WO2010126054A1 - 光学フィルム用粘着剤組成物、光学フィルム用粘着剤層、粘着型光学フィルムおよび画像表示装置 - Google Patents
光学フィルム用粘着剤組成物、光学フィルム用粘着剤層、粘着型光学フィルムおよび画像表示装置 Download PDFInfo
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- G02B1/105—
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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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
-
- 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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
Definitions
- a pressure-sensitive adhesive layer is formed on at least one surface of an optical film by the pressure-sensitive adhesive composition for optical films having excellent removability (reworkability) and excellent durability in an adhesive state, and the pressure-sensitive adhesive composition.
- the present invention relates to an adhesive optical film.
- the present invention relates to an image display device such as a liquid crystal display device, an organic EL display device and a PDP using the adhesive optical film.
- the optical film a polarizing plate, a phase difference plate, an optical compensation film, a brightness enhancement film, and a film in which these are laminated can be used.
- polarizing elements In the liquid crystal display device and the like, it is indispensable to dispose polarizing elements on both sides of the liquid crystal cell because of its image forming method, and generally a polarizing plate is attached.
- various optical elements have been used for liquid crystal panels in order to improve the display quality of displays.
- a retardation plate for preventing coloring For example, a viewing angle widening film for improving the viewing angle of a liquid crystal display, and a brightness enhancement film for increasing the contrast of the display are used. These films are collectively called optical films.
- an adhesive is usually used.
- the adhesion between the optical film and the liquid crystal cell, or the optical film is usually in close contact with each other using an adhesive in order to reduce the loss of light.
- the adhesive since the adhesive has the merit that a drying step is not required for fixing the optical film, the adhesive is an adhesive optical film provided in advance as an adhesive layer on one side of the optical film. Generally used.
- Necessary characteristics required for the pressure-sensitive adhesive include that when the optical film is bonded to the liquid crystal cell, the optical film is removed from the liquid crystal panel even when the bonding position is wrong or a foreign object is caught in the bonding surface.
- the liquid crystal cell may be reused by peeling off. In such a peeling step, re-peelability (reworkability) that can easily peel off the optical film from the liquid crystal panel without adhesive residue is required.
- re-peelability reworkability
- the use of thin liquid crystal panels using chemically etched glass has increased, making it difficult to maintain reworkability and workability of optical films from the thin liquid crystal panels. It has become.
- the pressure-sensitive adhesive can be processed without forming a pressure-sensitive adhesive stain or missing after forming a pressure-sensitive adhesive layer on the optical film, and further by heating and humidification normally performed as an environmental promotion test. For the durability test, it is required that defects such as peeling and floating due to the adhesive do not occur.
- the optical film pressure-sensitive adhesive is required to improve display unevenness (peripheral unevenness and corner unevenness) due to white spots on the periphery.
- an adhesive for optical films for example, an acrylic resin (1) having a weight average molecular weight of 1,000,000 to 2,000,000, an acrylic resin (2) having a weight average molecular weight of 50,000 to 500,000, a silicone oligomer (3), and a crosslinking agent (4).
- a pressure-sensitive adhesive obtained by blending has been proposed (Patent Document 1).
- a copolymer having a weight average molecular weight of 1,000,000 to 2,000,000 obtained by polymerizing a monomer (a) having a reactive functional group and a monomer (b) copolymerizable with the monomer (a) ( A) 100 parts, 20 to 150 parts of copolymer (B) having a weight average molecular weight of 10,000 to 100,000 obtained by polymerizing monomers (c) and (d) in the presence of copolymer (A)
- a pressure-sensitive adhesive composition containing 0.1 to 10 parts of a polyol (C) that is liquid at a polymerization degree of 3 or more and 25 ° C. and 0.003 to 3 parts of a polyfunctional compound (D) has been proposed (Patent Document 2). ).
- the adhesive for optical films is required to have durability in an adhesive state in addition to reworkability.
- an adhesive for optical films for example, a) 100 parts by weight of an acrylic copolymer containing a hydroxy group but not containing a carboxyl group, b) 0.01 to 10 parts by weight of a crosslinking agent, and c) HLB
- An acrylic pressure-sensitive adhesive composition containing 0.01 to 5.0 parts by weight of a polyether-modified polydimethylsiloxane copolymer having a value of 4 to 13 has been proposed (Patent Document 3).
- an acrylic system obtained by copolymerizing a silane compound (a) having a polymerizable double bond group and an alkoxy group, a functional group-containing monomer (b), and a non-functional alkyl (meth) acrylate monomer (c).
- An adhesive composition comprising an oligomer type silane coupling agent (A), an acrylic copolymer (B) other than the silane coupling agent (A), and a crosslinking agent (C) has been proposed (patent) Reference 4).
- the optical film pressure-sensitive adhesive is required to improve display unevenness (peripheral unevenness and corner unevenness) due to white spots in the periphery, and to improve durability in addition to reworkability.
- a pressure-sensitive adhesive composition capable of improving the viscosity.
- the present invention provides a pressure-sensitive adhesive layer that can satisfy reworkability that allows an optical film to be easily peeled off from a liquid crystal panel or the like without adhesive residue, and durability that does not cause peeling or floating when the optical film is bonded. It aims at providing the adhesive composition for optical films which can be formed.
- the present invention can satisfy reworkability that allows an optical film to be easily peeled off from a liquid crystal panel or the like without adhesive residue, and durability that does not cause peeling or floating when the optical film is bonded, and It aims at providing the adhesive composition for optical films which can form the adhesive layer which can improve the display nonuniformity by the white blank of a part.
- Another object of the present invention is to provide a pressure-sensitive adhesive optical film having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition for optical films, and further to provide an image display device using the pressure-sensitive adhesive optical film.
- the present invention comprises a (meth) acrylic polymer (A); and a polyether skeleton, and at least one terminal, Formula (1): —SiR a M 3-a
- R is an optionally substituted monovalent organic group having 1 to 20 carbon atoms
- M is a hydroxyl group or a hydrolyzable group
- a is an integer of 1 to 3
- the plurality of R may be the same or different from each other
- the plurality of M may be the same or different from each other.
- the present invention relates to a pressure-sensitive adhesive composition for an optical film comprising a polyether compound (B) having a reactive silyl group.
- the polyether skeleton of the polyether compound (B) is preferably a repeating structural unit of a linear or branched oxyalkylene group having 1 to 10 carbon atoms. .
- R is an optionally substituted monovalent organic group having 1 to 20 carbon atoms
- M is a hydroxyl group or a hydrolyzable group
- a is an integer of 1 to 3
- the plurality of R may be the same or different from each other
- the plurality of M may be the same or different from each other.
- Z is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms
- R, M, X and Y are the same as above.
- OA is the same as the above AO
- n is the same as the above.
- Q is a divalent or higher valent hydrocarbon group having 1 to 10 carbon atoms.
- M is the same as the valence of the hydrocarbon group. ) Is preferred.
- the reactive silyl group in the polyether compound (B) is represented by the following general formula (3): Wherein R 1 , R 2 and R 3 are monovalent hydrocarbon groups having 1 to 6 carbon atoms and may be the same or different in the same molecule. A silyl group is preferred.
- the polyether compound (B) is a compound represented by the general formula (2), Formula (4): Z 0 —A 2 —O— (A 1 O) n —Z 1
- a 1 O is an oxyalkylene group having 2 to 6 carbon atoms
- n is 1 to 1700, and represents the average number of moles of A 1 O.
- Z 1 is a hydrogen atom, or —A 2 .
- a 2 is -Z 0 is an alkylene group having 2 to 6 carbon atoms.
- Z 0 represents the general formula (3): Wherein R 1 , R 2 and R 3 are monovalent hydrocarbon groups having 1 to 6 carbon atoms and may be the same or different in the same molecule. It is a silyl group. ) Is preferred.
- the polyether compound (B) is a compound represented by the general formula (2), Formula (5): Z 0 —A 2 —NHCOO— (A 1 O) n —Z 2 (Wherein A 1 O is an oxyalkylene group having 2 to 6 carbon atoms, n is 1 to 1700, and represents the average number of moles added of A 1 O.
- Z 2 represents a hydrogen atom or —CONH— A 2 -Z 0.
- a 2 is an alkylene group having 2 to 6 carbon atoms.
- Z 0 represents the general formula (3): Wherein R 1 , R 2 and R 3 are monovalent hydrocarbon groups having 1 to 6 carbon atoms and may be the same or different in the same molecule. It is a silyl group. ) Is more preferable.
- the polyether compound (B) is a compound represented by the general formula (2), Formula (6): Z 3 -O- ( A 1 O) n -C ⁇ -CH 2 - (A 1 O) n -Z 3 ⁇ 2
- a 1 O is an oxyalkylene group having 2 to 6 carbon atoms
- n is 1 to 1700, and represents the average number of moles added of A 1 O.
- Z 3 represents a hydrogen atom or —A 2 -Z 0 and at least one Z 3 is -A 2 -Z 0.
- a 2 is an alkylene group having 2 to 6 carbon atoms.
- Z 0 represents the general formula (3): Wherein R 1 , R 2 and R 3 are monovalent hydrocarbon groups having 1 to 6 carbon atoms and may be the same or different in the same molecule. It is a silyl group. ) Is more preferable.
- the polyether compound (B) preferably has a number average molecular weight of 300 to 100,000.
- the optical film pressure-sensitive adhesive composition preferably contains 0.001 to 20 parts by weight of the polyether compound (B) with respect to 100 parts by weight of the (meth) acrylic polymer (A).
- the (meth) acrylic polymer (A) can preferably be one containing an alkyl (meth) acrylate and a hydroxyl group-containing monomer as monomer units.
- the (meth) acrylic polymer (A) may preferably be one containing an alkyl (meth) acrylate and a carboxyl group-containing monomer as monomer units.
- the (meth) acrylic polymer (A) contains, as monomer units, an alkyl (meth) acrylate and a polymerizable aromatic ring-containing monomer (meth) acrylic polymer (A ′). Can be preferably used.
- the (meth) acrylic polymer (A ′) preferably contains 1 to 50% by weight of a polymerizable aromatic ring-containing monomer as a monomer unit.
- (meth) acrylic polymer (A ′) a monomer unit further containing a hydroxyl group-containing monomer can be preferably used.
- (meth) acrylic polymer (A ′) a monomer unit further containing a carboxyl group-containing monomer can be preferably used.
- the optical film pressure-sensitive adhesive composition may further contain a crosslinking agent.
- the crosslinking agent (C) is preferably contained in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (A).
- the crosslinking agent (C) is preferably at least one selected from an isocyanate compound and a peroxide.
- the optical film pressure-sensitive adhesive composition may further contain 0.001 to 5 parts by weight of the silane coupling agent (D) with respect to 100 parts by weight of the (meth) acrylic polymer (A).
- the weight average molecular weight of the (meth) acrylic polymer (A) is preferably 500,000 to 4,000,000.
- the present invention also relates to an optical film pressure-sensitive adhesive layer, which is formed of the optical film pressure-sensitive adhesive composition.
- the present invention also relates to an adhesive optical film characterized in that the optical film adhesive layer is formed on at least one side of the optical film.
