Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/062—Copolymers with monomers not covered by C09J133/06
  • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/22—Plastics; Metallised plastics
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2433/00—Presence of (meth)acrylic polymer
• • 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
  • C09J2471/00—Presence of polyether

Definitions

• the present invention is an optical film pressure-sensitive adhesive capable of forming a pressure-sensitive adhesive layer capable of coexistence of reworkability capable of easily peeling an optical film from a liquid crystal panel or the like without adhesive residue and durability after long-term storage.
• the present invention relates to an optical film with an adhesive layer in which an adhesive layer is formed on at least one surface of the optical film by the composition and the adhesive composition.
• 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 optical film with the pressure-sensitive adhesive layer.
• a polarizing film, 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 liquid crystal display devices 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 film is attached.
• various optical elements have been used for liquid crystal panels in order to improve the display quality of displays. For example, a retardation plate for preventing coloring, 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 has the advantage that a drying step is not required to fix the optical film, so that the adhesive is an optical layer with an adhesive layer provided in advance as an adhesive layer on one side of the optical film.
• a film is generally used.
• the optical film when an optical film is bonded to a liquid crystal cell, the optical film is peeled off from the liquid crystal panel and the liquid crystal cell is reused even if the bonding position is wrong or a foreign object is caught in the bonding surface.
• the required properties required for the pressure-sensitive adhesive include re-peelability (reworkability) that allows the optical film to be easily peeled off from the liquid crystal panel in the peeling step.
• 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 adhesive is required not to suffer from problems such as peeling and floating due to the adhesive, with respect to durability tests such as heating and humidification normally performed as an environmental promotion test.
• some products may be used after long-term storage of, for example, 6 months or more, and even such long-term storage products prevent the occurrence of problems such as peeling and floating due to a decrease in adhesive adhesive strength. Is required.
• the adhesive strength of the pressure-sensitive adhesive is lowered, the reworkability tends to be improved, but the adhesive strength after long-term storage is also lowered, so that the durability tends to deteriorate.
• Patent Document 1 100 parts by weight of an acrylic copolymer having a weight average molecular weight of 500,000 or more containing 0.5 to 15% by weight of a vinyl monomer having a carboxyl group as a monomer unit, a secondary or tertiary amine compound
• An acrylic pressure-sensitive adhesive composition comprising 1 to 3 parts by weight and 1 to 50 parts by weight of a polyether and / or acrylic polymer having one or more alkoxysilyl groups in the molecule is described.
• Patent Document 2 a monomer composition containing 0.5 to 15 wt% of a carboxyl group-containing vinyl monomer is polymerized, and the weight average molecular weight Mw is 700,000 to 2 million, and the weight average molecular weight Mw is 100 parts by weight of an acrylic polymer having a ratio Mw / Mn of 1.5 to 4 and a number average molecular weight Mn, each having a plurality of functional groups capable of forming a crosslink with a carboxyl group, organic compounds, organic 0.001 to 5 parts by weight of at least one crosslinking agent selected from the group consisting of metal compounds and metal salts, 0.01 to 5 parts by weight of polyether-modified silicone oil, and at least one alkoxysilyl per molecule
• An acrylic pressure-sensitive adhesive composition containing 0.1 to 10 parts by weight of a polyether having a group is described.
• the pressure-sensitive adhesive obtained from the pressure-sensitive adhesive composition described in these documents has a high adhesive force and tends to have poor reworkability.
• Patent Document 3 a pressure-sensitive adhesive composition for an optical film containing a (meth) acrylic polymer and a polyether compound having a reactive silyl group is described.
• the pressure-sensitive adhesive obtained from such a pressure-sensitive adhesive composition can easily peel off an optical film from a liquid crystal panel or the like without adhesive residue, and is excellent in reworkability.
