acrylic resin having a lactone ring structure is less than 5% by weight, the heat resistance, solvent resistance, and surface hardness are low. May be insufficient. If the content of the lactone ring structure represented by the general formula (Chemical Formula 1) in the structure of the (meth) acrylic resin having a lactone ring structure is more than 90% by weight, molding processability may be poor.
- the (meth) acrylic resin having a lactone ring structure has a mass average molecular weight (sometimes referred to as a weight average molecular weight) of preferably 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, and particularly preferably. Is from 50,000 to 500,000. If the mass average molecular weight is out of the above range, it is not preferable from the viewpoint of moldability.
- the (meth) acrylic resin having a lactone ring structure preferably has a Tg of 115 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 125 ° C. or higher, and particularly preferably 130 ° C. or higher. Since Tg is 115 ° C. or higher, for example, when incorporated into a polarizing plate as a transparent protective film, it has excellent durability.
- the upper limit of Tg of the (meth) acrylic resin having the lactone ring structure is not particularly limited, it is preferably 170 ° C. or less from the viewpoint of moldability and the like.
- the (meth) acrylic resin having a lactone ring structure is more preferable as the total light transmittance of a molded product obtained by injection molding measured by a method according to ASTM-D-1003 is higher, preferably 85 % Or more, more preferably 88% or more, and still more preferably 90% or more.
- the total light transmittance is a measure of transparency. If the total light transmittance is less than 85%, the transparency may be lowered.
- the transparent protective film may be subjected to surface modification treatment in order to improve adhesiveness with the polarizer before applying the adhesive.
- Specific examples of the treatment include corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, glow treatment, saponification treatment, and treatment with a coupling agent.
- an antistatic layer can be appropriately formed.
- the surface of the transparent protective film to which the polarizer is not adhered may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, antisticking, diffusion or antiglare.
- the support such as an optical film
- examples of the support include a reflection plate, an anti-transmission plate, a liquid crystal display device such as the retardation plate (including wavelength plates such as 1/2 and 1/4), a visual compensation film, and a brightness enhancement film.
- an optical layer that may be used for the formation of the like. These can be used alone as an optical film, or can be laminated on the polarizing plate for practical use and used as one layer or two or more layers.
- the pressure-sensitive adhesive sheet of the present invention is not limited, it can be preferably used for forming various image display devices such as liquid crystal display devices.
- the liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, an adhesive sheet, and a lighting system as necessary, and incorporating a drive circuit. There is no limitation in particular except the point which uses an adhesive sheet, and it can apply according to the past.
- an arbitrary type such as an arbitrary type such as a TN type, STN type, ⁇ type, VA type, or IPS type can be used.
- Appropriate liquid crystal display devices such as a liquid crystal display device in which an adhesive sheet is disposed on one side or both sides of a liquid crystal cell and a backlight or a reflector used in an illumination system can be formed.
- the optical film according to the present invention can be installed on one side or both sides of the liquid crystal cell.
- optical films may be the same or different.
- a liquid crystal display device for example, a single layer or a suitable part such as a diffusing plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusing plate, a backlight, etc. Two or more layers can be arranged.
- the weight average molecular weight of the obtained (meth) acrylic polymer was measured by GPC (gel permeation chromatography).
- the sample used was a filtrate obtained by dissolving the sample in tetrahydrofuran to make a 0.1 wt% solution, which was allowed to stand overnight, and then filtered through a 0.45 ⁇ m membrane filter.
- Example 1 (Preparation of acrylic polymer)
- 100 parts by weight of n-butyl acrylate, 1 part by weight of 4-hydroxybutyl acrylate, and 2,2′-azobis as a polymerization initiator
- nitrogen gas was introduced with gentle stirring and the atmosphere was purged with nitrogen for 1 hour.
- a polymerization reaction was carried out for 15 hours to prepare an acrylic polymer solution having a weight average molecular weight of 600,000.
- a silicone compound (KR-9706 manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 100 parts by weight of titanium oxide (TTO-51C manufactured by Ishihara Sangyo), and a bead mill (Ultra Apex Mill manufactured by Kogyo Kogyo Co., Ltd.) using 460 parts by weight of methyl ethyl ketone as a dispersion medium. ) For 2 hours to obtain a 40 nm titania dispersion.