- the said adhesive optical film can have an easily bonding layer between an optical film and the adhesive layer for optical films.
- the present invention also relates to an image display device characterized by using at least one adhesive optical film.
- the pressure-sensitive adhesive composition for an optical film of the present invention is a polyether having a polyether skeleton and a reactive silyl group at least at one end in addition to the (meth) acrylic polymer (A) as a base polymer.
- the pressure-sensitive adhesive optical film having the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition for optical films of the present invention contains the polyether compound (B), whereby the pressure-sensitive adhesive optical film is used as a liquid crystal cell or the like. Adhesive optical film can be easily removed from the liquid crystal cell, etc., even if it has been pasted for a long time due to various processes or stored at a high temperature.
- the adhesive optical film can be easily peeled from the large liquid crystal cell.
- the pressure-sensitive adhesive optical film of the present invention has good durability and can suppress the occurrence of peeling or floating in a state of being attached to a liquid crystal cell or the like.
- the adhesive optical film has good durability against various optical films (for example, triacetyl cellulose resin, (meth) acrylic resin, or norbornene resin), and can be peeled off when attached to a liquid crystal cell or the like. The occurrence of floating etc. can be suppressed.
- the (meth) acrylic polymer (A) is the (meth) acrylic polymer (A ′)
- the following effects are obtained. That is, when an image display device such as a liquid crystal display device using an adhesive optical film such as an adhesive polarizing plate is subjected to heating or humidifying conditions, peripheral unevenness or corner unevenness is caused in the peripheral portion of the liquid crystal panel or the like. Although white unevenness may cause display unevenness and display failure may occur, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive optical film of the present invention uses the above pressure-sensitive adhesive composition for optical films, so the periphery of the display screen The display unevenness of the part can be suppressed.
- the base polymer (meth) acrylic polymer (A) contains a polymerizable aromatic ring-containing monomer in addition to the alkyl (meth) acrylate as a monomer unit. Therefore, it is considered that display unevenness in the peripheral portion is suppressed by the polymerizable aromatic ring-containing monomer.
- the pressure-sensitive adhesive composition for an optical film of the present invention contains a (meth) acrylic polymer (A) as a base polymer.
- the (meth) acrylic polymer (A) usually contains an alkyl (meth) acrylate as a main component as a monomer unit.
- (Meth) acrylate refers to acrylate and / or methacrylate, and (meth) of the present invention has the same meaning.
- alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer (A) include linear or branched alkyl groups having 1 to 18 carbon atoms.
- the alkyl group includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, hexyl group, cyclohexyl group, heptyl group, 2-ethylhexyl group, isooctyl group, nonyl group, decyl group.
- alkyl groups preferably have an average carbon number of 3 to 9.
- alkyl (meth) acrylates containing an aromatic ring such as phenoxyethyl (meth) acrylate can be used.
- the alkyl (meth) acrylate containing an aromatic ring can be used by mixing a polymer obtained by polymerizing it with the (meth) acrylic polymer exemplified above, but from the viewpoint of transparency, it contains an aromatic ring.
- the alkyl (meth) acrylate is preferably copolymerized with the alkyl (meth) acrylate.
- the (meth) acrylic polymer (A) has a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group for the purpose of improving adhesiveness and heat resistance.
- One or more copolymerization monomers can be introduced by copolymerization.
- copolymerized monomers include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid 6 Hydroxyl-containing monomers such as hydroxyhexyl, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate and (4-hydroxymethylcyclohexyl) -methyl acrylate Carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; acid anhydrides such as maleic anhydride and itaconic anhydride Monomer-containing monomer; Caprolac of acrylic acid Adducts such as styrene sulfonic acid
- (N-substituted) amides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, etc.
- Further modifying monomers include vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine, N- Vinyl monomers such as vinylcarboxylic amides, styrene, ⁇ -methylstyrene, N-vinylcaprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; (Meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) acrylic acid meso Glycol acrylic ester monomers such as xypolypropylene glycol; acrylic ester monomers such as
- examples of copolymerizable monomers other than the above include silane-based monomers containing silicon atoms.
- examples of the silane monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyltrimethoxysilane.
- copolymer monomers examples include tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate (Meth) acryloyl such as esterified product of (meth) acrylic acid and polyhydric alcohol such as caprolactone-modified dipentaerythritol hexa (meth) acrylate A polyfunctional monomer having
- the (meth) acrylic polymer (A) is mainly composed of alkyl (meth) acrylate in the weight ratio of all constituent monomers, and the proportion of the copolymerized monomer in the (meth) acrylic polymer (A) is particularly limited.
- the proportion of the copolymerization monomer is preferably about 0 to 20%, about 0.1 to 15%, and more preferably about 0.1 to 10% in the weight ratio of all the constituent monomers.
- hydroxyl group-containing monomers and carboxyl group-containing monomers are preferably used from the viewpoint of adhesion and durability.
- a hydroxyl group-containing monomer and a carboxyl group-containing monomer can be used in combination.
- These copolymerization monomers serve as reaction points with the crosslinking agent when the pressure-sensitive adhesive composition contains a crosslinking agent. Since a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and the like are rich in reactivity with an intermolecular crosslinking agent, they are preferably used for improving the cohesiveness and heat resistance of the resulting pressure-sensitive adhesive layer.
- a hydroxyl group-containing monomer is preferable from the viewpoint of reworkability, and a carboxyl group-containing monomer is preferable from the viewpoint of achieving both durability and reworkability.
- the proportion is preferably 0.01 to 2% by weight, more preferably 0.03 to 1.5% by weight, and even more preferably 0.05 to 1% by weight. Is preferred.
- the proportion is preferably 0.1 to 10% by weight, more preferably 0.2 to 8% by weight, and further preferably 0.6 to 6% by weight. .
- the (meth) acrylic polymer (A) preferably contains an alkyl (meth) acrylate and a polymerizable aromatic ring-containing monomer as monomer units.
- this (meth) acrylic polymer (A) will be shown as (meth) acrylic polymer (A ′).
- the content of the alkyl (meth) acrylate in the (meth) acrylic polymer (A ′) is a (meth) acrylic polymer (A ′) including a polymerizable aromatic ring-containing monomer and further the following copolymerizable monomer.
- the content of the alkyl (meth) acrylate is preferably 40% by weight or more, and more preferably 50% by weight or more. Further, it is preferably 60% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more.
- the polymerizable aromatic ring-containing monomer is a compound containing an aromatic group in its structure and a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
- the aromatic group include a benzene ring, a naphthalene ring, a biphenyl ring, and a heterocyclic ring.
- the heterocyclic ring include a morpholine ring, a piperidine ring, a pyrrolidine ring, and a piperazine ring.
- the compound include (meth) acrylates containing an aromatic group.
- (meth) acrylates containing aromatic groups include, for example, benzyl (meth) acrylate, phenyl (meth) acrylate, o-phenylphenol (meth) acrylate phenoxy (meth) acrylate, and phenoxyethyl (meth) acrylate.
- examples of the (meth) acrylate containing a heterocyclic ring include thiol (meth) acrylate, pyridyl (meth) acrylate, pyrrole (meth) acrylate, and the like.
- examples of the (meth) acrylic monomer containing a heterocyclic ring include N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, and N-acryloylpyrrolidine.
- vinyl compound containing an aromatic group examples include, for example, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine, N-vinyl carboxylic acid amides, Examples thereof include styrene and ⁇ -methylstyrene.
- the polymerizable aromatic ring-containing monomer may contain a functional group such as sulfonic acid in addition to the polymerizable unsaturated double bond such as (meth) acryloyl group and vinyl group.
- a functional group such as sulfonic acid
- examples of the polymerizable aromatic ring-containing monomer having the functional group include styrene sulfonic acid and (meth) acryloyloxynaphthalene sulfonic acid.
- the polymerizable aromatic ring-containing monomer is preferably a (meth) acrylate containing an aromatic group from the viewpoint of adhesive properties and durability, among which benzyl (meth) acrylate and phenoxyethyl (meth) acrylate are preferable, Particularly preferred is benzyl (meth) acrylate.
- the ratio of the polymerizable aromatic ring-containing monomer in the (meth) acrylic polymer (A ′) is 1 to 50 wt% in the weight ratio of all the constituent monomers (100 wt%) of the (meth) acrylic polymer (A ′). It is preferable to contain it in the ratio of%. Further, the content of the polymerizable aromatic ring-containing monomer is preferably 1 to 35% by weight, more preferably 1 to 20% by weight, further preferably 7 to 18% by weight, and further preferably 10 to 16% by weight.
- (meth) acrylic polymer (A ′) a copolymerization monomer represented by the (meth) acrylic polymer (A) can be used.
- the proportion of the copolymerization monomer in the (meth) acrylic polymer (A ′) is such that all constituent monomers (100) of the (meth) acrylic polymer (A ′) including the alkyl (meth) acrylate and the polymerizable aromatic ring-containing monomer.
- the weight ratio is preferably about 0 to 20%, more preferably about 0.1 to 15%, and further preferably about 0.1 to 10%.
- hydroxyl group-containing monomers and carboxyl group-containing monomers are preferably used from the viewpoint of adhesion and durability.
- a hydroxyl group-containing monomer and a carboxyl group-containing monomer can be used in combination.
- These copolymerization monomers serve as reaction points with the crosslinking agent when the pressure-sensitive adhesive composition contains a crosslinking agent. Since a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and the like are rich in reactivity with an intermolecular crosslinking agent, they are preferably used for improving the cohesiveness and heat resistance of the resulting pressure-sensitive adhesive layer.
- a hydroxyl group-containing monomer is preferable from the viewpoint of reworkability, and a carboxyl group-containing monomer is preferable from the viewpoint of achieving both durability and reworkability.
- the proportion is preferably 0.01 to 2% by weight, more preferably 0.03 to 1.5% by weight, and even more preferably 0.05 to 1% by weight. Is preferred.
- the proportion is preferably 0.1 to 10% by weight, more preferably 0.2 to 8% by weight, and further preferably 0.6 to 6% by weight. .
- the (meth) acrylic polymer (A) of the present invention usually has a weight average molecular weight in the range of 500,000 to 4,000,000. In view of durability, particularly heat resistance, it is preferable to use those having a weight average molecular weight of 800,000 to 3,000,000. Furthermore, it is preferably 1,400,000 to 2,700,000, more preferably 1,700,000 to 2,500,000, and even more preferably 1,800,000 to 2,400,000. A weight average molecular weight of less than 500,000 is not preferable in terms of heat resistance. Moreover, when a weight average molecular weight becomes larger than 4 million, it is unpreferable also at the point which bonding property and adhesive force fall.
- the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
- the (meth) acrylic polymer (A) to be 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 the (meth) acrylic polymer (A) can be controlled by the amount of polymerization initiator, the amount of chain transfer agent used, and the reaction conditions, and the amount used is appropriately adjusted according to these types.
- 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 preferably about 0.06 to 0.2 parts by weight, more preferably about 0.08 to 0.175 parts by weight, based on 100 parts by weight of the total amount of monomer 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, polyoxyethylene-polyoxypropylene block polymer and the like can be mentioned. 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 Asahi Denka Kogyo Co., Ltd.), 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 pressure-sensitive adhesive composition of the present invention contains a polyether compound (B) in addition to the (meth) acrylic polymer (A).