• the combination of the (meth) acrylic polymer and the polyether compound having a reactive silyl group is excellent in the reworkability of the resulting pressure-sensitive adhesive, but has undergone, for example, long-term storage for 6 months or more. When used, it has been found that there is room for further improvement in terms of durability.
• the present invention is an optical film pressure-sensitive adhesive capable of forming a pressure-sensitive adhesive layer capable of coexistence of reworkability capable of easily peeling an optical film from a liquid crystal panel or the like without adhesive residue and durability after long-term storage.
• An object is to provide a composition.
• this invention provides the optical film with an adhesive layer which has an adhesive layer formed with the said adhesive composition for optical films, Furthermore, the image display apparatus using the said optical film with an adhesive layer is provided. The purpose is to do.
• the present invention provides a (meth) acrylic polymer (A) containing a hydroxyl group-containing monomer as a monomer unit; Having a repeating structural unit of an oxyalkylene group and at least one terminal, Formula (1): —SiR a M 3-a (Wherein 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 0 to 2) However, when a plurality of R are present, the plurality of R may be the same or different from each other, and when a plurality of M are present, the plurality of M may be the same or different from each other. And a silane coupling agent (C) having an acetoacetyl group.
• the present invention relates to a pressure-sensitive adhesive composition for optical films, comprising: a polyether compound (B) having a reactive silyl group;
• the hydroxyl group-containing monomer is preferably 4-hydroxybutyl (meth) acrylate.
• the polyether compound (B) is: Formula (2): R a M 3-a Si—XY— (AO) n —Z (Wherein 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 0 to 2)
• 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 0 to 2
• 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.
• Y represents a chain bond or a branched chain alkylene group, and Y represents an ether bond, an ester bond, a urethane bond, or a carbonate bond.
• Z is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms
• 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. It is preferable that it is a compound represented by this.
• 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— (AO) n —Z 1
• AO is the same as described above, n is 1 to 1700, and represents the average number of added moles of AO.
• Z 1 is a hydrogen atom or —A 2 —Z 0.
• a 2 is the number of carbon atoms. 2 to 6 alkylene groups.
• 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. 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— (AO) n —Z 2 (Wherein AO is a linear or branched structure containing an oxyalkylene group as a repeating structural unit, n is 1 to 1700, and represents the average number of moles added of AO.
• Z 2 is 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. A silyl group. ) Is more preferable.
• the polyether compound (B) is a compound represented by the general formula (2), General formula (6): Z 3- (AO) n -OG-CR 4 ⁇ -GO- (AO) n -Z 3 ⁇ 2
• AO is a linear or branched structure containing an oxyalkylene group as a repeating structural unit
• n is 1 to 1700, and indicates the average number of added moles of AO.
• Z 3 is a hydrogen atom, Or -A 2 -Z 0 , and at least one of Z 3 is -A 2 -Z 0.
• a 2 is an alkylene group having 2 to 6 carbon atoms
• R 4 is a hydrogen atom or carbon number 1 to 3 represents an alkylene group
• G represents a single bond or a methylene group.
• 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 silane coupling agent (C) having an acetoacetyl group may be contained with respect to 100 parts by weight of the (meth) acrylic polymer (A). preferable.
• those containing 0.001 to 5 parts by weight of the polyether compound (B) with respect to 100 parts by weight of the (meth) acrylic polymer (A) can be preferably used.
• those containing 0.01 to 2 parts by weight of a peroxide as the crosslinking agent (D) with respect to 100 parts by weight of the (meth) acrylic polymer (A) are preferably used. be able to.
• 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 optical film with an adhesive layer, wherein the optical film adhesive layer is formed on at least one side of the optical film.
• the said optical film with an adhesive layer 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 using at least one optical film with an adhesive layer.
• optical film pressure-sensitive adhesive composition of the present invention in addition to the base polymer (meth) acrylic polymer (A), it has a repeating structural unit of an oxyalkylene group and has a reactive silyl group at at least one terminal. And a silane coupling agent (C) having an acetoacetyl group.