- the thickness of the pressure-sensitive adhesive layer after drying is 20 ⁇ m on one side of a 38 ⁇ m polyethylene terephthalate (PET) film (DIAFOIL MRF38, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) subjected to silicone treatment. And dried at 150 ° C. for 3 minutes to form an adhesive layer and prepare an adhesive sheet.
- PET polyethylene terephthalate
- Example 2 (Preparation of acrylic polymer) The same operation as in Example 1 was carried out except that the styrene low molecular weight polymer was changed to 200 parts by weight as the solid content and the titania nanoparticles were changed to 300 parts by weight as the solid content to obtain the pressure-sensitive adhesive sheet of Example 2. It was.
- Comparative Example 1 In Example 1, the same operation was performed except that the styrene low molecular weight polymer was changed to 60 parts by weight as a solid content and the titania nanoparticles were changed to 60 parts by weight as a solid content to obtain a pressure-sensitive adhesive sheet of Comparative Example 1. .
- Comparative Example 2 Exactly the same operation was performed except that the styrene low molecular weight polymer was changed to Crystallex 3085 (Mw950, manufactured by Eastman Chemical Co., Ltd.) in Example 2, and the pressure-sensitive adhesive sheet of Comparative Example 2 was obtained.
- Comparative Example 3 Exactly the same operation was performed except that the styrene low molecular weight polymer was changed to Picotex LC (Mw 1110, manufactured by Rika Finetech Co., Ltd.) in Example 2 to obtain an adhesive sheet of Comparative Example 3.
- Picotex LC Mw 1110, manufactured by Rika Finetech Co., Ltd.
- Comparative Example 4 Exactly the same operation was performed except that the styrene low molecular weight polymer was changed to Crystallex 1120 (Mw2250, manufactured by Eastman Chemical Co., Ltd.) in Example 2, and the pressure-sensitive adhesive sheet of Comparative Example 4 was obtained.
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- Health & Medical Sciences (AREA)
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Abstract
Description
該(メタ)アクリル系ポリマー100重量部に対して、120~400重量部の、不飽和二重結合を有する重合性の官能基を有しかつ芳香族環を有する芳香族環含有モノマーから構成される、ゲルパーミネーションクロマトグラフィーによる重量平均分子量が200以上900以下の芳香族系ポリマー;および
該(メタ)アクリル系ポリマー100重量部に対して、150~600重量部の、平均粒径100nm以下のチタン系ナノ粒子を含有してなることを特徴とする粘着剤組成物、に関する。
前記透明保護フィルムは、接着剤を塗工する前に、偏光子との接着性を向上させるために、表面改質処理を行ってもよい。具体的な処理としては、コロナ処理、プラズマ処理、フレーム処理、オゾン処理、プライマー処理、グロー処理、ケン化処理、カップリング剤による処理などがあげられる。また適宜に帯電防止層を形成することができる。