- the polyether compound (B) has a polyether skeleton, and at least one terminal has the following general formula (1): —SiR a M 3-a (In the formula, R is an optionally substituted monovalent organic group having 1 to 20 carbon atoms, M is a hydroxyl group or a hydrolyzable group, and a is an integer of 1 to 3)
- R is an optionally substituted monovalent organic group having 1 to 20 carbon atoms
- M is a hydroxyl group or a hydrolyzable group
- a is an integer of 1 to 3
- the plurality of R may be the same or different from each other
- the plurality of M may be the same or different from each other. It has a reactive silyl group represented.
- the reactive silyl group in the polyether compound (B) has at least one terminal per molecule.
- the polyether compound (B) is a straight-chain compound, it has one or two reactive silyl groups at the terminal, but preferably has two at the terminal.
- the end includes a side chain end in addition to the main chain end, and has at least one reactive silyl group at the end.
- the number of reactive silyl groups is preferably 2 or more, more preferably 3 or more.
- the polyether compound (B) having a reactive silyl group has the above-mentioned reactive silyl group at least at a part of its molecular end, and at least one, preferably 1.1 to 5, more preferably in the molecule. Preferably has 1.1 to 3 reactive silyl groups.
- R is a monovalent organic group having 1 to 20 carbon atoms which may have a substituent.
- R is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms, or a phenyl group, and more preferably an alkyl group having 1 to 6 carbon atoms. Particularly preferred is a methyl group.
- M is a hydroxyl group or a hydrolyzable group.
- the hydrolyzable group is directly bonded to a silicon atom and generates a siloxane bond by a hydrolysis reaction and / or a condensation reaction.
- the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, an alkenyloxy group, a carbamoyl group, an amino group, an aminooxy group, and a ketoximate group.
- the hydrolyzable group has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less.
- an alkoxy group or an alkenyloxy group having 4 or less carbon atoms is preferable, and a methoxy group or an ethoxy group is particularly preferable.
- the plurality of M may be the same or different from each other.
- the reactive silyl group represented by the general formula (1) is represented by the following general formula (3): Wherein R 1 , R 2 and R 3 are monovalent hydrocarbon groups having 1 to 6 carbon atoms and may be the same or different in the same molecule. A silyl group is preferred.
- R 1 examples of R 2 and R 3 for example, a straight or branched chain alkyl group having 1 to 6 carbon atoms, straight or carbon branched Examples thereof include an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, and a phenyl group.
- Specific examples of —OR 1 , —OR 2 and —OR 3 in the formula include, for example, methoxy group, ethoxy group, propoxy group, propenyloxy group, phenoxy group and the like. Of these, a methoxy group and an ethoxy group are preferable, and a methoxy group is particularly preferable.
- the polyether skeleton of the polyether compound (B) preferably has a repeating structural unit of a linear or branched oxyalkylene group having 1 to 10 carbon atoms.
- the structural unit of the oxyalkylene group preferably has 2 to 6 carbon atoms, and more preferably 3 carbon atoms.
- the repeating structural unit of the oxyalkylene group may be a repeating structural unit of one kind of oxyalkylene group, or may be a repeating structural unit of a block unit or random unit of two or more kinds of oxyalkylene groups.
- Examples of the oxyalkylene group include an oxyethylene group, an oxypropylene group, and an oxybutylene group.
- these oxyalkylene groups those having a structural unit of an oxypropylene group (particularly —CH 2 CH (CH 3 ) O—) are preferable from the viewpoint of ease of production of the material, material stability, and the like.
- the polyether compound (B) preferably has a main chain substantially composed of a polyether skeleton, in addition to the reactive silyl group.
- the main chain substantially consists of a polyoxyalkylene chain means that a small amount of other chemical structures may be included.
- other chemical structures it indicates that, for example, a chemical structure of an initiator in the case of producing a repeating structural unit of an oxyalkylene group related to a polyether skeleton and a linking group with a reactive silyl group may be included.
- the repeating structural unit of the oxyalkylene group related to the polyether skeleton is preferably 50% by weight or more, and more preferably 80% by weight or more of the total weight of the polyether compound (B).
- R is an optionally substituted monovalent organic group having 1 to 20 carbon atoms
- M is a hydroxyl group or a hydrolyzable group
- a is an integer of 1 to 3
- the plurality of R may be the same or different from each other
- the plurality of M may be the same or different from each other.
- Z is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms
- R, M, X and Y are the same as above.
- OA is the same as the above AO
- n is the same as the above.
- Q is a divalent or higher valent hydrocarbon group having 1 to 10 carbon atoms.
- M is the same as the valence of the hydrocarbon group. ).
- X in the general formula (2) is a linear or branched alkylene group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 3.
- Y in the general formula (2) is a linking group formed by reaction with a hydroxyl group at the terminal of the oxyalkylene group related to the polyether skeleton, preferably an ether bond or a urethane bond, more preferably It is a urethane bond.
- Z corresponds to a hydroxy compound having a hydroxyl group that is an initiator of an oxyalkylene polymer involved in the production of the compound represented by the general formula (2).
- Z at the other end is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. is there.
- Z is a hydrogen atom, it is a case where the same structural unit as the oxyalkylene polymer is used as the hydroxy compound, and when Z is a monovalent hydrocarbon group having 1 to 10 carbon atoms, This is a case where a hydroxy compound having one hydroxyl group is used as the hydroxy compound.
- the terminal when the terminal has a plurality of reactive silyl groups, it relates to the case where Z is the general formula (2A) or (2B).
- Z is the general formula (2A)
- Z is a case where the same structural unit as the oxyalkylene polymer is used as the hydroxy compound
- Z is the general formula (2B)
- the hydroxy compound is an oxyalkylene.
- Y ⁇ 1 > is the bonding group formed by reacting with the hydroxyl group of the terminal of the oxyalkylene group which concerns on a polyether frame
- Formula (4) Z 0 —A 2 —O— (A 1 O) n —Z 1 (In the formula, A 1 O is an oxyalkylene group having 2 to 6 carbon atoms, n is 1 to 1700, and represents the average number of moles of A 1 O. Z 1 is a hydrogen atom, or —A 2 -Z 0.
- a 2 is an alkylene group having 2 to 6 carbon atoms.); Formula (5): Z 0 —A 2 —NHCOO— (A 1 O) n —Z 2 (Wherein A 1 O is an oxyalkylene group having 2 to 6 carbon atoms, n is 1 to 1700, and represents the average number of moles added of A 1 O. Z 2 represents a hydrogen atom or —CONH— A 2 -Z 0.
- a 2 is an alkylene group having 2 to 6 carbon atoms);
- General formula (6) Z 3 —O— (A 1 O) n —C ⁇ —CH 2 — (A 1 O) n —Z 3 ⁇ 2
- a 1 O is an oxyalkylene group having 2 to 6 carbon atoms
- n is 1 to 1700, and represents the average number of moles added of A 1 O.
- Z 3 represents a hydrogen atom or —A 2 -Z 0 , and at least one Z 3 is -A 2 -Z 0.
- a 2 is an alkylene group having 2 to 6 carbon atoms).
- Z 0 is a alkoxysilyl group represented by either the general formula (3).
- the oxyalkylene group of A 1 O may be either linear or branched, and is particularly preferably an oxypropylene group.
- the alkylene group for A 2 may be either linear or branched, and is particularly preferably a propylene group.
- the polyether compound (B) preferably has a number average molecular weight of 300 to 100,000 from the viewpoint of reworkability.
- the lower limit of the number average molecular weight is 500 or more, more preferably 1000 or more, further 2000 or more, more preferably 3000 or more, further 4000 or more, more preferably 5000 or more, while the upper limit is 50000 or less, It is preferably 40000 or less, more preferably 30000 or less, further 20000 or less, and further preferably 10,000 or less.
- the number average molecular weight can be set within a preferable range by adopting the upper limit value or the lower limit value.
- N in the polyether compound (B) represented by the general formula (2), (4), (5) or (6) is an average addition mole number of the oxyalkylene group related to the polyether skeleton,
- the polyether compound (B) is preferably controlled so that the number average molecular weight falls within the above range.
- the n is usually 10 to 1700 when the number average molecular weight of the polyether compound (B) is 1000 or more.
- Mw (weight average molecular weight) / Mn (number average molecular weight) of the polymer is preferably 3.0 or less, more preferably 1.6 or less, and particularly preferably 1.5 or less.
- an oxy produced by polymerizing a cyclic ether in the presence of an initiator, particularly using the following double metal cyanide complex as a catalyst is particularly preferable to use an alkylene polymer, and the most preferable method is to modify the terminal of such a raw material oxyalkylene polymer into a reactive silyl group.
- the polyether compound (B) represented by the general formula (2), (4), (5) or (6) uses, for example, an oxyalkylene polymer having a functional group at the molecular terminal as a raw material, and the molecule It can be produced by bonding a reactive silyl group to an end via an organic group such as an alkylene group.
- the oxyalkylene polymer used as a raw material is preferably a hydroxyl-terminated polymer obtained by subjecting a cyclic ether to a ring-opening polymerization reaction in the presence of a catalyst and an initiator.
- a compound having one or more active hydrogen atoms per molecule for example, a hydroxy compound having one or more hydroxyl groups per molecule can be used.
- the initiator include ethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexamethylene glycol, hydrogenated bisphenol A, neopentyl glycol, polybutadiene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, allyl alcohol, and methallyl alcohol.
- An initiator can use only 1 type and can also use 2 or more types together.
- a polymerization catalyst can be used when ring-opening polymerization of a cyclic ether in the presence of an initiator.
- the polyoxyalkylene chain in the polyether compound (B) represented by the general formula (2), (4), (5) or (6) is formed by ring-opening polymerization of an alkylene oxide having 2 to 6 carbon atoms.
- it is composed of repeating structural units of oxyalkylene groups formed by ring-opening polymerization of one or more alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide. More preferably, it is particularly preferably composed of repeating structural units of oxyalkylene formed by ring-opening polymerization of propylene oxide.
- the polyoxyalkylene chain is composed of repeating structural units of two or more oxyalkylene groups, the arrangement of the repeating structural units of two or more oxyalkylene groups may be block or random.
- the polyether compound (B) represented by the general formula (5) includes, for example, a polymer having a polyoxyalkylene chain and a hydroxy group, and a reactive silyl group and an isocyanate represented by the general formula (1). It can be obtained by urethanizing a compound having a group.
- an oxyalkylene polymer having an unsaturated group for example, an allyl-terminated polyoxypropylene monool obtained by polymerizing alkylene oxide using allyl alcohol as an initiator, an addition reaction of hydrosilane or mercaptosilane to the unsaturated group. It is also possible to use a method of introducing a reactive silyl group represented by the general formula (1) into the molecular terminal.
- the reactive silyl group represented by the general formula (1) is introduced into the terminal group of a hydroxyl-terminated oxyalkylene polymer (also referred to as a raw material oxyalkylene polymer) obtained by ring-opening polymerization of a cyclic ether in the presence of an initiator.