• the optical film with the pressure-sensitive adhesive layer having the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition for optical films of the present invention comprises the polyether compound (B), whereby the optical film with the pressure-sensitive adhesive layer.
• the optical film with the pressure-sensitive adhesive layer can be easily peeled off from the cell or the like, has excellent reworkability, and can be reused without damaging or contaminating the liquid crystal cell.
• the optical film with the pressure-sensitive adhesive layer can be easily peeled from the large-sized liquid crystal cell. .
• the polyether compound (B) having a reactive silyl group at at least one terminal is present in the pressure-sensitive adhesive layer for a long period of time, the reactive silyl group is hydrolyzed and the highly reactive silyl group is hydrophilic. It changes to highly silanol.
• the polyether compound (B) in the pressure-sensitive adhesive layer easily moves to the adherend side, the adhesive force between the pressure-sensitive adhesive layer and the adherend is reduced, and durability deterioration after long-term storage is expected.
• the deterioration in durability is caused by a polyether compound having a highly hydrophilic silanol when the optical film with the pressure-sensitive adhesive layer is laminated on glass or the like (when the pressure-sensitive adhesive layer is laminated on glass as an adherend) ( Since B) tends to shift to the glass side, durability deterioration accompanying a decrease in adhesive strength between the pressure-sensitive adhesive layer and the glass is expected after long-term storage.
• the silane coupling agent (C) which has an acetoacetyl group, the oxyalkylene group and acetoacetyl group in a polyether compound (B) interact through a hydrogen bond etc., and an adhesive layer It prevents that the polyether compound (B) inside transfers to the adherend side. As a result, even after long-term storage, the adhesive force between the pressure-sensitive adhesive layer and the adherend can be prevented from being lowered, and the durability can be improved.
• 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.
• (Meth) acrylic polymer (A) contains a hydroxyl group-containing monomer as a monomer unit.
• the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, (meth) Examples thereof include 8-hydroxyoctyl acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) -methyl acrylate. Among these, 4-hydroxybutyl (meth) acrylate is preferable.
• the (meth) acrylic polymer (A) contains a hydroxyl group-containing monomer as a monomer unit, preferably 0.3 parts by weight or more, more preferably 0.5 parts by weight or more, more preferably 1 part by weight or more.
• a hydroxyl group-containing monomer preferably 0.3 parts by weight or more, more preferably 0.5 parts by weight or more, more preferably 1 part by weight or more.
• the adhesive force is increased and reworkability is disadvantageous, so that it is preferably 10 parts by weight or less, The amount is more preferably 7 parts by weight or less, and further preferably 5 parts by weight or less.
• 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.
• copolymerization monomers include, for example, (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like containing carboxyl groups Monomer; Monomer anhydride, itaconic anhydride and other acid anhydride group-containing monomers; acrylic acid caprolactone adduct; styrene sulfonic acid and allyl sulfonic acid, 2- (meth) acrylamido-2-methylpropane sulfonic acid, (meth) Examples thereof include sulfonic acid group-containing monomers such as acrylamide propanesulfonic acid, sulfopropyl (meth) acrylate, and (meth) acryloyloxynaphthalene sulfonic acid; and phosphoric acid group-containing monomers such as 2-hydroxyethylacryloy
• (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.
• 8-vinyloctyltriethoxysilane 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, 10-acryloyloxydecyltriethoxysilane, and the like.
• 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.
• 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, and polyoxyethylene-polyoxypropylene block polymer are listed. These emulsifiers may be used alone or in combination of two or more.
• reactive emulsifiers emulsifiers into which radical polymerizable functional groups such as propenyl groups and allyl ether groups are introduced, specifically, for example, Aqualon HS-10, HS-20, KH-10, BC-05 BC-10, BC-20 (all of which are manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria soap SE10N (manufactured by 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 repeating structural unit of an oxyalkylene group and has at least one terminal at the following general formula (1): —SiR a M 3-a (Wherein 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 0 to 2) However, when a plurality of R are present, the plurality of R may be the same or different from each other, and when a plurality of M are present, 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 , R 2 and R 3 in the alkoxysilyl group represented by the general formula (3) are, for example, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched carbon 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 oxyalkylene 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, more preferably 2.