得られた(メタ)アクリル系ポリマーの重量平均分子量は、GPC(ゲル・パーミエー
ション・クロマトグラフィー)により測定した。サンプルは、試料をテトラヒドロフランに溶解して0.1重量%の溶液とし、これを一晩静置した後、0.45μmのメンブレンフィルターで濾過した濾液を用いた。
・分析装置:東ソー社製、HLC-8120GPC
・カラム:東ソー社製、(メタ)アクリル系ポリマー:GM7000HXL+GMHXL+GMHXL
芳香族系ポリマー:G3000HXL+2000HXL+G1000HXL
・カラムサイズ;各7.8mmφ×30cm 計90cm
・溶離液:テトラヒドロフラン(濃度0.1重量%)
・流量:0.8ml/min
・入口圧:1.6MPa
・検出器:示差屈折計(RI)
・カラム温度:40℃
・ 注入量:100μl
・ 溶離液:テトラヒドロフラン
・ 検出器:示差屈折計
・ 標準試料:ポリスチレン
乾燥・架橋した粘着剤(最初の重量W1)を、酢酸エチル溶液に浸漬して、室温で1週間放置した後、不溶分を取り出し、乾燥させた重量(W2)を測定し、下記のように求めた。
ゲル分率=(W2/W1)×100
(アクリル系ポリマーの調製)
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、n-ブチルアクリレート100重量部、4-ヒドロキシブチルアクリレート1重量部、重合開始剤として2,2’-アゾビスイソブチロニトリル0.1重量部を酢酸エチル100重量部とトルエン100重量部と共に仕込み、緩やかに攪拌しながら窒素ガスを導入して1時間窒素置換した後、フラスコ内の液温を55℃付近に保って15時間重合反応を行い、重量平均分子量60万のアクリル系ポリマー溶液を調製した。
(アクリル系ポリマーの調製)
実施例1において、スチレン低分子量ポリマーを固形分にして200重量部に、チタニアナノ粒子を固形分にして300重量部に変えた以外は、全く同じ操作を行い、実施例2の粘着剤シートを得た。
実施例1において、スチレン低分子量ポリマーを固形分にして60重量部に、チタニアナノ粒子を固形分にして60重量部に変えた以外は全く同じ操作を行い、比較例1の粘着剤シートを得た。
実施例2において、スチレン低分子量ポリマーをクリスタレックス3085(Mw950、イーストマンケミカル社製)に変えた以外は全く同じ操作を行い、比較例2の粘着剤シートを得た。
実施例2において、スチレン低分子ポリマーをピコテックスLC(Mw1110、理化ファインテク社製)に変えた以外は全く同じ操作を行い、比較例3の粘着剤シートを得た。
実施例2において、スチレン低分子量ポリマーをクリスタレックス1120(Mw2250、イーストマンケミカル社製)に変えた以外は全く同じ操作を行い、比較例4の粘着剤シートを得た。
実施例および比較例で得られたサンプルを、幅20mm×長さ約100mmに裁断し、厚さ0.5mmの無アルカリガラス板(コーニング社製、1737)に、2kgのロール一往復で貼付け、次いで50℃、0.5MPaで30分間オートクレーブ処理して完全に密着させた後、剥離角度90°、剥離速度300mm/分で剥離接着を測定した。
実施例および比較例で得られたサンプルに、25℃の雰囲気で、ナトリウムD線を照射し、アッベ屈折率計(ATAGO社製DR-M2)にて屈折率を測定した。
Claims (8)
- モノマー成分として、CH2=C(R1)COOR2(但し、R1は、水素またはメチル基、R2は、炭素数1から20までの無置換のアルキル基または置換されたアルキル基を表す)で表される(メタ)アクリレートを50重量%以上含有し、ゲルパーミネーションクロマトグラフィーによる重量平均分子量が50万以上300万以下の実質的に酸成分を含有しない(メタ)アクリル系ポリマー;
該(メタ)アクリル系ポリマー100重量部に対して、120~400重量部の、不飽和二重結合を有する重合性の官能基を有しかつ芳香族環を有する芳香族環含有モノマーから構成される、ゲルパーミネーションクロマトグラフィーによる重量平均分子量が200以上900以下の芳香族系ポリマー;および
該(メタ)アクリル系ポリマー100重量部に対して、150~600重量部の、平均粒径100nm以下のチタン系ナノ粒子を含有してなることを特徴とする粘着剤組成物。 - 前記(メタ)アクリル系ポリマーが、さらにCH2=C(R1)COOCnH2nOH(但し、R1は、水素またはメチル基、nは、1から10までの整数を表す)で表される水酸基含有(メタ)アクリレートによる単位を0.05~10重量%含有してなる共重合体であることを特徴とする請求項1記載の粘着剤組成物。
- さらに、前記(メタ)アクリル系ポリマー100重量部に対して、架橋剤を、0.02から2重量部含有することを特徴とする請求項1または2記載の粘着剤組成物。
- 前記(メタ)アクリル系ポリマーが、幹部を構成する主鎖とは異なる組成からなる側鎖を有するグラフトポリマーであることを特徴とする請求項1から3までのいずれかに記載の粘着剤組成物。
- 請求項1から4のいずれかに記載の粘着剤組成物から得られることを特徴とする粘着剤層。
- ゲル分率が40~90重量%であることを特徴とする請求項5記載の粘着剤層。
- ヘイズ値が20%以下であることを特徴とする請求項5または6記載の粘着剤層。
- 支持体の少なくとも片側に、請求項5から7までのいずれかに記載の粘着剤層が形成されていることを特徴とする粘着剤シート。
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