- a hydroxyl-terminated oxyalkylene polymer also referred to as a raw material oxyalkylene polymer
- obtained by ring-opening polymerization of a cyclic ether in the presence of an initiator.
- the method to do is not specifically limited, Usually, the method of the following (a) thru
- A-1) A method using a so-called hydrosilylation reaction in which a hydrosilyl compound is reacted with the unsaturated group in the presence of a catalyst such as a platinum compound.
- A-2) A method of reacting a mercaptosilane compound with an unsaturated group.
- Examples of the mercaptosilane compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriisopropenyloxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethylmonomethoxysilane, Examples include 3-mercaptopropylmethyldiethoxysilane.
- a compound such as a radical generator used as a radical polymerization initiator may be used. If desired, the reaction is performed by radiation or heat without using a radical polymerization initiator. May be.
- the radical polymerization initiator include peroxide-based, azo-based, and redox-based polymerization initiators, and metal compound catalysts. Specifically, 2,2′-azobisisobutyronitrile, 2, Examples include 2'-azobis-2-methylbutyronitrile, benzoyl peroxide, tert-alkyl peroxyester, acetyl peroxide, and diisopropyl peroxycarbonate.
- the reaction temperature is generally 20 to 200 ° C., preferably 50 to 150 ° C., depending on the decomposition temperature (half-life temperature) of the polymerization initiator.
- the reaction is preferably performed for several hours to several tens of hours.
- a functional group that can be linked to the terminal hydroxyl group of the raw material oxyalkylene polymer by an ether bond, an ester bond, a urethane bond, a carbonate bond, or the like examples thereof include a method in which a reactive agent having both groups is reacted with a raw material oxyalkylene polymer.
- an unsaturated group is introduced into at least a part of the terminal of the raw material oxyalkylene polymer by copolymerizing an unsaturated group-containing epoxy compound such as allyl glycidyl ether.
- a method can also be used. The reaction is preferably carried out at a temperature of 60 to 120 ° C., and the hydrosilylation reaction generally proceeds sufficiently within a reaction time of several hours.
- (B) A method in which a raw material oxyalkylene polymer having a hydroxyl group at the terminal is reacted with an isocyanate silane compound having a reactive silyl group.
- Such compounds include 1-isocyanatomethyltrimethoxysilane, 1-isocyanatemethyltriethoxysilane, 1-isocyanatepropyltrimethoxysilane, 1-isocyanatopropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane.
- 3-isocyanatopropyltrimethoxysilane and 1-isocyanatomethylmethyldimethoxysilane are more preferred, and 3-isocyanatopropyltrimethoxysilane is particularly preferred.
- a known urethanization reaction catalyst When reacting the hydroxyl group of the raw material oxyalkylene polymer with the isocyanate silane compound, a known urethanization reaction catalyst may be used.
- the reaction temperature and the reaction time required for completion of the reaction vary depending on whether or not the urethanization catalyst is used and the amount used, but the reaction is generally carried out at a temperature of 20 to 200 ° C., preferably 50 to 150 ° C. for several hours. preferable.
- An oxyalkylene polymer having a hydroxyl group at the molecular end is reacted with a polyisocyanate compound under an excess of isocyanate group to produce an oxyalkylene polymer having an isocyanate group at least at a part of the end.
- the functional group of the silicon compound is an active hydrogen-containing group selected from the group consisting of a hydroxyl group, a carboxyl group, a mercapto group, a primary amino group, and a secondary amino group.
- Examples of the silicon compound include N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, and 3-aminopropyl.
- Examples include aminosilane compounds such as methyldimethoxysilane and 3-aminopropylmethyldiethoxysilane; and mercaptosilane compounds such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane.
- a known urethanization reaction catalyst may be used.
- the reaction temperature and the reaction time required for completion of the reaction vary depending on whether or not the urethanization catalyst is used and the amount used, but the reaction is generally carried out at a temperature of 20 to 200 ° C., preferably 50 to 150 ° C. for several hours. preferable.
- polyether compound (B) examples include, for example, MS polymer S203, S303, S810 manufactured by Kaneka Corporation; SILYL EST 250, EST 280; Etc.
- the proportion of the polyether compound (B) in the pressure-sensitive adhesive composition of the present invention is preferably 0.001 to 20 parts by weight of the polyether compound (B) with respect to 100 parts by weight of the (meth) acrylic polymer (A). .
- the polyether compound (B) is preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight or more, further 0.1 parts by weight or more, and further preferably 0.5 parts by weight or more.
- the amount of the polyether compound (B) is more than 20 parts by weight, the moisture resistance is not sufficient, and peeling easily occurs in a reliability test or the like.
- the polyether compound (B) is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and further preferably 3 parts by weight or less.
- the ratio of the said polyether compound (B) can set the preferable range by employ
- the ratio of the said polyether compound (B) has described the preferable range, and a polyether compound (B) can be used suitably also in 1 weight part or less, Furthermore, 0.5 weight part or less. .
- the pressure-sensitive adhesive composition of the present invention can contain a crosslinking agent (C).
- a crosslinking agent C
- an organic crosslinking agent or a polyfunctional metal chelate can be used as the crosslinking agent (C).
- the organic crosslinking agent include an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, and an imine crosslinking agent.
- a polyfunctional metal chelate is one in which a polyvalent metal is covalently or coordinately bonded to 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.
- Examples of 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
- an isocyanate-based crosslinking agent and / or a peroxide-type crosslinking agent is preferable.
- the compound relating to the isocyanate-based crosslinking agent include isocyanate monomers such as tolylene diisocyanate, chlorophenylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and these isocyanate monomers.
- Examples include isocyanate compounds added with trimethylolpropane, isocyanurates, burette compounds, and urethane prepolymer isocyanates such as polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, and polyisoprene polyols. be able to.
- a polyisocyanate compound which is one or a polyisocyanate compound derived from one selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate.
- hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, polyol-modified is selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate or a polyisocyanate compound derived therefrom.
- examples include hexamethylene diisocyanate, polyol-modified hydrogenated xylylene diisocyanate, trimer-type hydrogenated xylylene diisocyanate, and polyol-modified isophorone diisocyanate.
- the exemplified polyisocyanate compound is preferable because the reaction with a hydroxyl group proceeds rapidly, particularly using an acid or base contained in the polymer as a catalyst, and thus contributes to the speed of crosslinking.
- any radical active species can be used as long as it generates radical active species by heating or light irradiation to advance the crosslinking of the base polymer of the pressure-sensitive adhesive composition.
- 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 amount of the crosslinking agent (C) used is preferably 0.01 to 20 parts by weight, and more preferably 0.03 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (A). If the crosslinking agent (C) is less than 0.01 parts by weight, the cohesive force of the pressure-sensitive adhesive tends to be insufficient, and foaming may occur during heating. On the other hand, if it exceeds 20 parts by weight, the moisture resistance is sufficient. Instead, peeling easily occurs in a reliability test or the like.
- the isocyanate-based crosslinking agent may be used singly or as a mixture of two or more, but the total content thereof is the (meth) acrylic polymer (A) 100
- the polyisocyanate compound crosslinking agent is preferably contained in an amount of 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, and more preferably 0.05 to 1.5 parts by weight. More preferably, it is contained in parts by weight. It can be appropriately contained in consideration of cohesive force and prevention of peeling in a durability test.
- the peroxide may be used alone or as a mixture of two or more, but the total content is 100 weight of the (meth) acrylic polymer (A).
- the peroxide is 0.01 to 2 parts by weight, preferably 0.04 to 1.5 parts by weight, and more 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.
- the pressure-sensitive adhesive composition of the present invention can contain a silane coupling agent (D).
- the durability can be improved by using the silane coupling agent (D).
- the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, Epoxy group-containing silane coupling agents such as 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl- Amino group-containing silane coupling agents such as N- (1,3-dimethylbutylidene) propylamine, N-phenyl- ⁇ -aminopropyltrimethoxysilane, 3-acryloxypropyltrimeth
- the silane coupling agent (D) may be used alone or as a mixture of two or more, but the total content thereof is the (meth) acrylic polymer (A) 100.
- the silane coupling agent is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, further preferably 0.02 to 1 part by weight, more preferably 0.05 to part by weight. ⁇ 0.6 parts by weight is preferred. It is an amount that improves durability and appropriately maintains the adhesive force to an optical member such as a liquid crystal cell.
- 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. Moreover, you may employ
- the pressure-sensitive adhesive composition forms a pressure-sensitive adhesive layer.
- it is necessary to fully consider the influence of the crosslinking treatment temperature and the crosslinking treatment time as well as adjusting the addition amount of the entire crosslinking agent. preferable.
- the crosslinking treatment temperature and crosslinking treatment time can be adjusted depending on the crosslinking agent used.
- the crosslinking treatment temperature is preferably 170 ° C. or lower.
- crosslinking treatment may be performed at the temperature during the drying step of the pressure-sensitive adhesive layer, or may be performed by providing a separate crosslinking treatment step after the drying step.
- the crosslinking treatment time can be set in consideration of productivity and workability, but is usually about 0.2 to 20 minutes, preferably about 0.5 to 10 minutes.
- the pressure-sensitive adhesive optical member such as the pressure-sensitive adhesive optical film of the present invention has a pressure-sensitive adhesive layer formed on at least one surface of the optical film with the pressure-sensitive adhesive.
- the pressure-sensitive adhesive layer for example, a method in which 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, and then transferred to an optical film, or
- the pressure-sensitive adhesive composition is prepared by applying the pressure-sensitive adhesive composition to an optical film, drying and removing a polymerization solvent, and the like to form a pressure-sensitive adhesive layer on the optical film.
- 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 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 film 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 perform 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 optical film can be used as a separator of an adhesive optical film as it is, and can simplify in the process surface.
- the optical film one used for forming an image display device such as a liquid crystal display device is used, and the type thereof is not particularly limited.
- a polarizing plate is mentioned as an optical film.
- a polarizing plate having a transparent protective film on one or both sides of a polarizer is generally used.
- an optical film for example, a triacetyl cellulose resin, a (meth) acrylic resin, or a norbornene resin is used as a transparent protective film.
- the adhesive optical film of the present invention is In particular, when the (meth) acrylic polymer (A) is the (meth) acrylic polymer (A ′), good durability is exhibited.
- 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.
- 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 mold release agent, an anti-coloring agent, 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.
- an optical film for example, it is used for forming a liquid crystal display device such as a reflection plate, an anti-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), a visual compensation film, and a brightness enhancement film And an optical layer that may be formed.
- a liquid crystal display device such as a reflection plate, an anti-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), a visual compensation film, and a brightness enhancement film And an optical layer that may be formed.
- a liquid crystal display device such as a reflection plate, an anti-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), a visual compensation film, and a brightness enhancement film And an optical layer that may be formed.
- An optical film in which the optical layer is laminated on a polarizing plate can be formed by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device or the like.
- an appropriate adhesive means such as an adhesive layer can be used for the lamination.
- their optical axes can be set at an appropriate arrangement angle in accordance with the target phase difference characteristic.
- the pressure-sensitive adhesive optical film of the present invention can be preferably used for forming various image display devices such as a liquid crystal display device.