• 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.
• the oxyalkylene group include an oxyethylene group, an oxypropylene group, and an oxybutylene group.
• those having an oxyethylene group structural unit have high skeleton hydrophilicity and small change in the amount transferred to the adherend due to the generation of silanol. Is particularly preferred because it is less likely to decrease.
• the polyether compound (B) preferably has a main chain consisting essentially of repeating structural units having an oxyalkylene group.
• the main chain substantially consists of repeating structural units of oxyalkylene groups 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 and a linking group with a reactive silyl group may be included.
• the repeating structural unit of the oxyalkylene group is preferably 50% by weight or more, more preferably 80% by weight or more of the total weight of the polyether compound (B).
• R a M 3-a Si—XY— (AO) n —Z (Wherein 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 0 to 2)
• 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 0 to 2
• 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.
• Y represents a chain bond or a branched chain alkylene group, and Y represents an ether bond, an ester bond, a urethane bond, or a carbonate bond.
• Z is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms
• 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, Y
• Formula (4) Z 0 —A 2 —O— (AO) n —Z 1 (Wherein AO is a linear or branched structure containing an oxyalkylene group as a repeating structural unit, n is 1 to 1700, and represents the average number of moles added of AO.
• 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— (AO) n —Z 2 (Wherein AO is a linear or branched structure containing an oxyalkylene group as a repeating structural unit, n is 1 to 1700, and represents the average number of moles added of AO. Z 2 is 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- (AO) n -OG-CR 4 ⁇ -GO- (AO) n -Z 3 ⁇ 2
• AO is a linear or branched structure containing an oxyalkylene group as a repeating structural unit, n is 1 to 1700, and indicates the average number of added moles of AO.
• Z 3 is a hydrogen atom, Or -A 2 -Z 0 , and at least one of Z 3 is -A 2 -Z 0.
• a 2 is an alkylene group having 2 to 6 carbon atoms, and R 4 is a hydrogen atom or carbon number A compound represented by 1 to 3 alkylene groups) is preferred.
• G represents a single bond or a methylene group.
• Z 0 is an alkoxysilyl group represented by the general formula (3).
• the oxyalkylene group of AO may be either linear or branched.
• the alkylene group for A 2 may be linear or branched, and an ethylene group is particularly preferable.
• 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 the average number of added moles of oxyalkylene group, and the polyether compound (B ) Is preferably controlled so that the number average molecular weight is in 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 oxyethylene groups formed by ring-opening polymerization of ethylene oxide.
• 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 polyoxyalkylene 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 EST250, EST280; SAT10, SAT200, SAT220, SAT350, SAT400, EXCESTAR S2410, S2420 manufactured by Asahi Glass Co., Ltd.
• Examples include SIB1824.82 and SIB1824.84 manufactured by GELEST.
• the proportion of the polyether compound (B) in the pressure-sensitive adhesive composition of the present invention is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (A).
• the polyether compound (B) is preferably 0.005 part by weight or more, and more preferably 0.01 part by weight or more.
• the amount of the polyether compound (B) is more than 5 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 1 part by weight or less, and more preferably 0.5 part by weight or less.
• the ratio of the said polyether compound (B) can set the preferable range by employ
• the pressure-sensitive adhesive composition of the present invention contains a silane coupling agent (C) having an acetoacetyl group in addition to the (meth) acrylic polymer (A) and the polyether compound (B).
• a silane coupling agent (C) having an acetoacetyl group in addition to the (meth) acrylic polymer (A) and the polyether compound (B).
• Specific examples of the silane coupling agent (C) include an acetoacetyl group and the following general formula (2): -SiR a M 3-a (2) (Wherein 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 0 to 2)
• 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 0 to 2
• the plurality of R may be the same or different
• the compound containing the reactive silyl group represented is mentioned.
• Examples of commercially available silane coupling agents (C) include A100 manufactured by Soken Chemical Co., Ltd.
• the proportion of the silane coupling agent (C) in the pressure-sensitive adhesive composition of the present invention is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (A). If the silane coupling agent (C) is less than 0.001 part by weight, peeling may occur after long-term storage. If the amount exceeds 5 parts by weight, it will be adhesive in both endurance tests immediately after production and after long-term storage. Peeling of the agent layer is likely to occur.
• the ratio of the silane coupling agent (C) in the adhesive composition of this invention 0.02 weight part or more is more preferable, and 0.1 weight part or more is further more preferable. Moreover, 3 weight part or less is more preferable, and 2 weight part or less is still more preferable.
• the pressure-sensitive adhesive composition of the present invention can contain a crosslinking agent (D).
• a crosslinking agent (D) an organic crosslinking agent or a polyfunctional metal chelate can be used.
• 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. can give.
• the atom in the organic compound that is covalently bonded or coordinated include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone
• an isocyanate-based crosslinking agent and / or a peroxide-type crosslinking agent is preferable.
• the compounds related 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 (D) used is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1 part by weight, based on 100 parts by weight of the (meth) acrylic polymer (A). If the crosslinking agent (D) 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 2 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 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 an optical film with a pressure-sensitive adhesive layer according to 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 carry out antistatic treatment such as.
• a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment, the peelability from the pressure-sensitive adhesive layer can be further improved.
• seat which carried out the peeling process used in preparation of said optical film with an adhesive layer can be used as a separator of an optical film with an adhesive layer as it is, and can simplify in a 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.
• the optical film includes a polarizing film.
• a polarizing film having a transparent protective film on one or both sides of a polarizer is generally used.
• the polarizer is not particularly limited, and various types can be used.
• polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
• hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
• examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
• a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable.
• the thickness of these polarizers is not particularly limited, but is generally about 5 to 80 ⁇ m.
• a polarizer in which a polyvinyl alcohol film is dyed with iodine and uniaxially stretched can be prepared, for example, by dyeing polyvinyl alcohol in an aqueous solution of iodine and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.
• Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching.
• the film can be stretched even in an aqueous solution such as boric acid or potassium iodide or in a water bath.
• a thin polarizer having a thickness of 10 ⁇ m or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 ⁇ m. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.
• the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition according to the present invention is obtained from the pressure-sensitive adhesive composition according to the present invention because the durability after long-term storage does not deteriorate even if the reworkability is improved.
• the obtained pressure-sensitive adhesive layer is particularly useful as a pressure-sensitive adhesive layer for a polarizing film with a pressure-sensitive adhesive layer having a thin polarizer in which a transparent protective film is laminated on one side or both sides.
• the thin polarizer typically, JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917, PCT / JP2010 / 001460, or Japanese Patent Application No. 2010- And a thin polarizing film described in Japanese Patent Application No. 269002 and Japanese Patent Application No. 2010-263692.
• These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state and a step of dyeing. With this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.
• PVA-based resin polyvinyl alcohol-based resin
• the thin polarizing film among the production methods including the step of stretching in the state of a laminate and the step of dyeing, WO2010 / 100917 pamphlet, PCT / PCT / PCT / JP 2010/001460 specification, or Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692, the one obtained by a production method including a step of stretching in a boric acid aqueous solution is preferable. What is obtained by the manufacturing method including the process of extending
• the thin high-performance polarizing film described in the specification of PCT / JP2010 / 001460 is a thin film having a thickness of 7 ⁇ m or less made of a PVA-based resin oriented with a dichroic material, which is integrally formed on a resin base material. It is a high-functional polarizing film, and has optical properties such as a single transmittance of 42.0% or more and a degree of polarization of 99.95% or more.