- 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 display panel such as a liquid crystal cell, an adhesive optical film, and an illumination system as required, and incorporating a drive circuit. There is no particular limitation except that the pressure-sensitive adhesive optical film according to the present invention is used.
- As the liquid crystal cell 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 optical film is disposed on one side or both sides of a display panel such as a liquid crystal cell, and a lighting system using a backlight or a reflecting plate can be formed.
- the optical film by this invention can be installed in the one side or both sides of display panels, such as a liquid crystal cell.
- optical films When optical films are provided on both sides, they may be the same or different.
- 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.
- Example ′ and Comparative Example ′ instead of the 80 ⁇ m thick triacetylcellulose film, a 30 ⁇ m thick acrylic film (lactone-modified acrylic resin film) or a 60 ⁇ m thick norbornene film (Zeonor film).
- a polarizing plate was prepared in the same manner as described above using ZB12 (manufactured by Zeon Corporation).
- ZB12 manufactured by Zeon Corporation
- Example ′ and Comparative Example ′ three types of polarizing plates having different transparent protective films thus obtained were used.
- Production Example 3 ⁇ Preparation of polyether compound (B1)> Polyoxypropylene diol (number average molecular weight 16000, hydroxyl value 7.7) obtained by ring-opening polymerization of propylene oxide to polyoxypropylene diol (number average molecular weight 1000) in the presence of a zinc hexacyanocobaltate-glyme complex catalyst The polymer (3000 g) was placed in a pressure resistant reactor (internal volume 5 L), dehydrated under reduced pressure while maintaining the internal temperature at 110 ° C., and then the atmosphere in the reactor was replaced with nitrogen gas, and the internal temperature was increased to 50 ° C.
- a pressure resistant reactor internal volume 5 L
- polyether compound (B1) was used.
- the polyether compound (B1) had a viscosity of 20.0 Pa ⁇ s (25 ° C.), a number average molecular weight of 15,000, and Mw / Mn of 1.38.
- the obtained polyether compound (B1) are the compounds of formula (5A), R 1, R 2 and R 3 are both methyl groups, a group Z 21 is represented by the general formula (5B) is there.
- Example 1 Preparation of adhesive composition
- 100 parts of the solid content of the acrylic polymer (A1) solution obtained in Production Example 1 0.02 part of the polyether compound (B1) prepared in Production Example 3 and an isocyanate crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd.) Coronate L, trimethylolpropane tolylene diisocyanate adduct body) 0.30 part was blended to prepare an acrylic pressure-sensitive adhesive composition solution (solid content 11%).
- an isocyanate crosslinking agent manufactured by Nippon Polyurethane Industry Co., Ltd.
- Coronate L trimethylolpropane tolylene diisocyanate adduct body
- Example 2 In Example 1, except that the amount of the polyether compound (B1) used was changed as shown in Table 1, and the silane coupling agent was used in the ratio shown in Table 1, the same as in Example 1, A polarizing plate with an adhesive layer was prepared.
- Example 7 As shown in Table 1, a polarizing plate with an adhesive layer was prepared in the same manner as in Example 1 except that the polyether compound (B1) was changed to Excestar 2420 or 3430 manufactured by Asahi Glass Urethane Co., Ltd. Produced.
- Example 9 Preparation of adhesive composition
- an isocyanate crosslinking agent manufactured by Mitsui Takeda Chemical Co., Ltd.
- benzoyl peroxide manufactured by Nippon Oil & Fats Co., Ltd., Nyper BMT
- Example 1 Comparative Example 1 In Example 1, except that the polyether compound (B1) was not used, or the type of acrylic polymer, the type of crosslinking agent or the amount used was changed as shown in Table 1, the same as in Example 1 Thus, a polarizing plate with an adhesive layer was produced.
- Example 10 to 25 and Comparative Examples 2 to 4 In Example 1, except that the type of polyether compound (B) or the amount of use thereof was changed, and the crosslinking agent and silane coupling agent were used in the proportions shown in Table 2, the same as in Example 1, A polarizing plate with an adhesive layer was prepared.
- Example 9 except that the type of polyether compound (B) or the amount of use thereof was changed, and the crosslinking agent and silane coupling agent were used in the proportions shown in Table 3, the same as in Example 9, A polarizing plate with an adhesive layer was prepared.
- the sample was cut into a width of 25 mm and a length of 100 mm, attached to a non-alkali glass plate (Corning Corp., 1737) with a thickness of 0.5 mm using a laminator, and then autoclaved at 50 ° C. and 5 atm for 15 minutes. And completely adhered (initial). Thereafter, a heat treatment was performed for 120 hours under a 60 ° C. dry condition (after heating). The adhesive strength of the sample was measured.
- the adhesive strength is the adhesive strength (N / 25 mm, when the sample is peeled off with a tensile tester (Autograph SHIMAZU AG-1 1OKN) at a peeling angle of 90 ° and a peeling speed of 300 mm / min. 80 m long).
- the measurement was sampled at an interval of 1 time / 0.5 s, and the average value was taken as the measurement value.
- the sample was 37 inches in size, and was attached to a non-alkali glass (Corning Corp., 1737) having a thickness of 0.7 mm using a laminator. Subsequently, the sample was autoclaved at 50 ° C. and 0.5 MPa for 15 minutes to completely adhere the sample to the acrylic-free glass. The sample thus treated was treated for 500 hours in an atmosphere of 60 ° C./90% RH (humidification test), and then subjected to an environment of 85 ° C. and ⁇ 40 ° C. for 300 cycles per hour for 1 hour. (Heat shock test) The appearance between the polarizing plate and the glass was visually evaluated according to the following criteria.
- A No change in appearance such as foaming, peeling, or no floating.
- ⁇ Slightly peeled off or foamed at the end, but no problem in practical use.
- ⁇ There is peeling or foaming at the end, but there is no practical problem unless it is a special use.
- X Remarkably peeled off at the end, causing practical problems.
- the sample was cut into a length of 420 mm and a width of 320 mm, attached to a non-alkali glass plate (Corning Corp., 1737) with a thickness of 0.7 mm using a laminator, and then autoclaved at 50 ° C. and 5 atm for 15 minutes. It was completely adhered (initial). Thereafter, a heat treatment was performed for 48 hours under 60 ° C. dry conditions (after heating). The adhesive strength of the sample was measured. The adhesive force was measured by the same method as described above.
- the sample was 37 inches in size, and was attached to a non-alkali glass (Corning Corp., 1737) having a thickness of 0.7 mm using a laminator. Subsequently, the sample was autoclaved at 50 ° C. and 0.5 MPa for 15 minutes to completely adhere the sample to the acrylic-free glass. Samples subjected to such treatment were treated for 500 hours in respective atmospheres of 80 ° C., 100 ° C., and 110 ° C. (heating test), and then each atmosphere of 60 ° C./90% RH and 65 ° C./95% RH.
- “* 1” in the polyether compound (B) represents the polyether compound (B1) prepared in Production Example 3.
- “* 2” means Excestar S2420 manufactured by Asahi Glass Co., Ltd.
- “* 3” refers to Excestar S3430 manufactured by Asahi Glass Co., Ltd.
- “* 4" is Kaneka's Silyl SAT10
- “* 5” refers to Kaneka's Silyl SAT350
- “* 6” represents Silyl SAX220 manufactured by Kaneka Corporation, and each is a polyether compound (B) having a reactive silyl group.
- the polyether compounds (B) of * 2, * 4 to * 6 are all compounds represented by the general formula (4), A 2 is —C 3 H 8 —, and Z 1 is —C 3. H 8 -Z 0 and the reactive silyl group (Z 0- ) is a dimethoxymethylsilyl group in which R 1 , R 2 and R 3 are all methyl groups. * 3
- the polyether compound (B) is a compound represented by the general formula (6), Z 3 is all —C 3 H 8 —Z 0 , and the reactive silyl group (Z 0 —) is Dimethoxymethylsilyl group.
- * 7 is a compound having the same structure as the polyether compound (B1) prepared in Production Example 3 except that the number average molecular weight is different.
- “* 8” represents ACX022 manufactured by Kaneka Corporation, which is a compound having an allyl group at both ends in place of —C 3 H 8 —Z 0 in the general formula (4).
- “C / L” in the cross-linking agent (C) is an isocyanate cross-linking agent (coronate L manufactured by Nippon Polyurethane Industry Co., Ltd., an adduct of tolylene diisocyanate of trimethylolpropane), and “D110N” is an isocyanate cross-linking agent (Takeshi Mitsui).
- Production Example 2′-13 ′ and Production Example 3 In the production example 1 ′, the acrylic polymers (A2 ′) to (A13 ′) are the same as the production example 1 ′ except that the type of monomer forming the acrylic polymer or the ratio thereof is changed as shown in Table 4. A solution of acrylic polymer (A3) was prepared. The weight average molecular weights of the acrylic polymers (A2 ′) to (A13 ′) and the acrylic polymer (A3) were all 2.2 million.
- BA butyl acrylate
- BzA benzyl acrylate
- PEA phenoxyethyl acrylate
- HBA 4-hydroxybutyl acrylate
- AA acrylic acid
- Example 1 (Preparation of adhesive composition)
- a polyether compound (B) having a reactive silyl group with respect to 100 parts of the solid content of the acrylic polymer (A1 ′) solution obtained in Production Example 1 ′ Silyl SAX220 (general formula (4) ), A 2 is —C 3 H 8 —, Z 1 is —C 3 H 8 —Z 0 , and the reactive silyl group (Z 0 —) is R 1 , R 2 and R 3 is a methyl dimethoxymethylsilyl group, and the number average molecular weight is 5000) 1 part, isocyanate cross-linking agent (coronate L manufactured by Nippon Polyurethane Industry Co., Ltd., adduct of tolylene diisocyanate of trimethylolpropane) 0.1 Part and 0.1 part of benzoyl peroxide (manufactured by NOF Corporation, Niper BMT) were blended to prepare an acrylic pressure-sensitive adhesive composition solution (solid content 11%).
- Example 2 Examples 2'-26 ', Example 34 and Comparative Examples 1-5'
- Example 1 As shown in Table 5, the type of acrylic polymer (A ′), the type of polyether compound (B) or the amount used (or not used), the type of cross-linking agent or the amount used are changed.
- a polarizing plate with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the silane coupling agent was used at the ratio shown in Table 5.
- the sample was 37 inches in size, and was attached to a non-alkali glass (Corning Corp., 1737) having a thickness of 0.7 mm using a laminator. Subsequently, the sample was autoclaved at 50 ° C. and 0.5 MPa for 15 minutes to completely adhere the sample to the acrylic-free glass. The sample subjected to such treatment was treated at 80 ° C. for 500 hours (heating test 1) and 100 ° C. for 500 hours (heating test 2), respectively, and then in an atmosphere of 60 ° C./90% RH.
- the sample is cut into a width of 25 mm and a length of 100 mm, and is attached to a non-alkali glass plate (Corning Corp., 1737) with a thickness of 0.7 mm using a laminator, and then autoclaved at 50 ° C. and 5 atm for 15 minutes. And completely adhered (initial). Thereafter, a heat treatment was performed for 48 hours under 60 ° C. dry conditions (after heating). The adhesive strength of the sample was measured.
- Adhesive strength is the adhesive strength (N / 25mm, 80m length when measured) when the sample is peeled with a tensile tester (Autograph SHIMAZU AG-1 1OKN) at a peeling angle of 90 ° and a peeling speed of 300mm / min. Obtained by measuring. The measurement was sampled at an interval of 1 time / 0.5 s, and the average value was taken as the measurement value.
- SAX220 is a compound represented by the general formula (6), Z 3 are all a -C 3 H 8 -Z 0, the reactive silyl group (Z 0 -) is dimethoxymethylsilyl group.
- “* 8” represents ACX022 manufactured by Kaneka Corporation, which is a compound having an allyl group at both ends in place of —C 3 H 8 —Z 0 in the general formula (4).
- C / L in the cross-linking agent (C) is an isocyanate cross-linking agent (coronate L manufactured by Nippon Polyurethane Industry Co., Ltd., an adduct of tolylene diisocyanate of trimethylolpropane), and “D110N” is an isocyanate cross-linking agent (Takeshi Mitsui). Chemical product Takenate D110N, trimethylolpropane xylylene diisocyanate).
- BPO in the crosslinking agent (C) represents benzoyl peroxide (manufactured by NOF Corporation, Nyper BMT).
- KBM-403 in the silane coupling agent indicates KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.
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Abstract
Description
ポリエーテル骨格を有し、かつ少なくとも1つの末端に、
一般式(1):-SiRaM3-a
(式中、Rは、置換基を有していてもよい、炭素数1~20の1価の有機基であり、Mは水酸基又は加水分解性基であり、aは1~3の整数である。但し、Rが複数存在するとき複数のRは互いに同一であっても異なっていてもよく、Mが複数存在するとき複数のMは互いに同一であっても異なっていてもよい。)で表される反応性シリル基を有するポリエーテル化合物(B)、を含有することを特徴とする光学フィルム用粘着剤組成物、に関する。
一般式(2):RaM3-aSi-X-Y-(AO)n-Z
(式中、Rは、置換基を有していてもよい、炭素数1~20の1価の有機基であり、Mは水酸基又は加水分解性基であり、aは1~3の整数である。但し、Rが複数存在するとき複数のRは互いに同一であっても異なっていてもよく、Mが複数存在するとき複数のMは互いに同一であっても異なっていてもよい。AOは、直鎖または分岐鎖の炭素数1~10のオキシアルキレン基を示し、nは1~1700であり、オキシアルキレン基の平均付加モル数を示す。Xは、炭素数1~20の直鎖または分岐鎖のアルキレン基を示す。Yは、エーテル結合、エステル結合、ウレタン結合、またはカーボネート結合を示す。
Zは、水素原子、1価の炭素数1~10の炭化水素基、
一般式(2A):-Y1-X-SiRaM3-a
(式中、R、M、Xは、前記と同じ。Y1は単結合、-CO-結合、-CONH-結合、または-COO-結合を示す。)、または、
一般式(2B):-Q{-(OA)n-Y-X-SiRaM3-a}m
(式中、R、M、X、Yは、前記と同じ。OAは前記のAOに同じで、nは前記と同じ。Qは、2価以上の炭素数1~10の炭化水素基であり、mは当該炭化水素基の価数と同じ。)で表される基である。)で表される化合物が好ましい。
(式中、R1、R2およびR3は、炭素数1~6の1価の炭化水素基であり、同一分子中で同一であっても異なっていてもよい。)で表されるアルコキシシリル基であることが好ましい。
一般式(4):Z0-A2-O-(A1O)n-Z1
(式中、A1Oは炭素数2~6のオキシアルキレン基であり、nは1~1700であり、A1Oの平均付加モル数を示す。Z1は、水素原子、または-A2-Z0である。A2は炭素数2~6のアルキレン基である。
Z0は、一般式(3):
(式中、R1、R2およびR3は、炭素数1~6の1価の炭化水素基であり、同一分子中で同一であっても異なっていてもよい。)で表されるアルコキシシリル基である。)で表される化合物が好ましい。
一般式(5):Z0-A2-NHCOO-(A1O)n-Z2
(式中、A1Oは炭素数2~6のオキシアルキレン基であり、nは1~1700であり、A1Oの平均付加モル数を示す。Z2は、水素原子、または-CONH-A2-Z0である。A2は炭素数2~6のアルキレン基である。
Z0は、一般式(3):
(式中、R1、R2およびR3は、炭素数1~6の1価の炭化水素基であり、同一分子中で同一であっても異なっていてもよい。)で表されるアルコキシシリル基である。)で表される化合物がより好ましい。
一般式(6):Z3-O-(A1O)n-C{-CH2-(A1O)n-Z3}2
(式中、A1Oは炭素数2~6のオキシアルキレン基であり、nは1~1700であり、A1Oの平均付加モル数を示す。Z3は、水素原子、または-A2-Z0であり、いずれか少なくとも1つのZ3は-A2-Z0である。A2は炭素数2~6のアルキレン基である。
Z0は、一般式(3):
(式中、R1、R2およびR3は、炭素数1~6の1価の炭化水素基であり、同一分子中で同一であっても異なっていてもよい。)で表されるアルコキシシリル基である。)で表される化合物がより好ましい。
(式中、Rは、置換基を有していてもよい、炭素数1~20の1価の有機基であり、Mは水酸基又は加水分解性基であり、aは1~3の整数である。但し、Rが複数存在するとき複数のRは互いに同一であっても異なっていてもよく、Mが複数存在するとき複数のMは互いに同一であっても異なっていてもよい。)で表される反応性シリル基を有する。
(式中、R1、R2およびR3は、炭素数1~6の1価の炭化水素基であり、同一分子中で同一であっても異なっていてもよい。)で表されるアルコキシシリル基が好ましい。
一般式(2):RaM3-aSi-X-Y-(AO)n-Z
(式中、Rは、置換基を有していてもよい、炭素数1~20の1価の有機基であり、Mは水酸基又は加水分解性基であり、aは1~3の整数である。但し、Rが複数存在するとき複数のRは互いに同一であっても異なっていてもよく、Mが複数存在するとき複数のMは互いに同一であっても異なっていてもよい。AOは、直鎖または分岐鎖の炭素数1~10のオキシアルキレン基を示し、nは1~1700であり、オキシアルキレン基の平均付加モル数を示す。Xは、炭素数1~20の直鎖または分岐鎖のアルキレン基を示す。Yは、エーテル結合、エステル結合、ウレタン結合、またはカーボネート結合を示す。
Zは、水素原子、1価の炭素数1~10の炭化水素基、
一般式(2A):-Y1-X-SiRaM3-a
(式中、R、M、Xは、前記と同じ。Y1は単結合、-CO-結合、-CONH-結合、または-COO-結合を示す。)、または、
一般式(2B):-Q{-(OA)n-Y-X-SiRaM3-a}m
(式中、R、M、X、Yは、前記と同じ。OAは前記のAOに同じで、nは前記と同じ。Qは、2価以上の炭素数1~10の炭化水素基であり、mは当該炭化水素基の価数と同じ。)で表される基である。)で表される化合物が挙げられる。
一般式(4):Z0-A2-O-(A1O)n-Z1
(式中、A1Oは炭素数2~6のオキシアルキレン基であり、nは1~1700であり、A1Oの平均付加モル数を示す。Z1は、水素原子、または-A2-Z0である。A2は炭素数2~6のアルキレン基である。);
一般式(5):Z0-A2-NHCOO-(A1O)n-Z2
(式中、A1Oは炭素数2~6のオキシアルキレン基であり、nは1~1700であり、A1Oの平均付加モル数を示す。Z2は、水素原子、または-CONH-A2-Z0である。A2は炭素数2~6のアルキレン基である。);
一般式(6):Z3-O-(A1O)n-C{-CH2-(A1O)n-Z3}2
(式中、A1Oは炭素数2~6のオキシアルキレン基であり、nは1~1700であり、A1Oの平均付加モル数を示す。Z3は、水素原子、または-A2-Z0であり、いずれか少なくとも1つのZ3は-A2-Z0である。A2は炭素数2~6のアルキレン基である。)で表される化合物が好ましい。Z0は、いずれも前記一般式(3)で表されるアルコキシシリル基である。A1Oのオキシアルキレン基は、直鎖または分岐鎖のいずれでもよく、特にオキシプロピレン基が好ましい。A2のアルキレン基は、直鎖または分岐鎖のいずれでもよく、特にプロピレン基が好ましい。
(式中、R1、R2およびR3は、炭素数1~6の1価の炭化水素基であり、同一分子中で同一であっても異なっていてもよい。nは1~1700であり、オキシプロピレン基の平均付加モル数を示す。
Z21は、水素原子、または一般式(5B):
(式中、R1、R2およびR3は前記と同じ。)で表されるトリアルコキシシリル基である。)で表される化合物が好適に用いられる。
(メタ)アクリル系ポリマー(A)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。
・分析装置:東ソー社製、HLC-8120GPC
・カラム:東ソー社製、G7000HXL+GMHXL+GMHXL
・カラムサイズ:各7.8mmφ×30cm 計90cm
・カラム温度:40℃
・流量:0.8ml/min
・注入量:100μl
・溶離液:テトラヒドロフラン
・検出器:示差屈折計(RI)
・標準試料:ポリスチレン
ポリエーテル化合物(B)の数平均分子量は、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。
・分析装置:東ソー社製,HLC-8120GPC
・カラム:TSKgel,SuperHZM‐H/HZ4000/HZ2000
・カラムサイズ:6.0mmI.D.×150mm
・カラム温度:40℃
・流量:0.6ml/min
・注入量:20μl
・溶離液:テトラヒドロフラン
・検出器:示差屈折計(RI)
・標準試料:ポリスチレン
厚さ80μmのポリビニルアルコールフィルムを、速度比の異なるロール間において、30℃、0.3%濃度のヨウ素溶液中で1分間染色しながら、3倍まで延伸した。その後、60℃、4%濃度のホウ酸、10%濃度のヨウ化カリウムを含む水溶液中に0.5分間浸漬しながら総合延伸倍率が6倍まで延伸した。次いで、30℃、1.5%濃度のヨウ化カリウムを含む水溶液中に10秒間浸漬することで洗浄した後、50℃で4分間乾燥を行い偏光子を得た。当該偏光子の両面に、けん化処理した厚さ80μmのトリアセチルセルロースフィルムをポリビニルアルコール系接着剤により貼り合せて偏光板を作成した。