• the thin high-performance polarizing film generates a PVA-based resin layer by applying and drying a PVA-based resin on a resin substrate having a thickness of at least 20 ⁇ m, and the generated PVA-based resin layer is dyed with a dichroic substance.
• the dichroic substance is adsorbed on the PVA resin layer by dipping in the solution, and the PVA resin layer on which the dichroic substance is adsorbed is integrated with the resin base material in the boric acid aqueous solution, based on the total draw ratio. It can manufacture by extending
• a method for producing a laminate film including a thin high-performance polarizing film in which a dichroic substance is oriented and includes a resin base material having a thickness of at least 20 ⁇ m and a PVA resin on one side of the resin base material.
• stacking containing the process of producing
• a polarizer having a thickness of 10 ⁇ m or less it is a continuous web polarizing film made of a PVA-based resin in which a dichroic material is oriented, and is formed on a thermoplastic resin substrate. What was obtained by extending
• stretching can be used.
• the thermoplastic resin substrate is preferably an amorphous ester thermoplastic resin substrate or a crystalline ester thermoplastic resin substrate.
• the thin polarizing films in the above-mentioned Japanese Patent Application Nos. 2010-269002 and 2010-263692 are continuous web polarizing films made of a PVA-based resin in which a dichroic material is oriented, and are amorphous.
• the laminate including the PVA-based resin layer formed on the ester-based thermoplastic resin base material was stretched in a two-stage stretching process consisting of air-assisted stretching and boric acid-water stretching, so that the thickness was 10 ⁇ m or less. Is.
• Such a thin polarizing film has P> ⁇ (10 0.929 T ⁇ 42.4 ⁇ 1) ⁇ 100 (where T ⁇ 42.3) and P ⁇ , where T is the single transmittance and P is the polarization degree. It is preferable that the optical properties satisfy 99.9 (where T ⁇ 42.3).
• the thin polarizing film is a stretch intermediate formed of an oriented PVA resin layer by high-temperature stretching in the air with respect to the PVA resin layer formed on the amorphous ester thermoplastic resin substrate of the continuous web.
• a colored intermediate product comprising a PVA-based resin layer in which a dichroic material (preferably iodine or a mixture of iodine and an organic dye) is oriented by adsorption of the dichroic material to the stretched intermediate product and a step of generating the product.
• a thin polarizing film comprising: a step of producing a product; and a step of producing a polarizing film having a thickness of 10 ⁇ m or less comprising a PVA resin layer in which a dichroic substance is oriented by stretching in a boric acid solution with respect to a colored intermediate product It can manufacture with the manufacturing method of.
• the total draw ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material by high-temperature drawing in air and drawing in boric acid solution should be 5 times or more. desirable.
• stretching can be 60 degreeC or more.
• the colored intermediate product is added to the aqueous boric acid solution whose liquid temperature does not exceed 40 ° C. It is desirable to do so by dipping.
• the amorphous ester-based thermoplastic resin base material is amorphous polyethylene containing copolymerized polyethylene terephthalate copolymerized with isophthalic acid, copolymerized polyethylene terephthalate copolymerized with cyclohexanedimethanol, or other copolymerized polyethylene terephthalate. It can be terephthalate and is preferably made of a transparent resin, and the thickness thereof can be 7 times or more the thickness of the PVA resin layer to be formed.
• the draw ratio of high-temperature drawing in the air is preferably 3.5 times or less, and the drawing temperature of high-temperature drawing in the air is preferably not less than the glass transition temperature of the PVA resin, specifically in the range of 95 ° C to 150 ° C.
• the total stretching ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material is preferably 5 to 7.5 times .
• the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin base material is 5 times or more and 8.5 times or less. Is preferred. More specifically, a thin polarizing film can be produced by the following method.