<アクリル系ポリマー(A1)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、ブチルアクリレート100部、アクリル酸5部、2-ヒドロキシエチルアクリレート1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部を酢酸エチル100g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窒素置換した後、フラスコ内の液温を55℃付近に保って8時間重合反応を行い、重量平均分子量220万のアクリル系ポリマー(A1)の溶液を調製した。
<アクリル系ポリマー(A2)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、ブチルアクリレート99部、4-ヒドロキシブチルアクリレート1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部を酢酸エチル100g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窒素置換した後、フラスコ内の液温を55℃付近に保って8時間重合反応を行い、重量平均分子量160万のアクリル系ポリマー(A2)の溶液を調製した。
<ポリエーテル化合物(B1)の調製>
亜鉛ヘキサシアノコバルテート-グライム錯体触媒の存在下、ポリオキシプロピレンジオール(数平均分子量1000)にプロピレンオキシドを開環重合させて得られるポリオキシプロピレンジオール(数平均分子量16000,水酸基価7.7)を重合体(3000g)を、耐圧反応器(内容積5L)に入れ、内温を110℃に保持しながら減圧脱水し、次いで、反応器内雰囲気を窒素ガスに置換し、内温を50℃に保持しながら、NCO/OHが0.97となるように、3-イソシアネートプロピルトリメトキシシラン(純度95%)の86.1gを投入し、つづいて、内温を80℃に8時間保持して、重合体1と3-イソシアネートプロピルトリメトキシシランをウレタン化反応させて得られる、両末端にトリメトキシシリル基を有するポリエーテル化合物(B1)を用いた。当該ポリエーテル化合物(B1)の粘度は20.0Pa・s(25℃)、数平均分子量は15000であり、Mw/Mnは1.38であった。なお、得られたポリエーテル化合物(B1)は、一般式(5A)において、R1、R2およびR3はいずれもメチル基であり、Z21は一般式(5B)で表される基である。
(粘着剤組成物の調製)
製造例1で得られたアクリル系ポリマー(A1)溶液の固形分100部に対して、製造例3で調製したポリエーテル化合物(B1)0.02部、およびイソシアネート架橋剤(日本ポリウレタン工業社製のコロネートL,トリメチロールプロパンのトリレンジイソシアネートのアダクト体)0.30部を配合して、アクリル系粘着剤組成物の溶液(固形分11%)を調製した。
次いで、上記アクリル系粘着剤溶液を、シリコーン処理を施した、38μmのポリエチレンテレフタレート(PET)フィルム(三菱化学ポリエステルフィルム(株)製,MRF38)の片面に、乾燥後の粘着剤層の厚さが23μmになるように塗布し、155℃で1分間乾燥を行い、偏光板(日東電工製、SEG)に転写し、粘着剤層付偏光板を作製した。
実施例1において、ポリエーテル化合物(B1)の使用量を表1に示すように変えたこと、シランカップリング剤を表1に示す割合で用いたこと以外は、実施例1と同様にして、粘着剤層付偏光板を作製した。
実施例1において、表1に示すように、ポリエーテル化合物(B1)を、旭ガラスウレタン社製のExcestar2420または3430に変えたこと以外は実施例1と同様にして、粘着剤層付偏光板を作製した。
(粘着剤組成物の調製)
製造例2で得られたアクリル系ポリマー(A2)溶液の固形分100部に対して、製造例3で調製したポリエーテル化合物(B1)0.02部、イソシアネート架橋剤(三井武田ケミカル社製のタケネートD110N,トリメチロールプロパンキシリレンジイソシアネート)0.02部、およびベンゾイルパーオキサイド(日本油脂社製,ナイパーBMT)0.3部を配合して、アクリル系粘着剤組成物の溶液(固形分15%)を調製した。
次いで、上記アクリル系粘着剤溶液を、シリコーン処理を施した、38μmのポリエチレンテレフタレート(PET)フィルム(三菱化学ポリエステルフィルム(株)製,MRF38)の片面に、乾燥後の粘着剤層の厚さが23μmになるように塗布し、155℃で1分間乾燥を行い、偏光板(日東電工製、SEG)に転写し、粘着剤層付偏光板を作製した。
実施例1において、ポリエーテル化合物(B1)を用いないこと、または、アクリル系ポリマーの種類、架橋剤の種類もしくは使用量を表1に示すように変えたこと以外は、実施例1と同様にして、粘着剤層付偏光板を作製した。
実施例1において、ポリエーテル化合物(B)の種類またはその使用量を変えたこと、架橋剤、シランカップリング剤を表2に示す割合で用いたこと以外は、実施例1と同様にして、粘着剤層付偏光板を作製した。
実施例9において、ポリエーテル化合物(B)の種類またはその使用量を変えたこと、架橋剤、シランカップリング剤を表3に示す割合で用いたこと以外は、実施例9と同様にして、粘着剤層付偏光板を作製した。
サンプルを、幅25mm×長さ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、ラミネーターを用いて貼り付け、次いで50℃、5atmで15分間オートクレーブ処理して完全に密着させた(初期)。その後、60℃乾燥条件下で120時間加熱処理を施した(加熱後)。かかるサンプルの接着力を測定した。
サンプルを、37インチサイズとし、厚さ0.7mmの無アルカリガラス(コーニング社製,1737)にラミネーターを用いて貼着した。次いで、50℃、0.5MPaで15分間オートクレーブ処理して、上記サンプルを完全に無アクリルガラスに密着させた。かかる処理の施されたサンプルに、60℃/90%RHの雰囲気下で500時間処理を施した後(加湿試験)、85℃と-40℃の環境を1サイクル1時間で300サイクル施した後(ヒートショック試験)、偏光板とガラスの間の外観を下記基準で目視にて評価した。
◎:発泡、剥がれ、浮きなしなどの外観上の変化が全くなし。
○:わずかながら端部に剥がれ、または発泡があるが、実用上問題なし。
△:端部に剥がれ、または発泡があるが、特別な用途でなければ、実用上問題なし。
×:端部に著しい剥がれあり、実用上問題あり。
サンプルを、縦420mm×横320mmに裁断し、厚さ0.7mmの無アルカリガラス板(コーニング社製,1737)に、ラミネーターを用いて貼り付け、次いで50℃、5atmで15分間オートクレーブ処理して完全に密着させた(初期)。その後、60℃乾燥条件下で48時間加熱処理を施した(加熱後)。かかるサンプルの接着力を測定した。接着力は、上記同様の方法により測定した。
◎:3枚とも糊残りやフィルムの破断がなく良好に剥離可能。
○:3枚中一部はフィルムが破断したが、再度の剥離によって剥がせた。
△:3枚ともフィルム破断したが、再度の剥離によって剥がせた。
×:3枚とも糊残りが生じるか、または何度は剥離してもフィルムが破断して剥がせなかった。
サンプルを、37インチサイズとし、厚さ0.7mmの無アルカリガラス(コーニング社製,1737)にラミネーターを用いて貼着した。次いで、50℃、0.5MPaで15分間オートクレーブ処理して、上記サンプルを完全に無アクリルガラスに密着させた。かかる処理の施されたサンプルに、80℃、100℃、110℃の各雰囲気下で500時間処理を施した後(加熱試験)、60℃/90%RH、65℃/95%RHの各雰囲気下で500時間処理を施した後(加湿試験)、85℃と-40℃の環境を1サイクル1時間で300サイクル施した後(ヒートショック試験)、偏光板とガラスの間の外観を下記基準で目視にて評価した。
◎:発泡、剥がれ、浮きなしなどの外観上の変化が全くなし。
○:わずかながら端部に剥がれ、または発泡があるが、実用上問題なし。
△:端部に剥がれ、または発泡があるが、特別な用途でなければ、実用上問題なし。
×:端部に著しい剥がれあり、実用上問題あり。
「*2」は旭硝子社製のExcestar S2420を、
「*3」は旭硝子社製のExcestar S3430を、
「*4」は、カネカ社製のサイリルSAT10を、
「*5」は、カネカ社製のサイリルSAT350を、
「*6」は、カネカ社製のサイリルSAX220を、を示し、いずれも、反応性シリル基を有するポリエーテル化合物(B)である。
なお、*2、*4乃至*6のポリエーテル化合物(B)は、いずれも一般式(4)で表される化合物であり、A2は-C3H8-、Z1は-C3H8-Z0であり、反応性シリル基(Z0‐)は、R1、R2およびR3がいずれもメチル基のジメトキシメチルシリル基である。*3のポリエーテル化合物(B)は一般式(6)で表される化合物であり、Z3は、全て、-C3H8-Z0であり、反応性シリル基(Z0‐)はジメトキシメチルシリル基である。
*7は、製造例3で調製したポリエーテル化合物(B1)と、数平均分子量が異なること以外は同様の構造を有する化合物である。
「*8」は、カネカ社製のACX022を示し、一般式(4)において、-C3H8-Z0の代わりに、両末端にアリル基を有する化合物である。
架橋剤(C)における、「C/L」は、イソシアネート架橋剤(日本ポリウレタン工業社製のコロネートL,トリメチロールプロパンのトリレンジイソシアネートのアダクト体)を、「D110N」はイソシアネート架橋剤(三井武田ケミカル社製のタケネートD110N,トリメチロールプロパンキシリレンジイソシアネート)を示す。
架橋剤(C)における、「BPO」は、ベンゾイルパーオキサイド(日本油脂社製,ナイパーBMT)を示す。
シランカップリング剤における「KBM‐403」は、信越化学工業(株)製のKBM403を示す。
<アクリル系ポリマー(A1´)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、ブチルアクリレート86部、ベンジルアクリレート13部、2-ヒドロキシエチルアクリレート1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部を酢酸エチル100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窒素置換した後、フラスコ内の液温を55℃付近に保って8時間重合反応を行い、重量平均分子量220万のアクリル系ポリマー(a1)の溶液を調製した。
製造例1´において、アクリル系ポリマーを形成するモノマーの種類またはその割合を表4に示すように変えた他は製造例1´と同様にして、アクリル系ポリマー(A2´)乃至(A13´)、およびアクリル系ポリマー(A3)の溶液を調製した。アクリル系ポリマー(A2´)乃至(A13´)、およびアクリル系ポリマー(A3)の重量平均分子量は、いずれも220万であった。
BA:ブチルアクリレート、BzA:ベンジルアクリレート、PEA:フェノキシエチルアクリレート、HBA:4-ヒドロキシブチルアクリレート、AA:アクリル酸、を示す。
(粘着剤組成物の調製)
製造例1´で得られたアクリル系ポリマー(A1´)溶液の固形分100部に対して、反応性シリル基を有するポリエーテル化合物(B)として、カネカ社製のサイリルSAX220(一般式(4)で表される化合物において、A2は-C3H8-、Z1は-C3H8-Z0であり、反応性シリル基(Z0‐)は、R1、R2およびR3がいずれもメチル基のジメトキシメチルシリル基であり、数平均分子量が5000)1部、イソシアネート架橋剤(日本ポリウレタン工業社製のコロネートL,トリメチロールプロパンのトリレンジイソシアネートのアダクト体)0.1部およびベンゾイルパーオキサイド(日本油脂社製,ナイパーBMT)0.1部を配合して、アクリル系粘着剤組成物の溶液(固形分11%)を調製した。