• a base material for a continuous web of isophthalic acid copolymerized polyethylene terephthalate (amorphous PET) in which 6 mol% of isophthalic acid is copolymerized is prepared.
• the glass transition temperature of amorphous PET is 75 ° C.
• a laminate comprising a continuous web of amorphous PET substrate and a polyvinyl alcohol (PVA) layer is prepared as follows. Incidentally, the glass transition temperature of PVA is 80 ° C.
• a 200 ⁇ m-thick amorphous PET base material and a 4-5% PVA aqueous solution in which PVA powder having a polymerization degree of 1000 or more and a saponification degree of 99% or more are dissolved in water are prepared.
• a PVA aqueous solution is applied to a 200 ⁇ m-thick amorphous PET substrate, dried at a temperature of 50 to 60 ° C., and a laminate having a 7 ⁇ m-thick PVA layer formed on the amorphous PET substrate is formed. obtain.
• a thin and highly functional polarizing film having a thickness of 3 ⁇ m is manufactured from the laminate including the PVA layer having a thickness of 7 ⁇ m through the following steps including a two-stage stretching process of air-assisted stretching and boric acid water stretching.
• the laminate including the 7 ⁇ m-thick PVA layer is integrally stretched with the amorphous PET substrate to produce a stretched laminate including the 5 ⁇ m-thick PVA layer.
• a laminate including a 7 ⁇ m-thick PVA layer is subjected to a stretching apparatus disposed in an oven set to a stretching temperature environment of 130 ° C. so that the stretching ratio is 1.8 times. Are stretched uniaxially at the free end.
• the PVA layer contained in the stretched laminate is changed to a 5 ⁇ m thick PVA layer in which PVA molecules are oriented.
• this colored laminate has a single layer transmittance of the PVA layer constituting the high-performance polarizing film that is finally produced by using the stretched laminate in a staining solution containing iodine and potassium iodide at a liquid temperature of 30 ° C.
• Iodine is adsorbed to the PVA layer contained in the stretched laminate by dipping for an arbitrary period of time so as to be 40 to 44%.
• the staining solution uses water as a solvent, and an iodine concentration within the range of 0.12 to 0.30% by weight and a potassium iodide concentration within the range of 0.7 to 2.1% by weight.
• concentration ratio of iodine and potassium iodide is 1 to 7.
• potassium iodide is required to dissolve iodine in water. More specifically, by immersing the stretched laminate in a dyeing solution having an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight for 60 seconds, iodine is applied to a 5 ⁇ m-thick PVA layer in which PVA molecules are oriented. A colored laminate is adsorbed on the substrate.
• the colored laminated body is further stretched integrally with the amorphous PET base material by the second stage boric acid underwater stretching step to produce an optical film laminate including a PVA layer constituting a highly functional polarizing film having a thickness of 3 ⁇ m.
• the optical film laminate is subjected to stretching by applying the colored laminate to a stretching apparatus provided in a treatment apparatus set to a boric acid aqueous solution having a liquid temperature range of 60 to 85 ° C. containing boric acid and potassium iodide. It is stretched uniaxially at the free end so that the magnification is 3.3 times. More specifically, the liquid temperature of the boric acid aqueous solution is 65 ° C.
• the colored laminate having an adjusted iodine adsorption amount is first immersed in an aqueous boric acid solution for 5 to 10 seconds. After that, the colored laminate is passed as it is between a plurality of sets of rolls with different peripheral speeds, which is a stretching apparatus installed in the processing apparatus, and the stretching ratio can be freely increased to 3.3 times over 30 to 90 seconds. Stretch uniaxially.
• the PVA layer contained in the colored laminate is changed into a PVA layer having a thickness of 3 ⁇ m in which the adsorbed iodine is oriented higher in one direction as a polyiodine ion complex.
• This PVA layer constitutes a highly functional polarizing film of the optical film laminate.