次いで、上記アクリル系粘着剤溶液を、シリコーン処理を施した、厚さ38μmのポリエチレンテレフタレート(PET)フィルム(三菱化学ポリエステルフィルム(株)製,MRF38)の片面に、乾燥後の粘着剤層の厚さが23μmになるように塗布し、155℃で1分間乾燥処理して粘着剤層を形成した。
上記3種の偏光板の粘着剤層を形成する透明保護フィルム側に、それぞれ、ワイヤーバーにて下塗り剤を塗布して、下塗り層(厚さ100nm)を形成した。下塗り剤には、チオフェン系ポリマーを含む溶液(ナガセケムテックス社製,商品名「デナトロンP521-AC」)を水とイソプロピルアルコールの混合溶液で希釈し、固形分濃度が0.6重量%となるように調製したものを用いた。次いで、下塗り層に、上記粘着剤層を形成したシリコーン処理を施したPETフィルムを、それぞれ転写し3種の粘着剤層付偏光板を作製した。
実施例1において、表5に示すように、アクリル系ポリマー(A´)の種類、ポリエーテル化合物(B)の種類またはその使用量(もしくは使用しない)、架橋剤の種類またはその使用量を変えたこと、また、表5に示す割合でシランカップリング剤を用いたこと以外は、実施例1と同様にして、粘着剤層付偏光板を作製した。
サンプルを、縦420mm×横320mmのサイズに切り出したものを2枚用意した。このサンプルを、厚さ0.07mmの無アルカリガラス板の両面にクロスニコルになるようにラミネーターにて貼り合せた。次いで、50℃、5atmで15分間のオートクレーブ処理を行って二次サンプルとして(初期)。次いで、二次サンプルを、90℃の条件下で24時間の処理を行った(加熱後)。初期および加熱後の二次サンプルを、1万カンデラのバックライト上に置き、光漏れを下記の基準により、目視で評価した。
◎:コーナームラの発生がなく、実用上問題ない。
○:コーナームラがわずかながら発生しているが、表示領域には表れていないので、実用上問題ない。
△:コーナームラが発生して表示領域にはわずかに表れているが、実用上問題ない。
×:コーナームラが発生して表示領域にはきつく表れており、実用上問題がある。
サンプルを、37インチサイズとし、厚さ0.7mmの無アルカリガラス(コーニング社製,1737)にラミネーターを用いて貼着した。次いで、50℃、0.5MPaで15分間オートクレーブ処理して、上記サンプルを完全に無アクリルガラスに密着させた。かかる処理の施されたサンプルに、80℃で500時間(加熱試験1)、100℃で500時間(加熱試験2)、の処理をそれぞれ施した後、また、60℃/90%RHの雰囲気下で500時間処理を施した後(加湿試験)、85℃と-40℃の環境を1サイクル1時間で300サイクル施した後(ヒートショック試験)、偏光板とガラスの間の外観を下記基準で目視にて評価した。
◎:発泡、剥がれ、浮きなしなどの外観上の変化が全くなし。
○:わずかながら端部に剥がれ、または発泡があるが、実用上問題なし。
△:端部に剥がれ、または発泡があるが、特別な用途でなければ、実用上問題なし。
×:端部に著しい剥がれあり、実用上問題あり。
サンプルを、幅25mm×長さ100mmに裁断し、厚さ0.7mmの無アルカリガラス板(コーニング社製,1737)に、ラミネーターを用いて貼り付け、次いで50℃、5atmで15分間オートクレーブ処理して完全に密着させた(初期)。その後、60℃乾燥条件下で48時間加熱処理を施した(加熱後)。かかるサンプルの接着力を測定した。
◎:3枚とも糊残りやフィルムの破断がなく良好に剥離可能。
○:3枚中一部はフィルムが破断したが、再度の剥離によって剥がせた。
△:3枚ともフィルム破断したが、再度の剥離によって剥がせた。
×:3枚とも糊残りが生じるか、または何度は剥離してもフィルムが破断して剥がせなかった。
「*4」は、カネカ社製のサイリルSAT10を、
「*6」は、カネカ社製のサイリルSAX220を、を示し、いずれも、反応性シリル基を有するポリエーテル化合物(B)である。
なお、*4および*6のポリエーテル化合物(B)は、いずれも一般式(4)で表される化合物であり、A2は-C3H8-、Z1は-C3H8-Z0であり、反応性シリル基(Z0‐)は、R1、R2およびR3がいずれもメチル基のジメトキシメチルシリル基である。SAX220は一般式(6)で表される化合物であり、Z3は、全て、-C3H8-Z0であり、反応性シリル基(Z0‐)はジメトキシメチルシリル基である。
「*8」は、カネカ社製のACX022を示し、一般式(4)において、-C3H8-Z0の代わりに、両末端にアリル基を有する化合物である。
架橋剤(C)における、「C/L」は、イソシアネート架橋剤(日本ポリウレタン工業社製のコロネートL,トリメチロールプロパンのトリレンジイソシアネートのアダクト体)を、「D110N」はイソシアネート架橋剤(三井武田ケミカル社製のタケネートD110N,トリメチロールプロパンキシリレンジイソシアネート)を示す。
架橋剤(C)における、「BPO」は、ベンゾイルパーオキサイド(日本油脂社製,ナイパーBMT)を示す。
シランカップリング剤における「KBM‐403」は、信越化学工業(株)製のKBM403を示す。
Claims (24)
- (メタ)アクリル系ポリマー(A);および
ポリエーテル骨格を有し、かつ少なくとも1つの末端に、
一般式(1):-SiRaM3-a
(式中、Rは、置換基を有していてもよい、炭素数1~20の1価の有機基であり、Mは水酸基又は加水分解性基であり、aは1~3の整数である。但し、Rが複数存在するとき複数のRは互いに同一であっても異なっていてもよく、Mが複数存在するとき複数のMは互いに同一であっても異なっていてもよい。)で表される反応性シリル基を有するポリエーテル化合物(B)、を含有することを特徴とする光学フィルム用粘着剤組成物。 - ポリエーテル化合物(B)が有するポリエーテル骨格は、炭素数1~10の直鎖または分岐鎖のオキシアルキレン基の繰り返し構造単位とすることを特徴とする請求項1記載の光学フィルム用粘着剤組成物。
- ポリエーテル化合物(B)が、
一般式(2):RaM3-aSi-X-Y-(AO)n-Z
(式中、Rは、置換基を有していてもよい、炭素数1~20の1価の有機基であり、Mは水酸基又は加水分解性基であり、aは1~3の整数である。但し、Rが複数存在するとき複数のRは互いに同一であっても異なっていてもよく、Mが複数存在するとき複数のMは互いに同一であっても異なっていてもよい。AOは、直鎖または分岐鎖の炭素数1~10のオキシアルキレン基を示し、nは1~1700であり、オキシアルキレン基の平均付加モル数を示す。Xは、炭素数1~20の直鎖または分岐鎖のアルキレン基を示す。Yは、エーテル結合、エステル結合、ウレタン結合、またはカーボネート結合を示す。
Zは、水素原子、1価の炭素数1~10の炭化水素基、
一般式(2A):-Y1-X-SiRaM3-a
(式中、R、M、Xは、前記と同じ。Y1は単結合、-CO-結合、-CONH-結合、または-COO-結合を示す。)、または、
一般式(2B):-Q{-(OA)n-Y-X-SiRaM3-a}m
(式中、R、M、X、Yは、前記と同じ。OAは前記のAOに同じで、nは前記と同じ。Qは、2価以上の炭素数1~10の炭化水素基であり、mは当該炭化水素基の価数と同じ。)で表される基である。)で表される化合物であることを特徴とする請求項2記載の光学フィルム用粘着剤組成物。 - ポリエーテル化合物(B)が、
一般式(6):Z3-O-(A1O)n-C{-CH2-(A1O)n-Z3}2
(式中、A1Oは炭素数2~6のオキシアルキレン基であり、nは1~1700であり、A1Oの平均付加モル数を示す。Z3は、水素原子、または-A2-Z0であり、いずれか少なくとも1つのZ3は-A2-Z0である。A2は炭素数2~6のアルキレン基である。
Z0は、一般式(3):
(式中、R1、R2およびR3は、炭素数1~6の1価の炭化水素基であり、同一分子中で同一であっても異なっていてもよい。)で表されるアルコキシシリル基である。)で表される化合物であることを特徴とする請求項3または4記載の光学フィルム用粘着剤組成物。 - ポリエーテル化合物(B)の数平均分子量が、300~100000であることを特徴とする請求項1~7のいずれかに記載の光学フィルム用粘着剤組成物。
- (メタ)アクリル系ポリマー(A)100重量部に対して、ポリエーテル化合物(B)を0.001~20重量部含有することを特徴とする請求項1~8のいずれかに記載の光学フィルム用粘着剤組成物。
- (メタ)アクリル系ポリマー(A)が、モノマー単位として、アルキル(メタ)アクリレートおよびヒドロキシル基含有モノマーを含有することを特徴とする請求項1~9のいずれかに記載の光学フィルム用粘着剤組成物。
- (メタ)アクリル系ポリマー(A)が、モノマー単位として、アルキル(メタ)アクリレートおよびカルボキシル基含有モノマーを含有することを特徴とする請求項1~10のいずれかに記載の光学フィルム用粘着剤組成物。
- (メタ)アクリル系ポリマー(A)が、モノマー単位として、アルキル(メタ)アクリレートおよび重合性芳香環含有モノマーを含有する(メタ)アクリル系ポリマー(A´)であることを特徴とする請求項1~9のいずれかに記載の光学フィルム用粘着剤組成物。
- (メタ)アクリル系ポリマー(A´)が、モノマー単位として、重合性芳香環含有モノマーを1~50重量%を含有することを特徴とする請求項12記載の光学フィルム用粘着剤組成物。
- (メタ)アクリル系ポリマー(A´)が、モノマー単位として、さらに、ヒドロキシル基含有モノマーを含有することを特徴とする請求項12または13に記載の光学フィルム用粘着剤組成物。
- (メタ)アクリル系ポリマー(A´)が、モノマー単位として、さらに、カルボキシル基含有モノマーを含有することを特徴とする請求項12~14のいずれかに記載の光学フィルム用粘着剤組成物。
- さらに、架橋剤を含有することを特徴とする請求項1~15のいずれかに記載の光学フィルム用粘着剤組成物。
- 架橋剤(C)は、(メタ)アクリル系ポリマー(A)100重量部に対して、0.01~20重量部含有することを特徴とする請求項16記載の光学フィルム用粘着剤組成物。
- 架橋剤(C)が、イソシアネート系化合物および過酸化物から選ばれるいずれか少なくとも1種であることを特徴とする請求項16または17記載の光学フィルム用粘着剤組成物。
- (メタ)アクリル系ポリマー(A)100重量部に対して、さらに、シランカップリング剤(D)を0.001~5重量部含有することを特徴とする請求項1~18のいずれかに記載の光学フィルム用粘着剤組成物。
- (メタ)アクリル系ポリマー(A)の重量平均分子量が、50万~400万であることを特徴とする請求項1~19のいずれかに記載の光学フィルム用粘着剤組成物。
- 請求項1~20のいずれかに記載の光学フィルム用粘着剤組成物により形成されていることを特徴とする光学フィルム用粘着剤層。
- 光学フィルムの少なくとも片側に、請求項21に記載の光学フィルム用粘着剤層が形成されていることを特徴とする粘着型光学フィルム。
- 光学フィルムと、光学フィルム用粘着剤層の間に、易接着層を有することを特徴とする請求項22記載の粘着型光学フィルム。
- 請求項22または23記載の粘着型光学フィルムを少なくとも1つ用いたことを特徴とする画像表示装置。
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US13/266,946 US20120121824A1 (en) | 2009-04-30 | 2010-04-27 | Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer for optical film, pressure-sensitive adhesive optical film and image display |
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