• the optical film laminate was removed from the boric acid aqueous solution and adhered to the surface of the 3 ⁇ m-thick PVA layer formed on the amorphous PET substrate by the washing step. It is preferable to wash boric acid with an aqueous potassium iodide solution. Thereafter, the washed optical film laminate is dried by a drying process using hot air at 60 ° C.
• the cleaning process is a process for eliminating appearance defects such as boric acid precipitation.
• an adhesive is applied to the surface of a 3 ⁇ m-thick PVA layer formed on an amorphous PET substrate by a bonding and / or transfer process.
• the amorphous PET base material can be peeled off, and the 3 ⁇ m thick PVA layer can be transferred to the 80 ⁇ m thick triacetyl cellulose film.
• the manufacturing method of said thin-shaped polarizing film may include another process other than the said process.
• Examples of other steps include an insolubilization step, a crosslinking step, and a drying (adjustment of moisture content) step.
• the other steps can be performed at any appropriate timing.
• the insolubilization step is typically performed by immersing the PVA resin layer in a boric acid aqueous solution. By performing the insolubilization treatment, water resistance can be imparted to the PVA resin layer.
• the concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water.
• the liquid temperature of the insolubilizing bath (boric acid aqueous solution) is preferably 20 ° C.
• the insolubilization step is performed after the laminate is manufactured and before the dyeing step and the underwater stretching step.
• the crosslinking step is typically performed by immersing the PVA resin layer in an aqueous boric acid solution.
• the concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water.
• blend iodide it is preferable to mix
• the blending amount of iodide is preferably 1 to 5 parts by weight with respect to 100 parts by weight of water. Specific examples of the iodide are as described above.
• the liquid temperature of the crosslinking bath is preferably 20 ° C. to 50 ° C.
• the crosslinking step is performed before the second boric acid aqueous drawing step.
• the dyeing step, the crosslinking step, and the second boric acid aqueous drawing step are performed in this order.
• thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is used.
• thermoplastic resins include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, cyclic Examples thereof include polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.
• a transparent protective film is bonded to one side of the polarizer by an adhesive layer.
• thermosetting resin such as a system or an ultraviolet curable resin
• a thermosetting resin such as a system or an ultraviolet curable resin
• the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent.
• the content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. .
• content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.
• 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. These can be used alone as an optical film, or can be laminated on the polarizing film for practical use to use one layer or two or more layers.
• An optical film obtained by laminating the optical layer on a polarizing film can be formed by a method of laminating separately sequentially 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 a target retardation characteristic or the like.
• the optical film with an adhesive layer 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 optical film with an adhesive layer, and an illumination system as necessary, and incorporating a drive circuit.
• a liquid crystal display device is generally formed by appropriately assembling components such as a display panel such as a liquid crystal cell, an optical film with an adhesive layer, and an illumination system as necessary, and incorporating a drive circuit.
• 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.
• liquid crystal display devices such as a liquid crystal display device in which an optical film with an adhesive layer is disposed on one side or both sides of a display panel such as a liquid crystal cell, or a lighting system using a backlight or a reflector 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 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.
• a diffusing plate for example, 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.
• a protective plate such as a prism array, a lens array sheet, a light diffusing plate, a backlight, etc.
• a prism array such as a prism array, a lens array sheet, a light diffusing plate, a backlight, etc.
• polarizing film 1 (SEG)
• SEG polarizing film 1
• a polyvinyl alcohol film having a thickness of 80 ⁇ m was stretched up to 3 times while being dyed for 1 minute in an iodine solution of 0.3% concentration at 30 ° C. between rolls having different speed ratios. Thereafter, the total draw ratio was stretched to 6 times while being immersed in an aqueous solution containing 60% at 4% concentration of boric acid and 10% concentration of potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5% concentration for 10 seconds, drying was performed at 50 ° C. for 4 minutes to obtain a polarizer (thickness 30 ⁇ m).
• a polarizing film 1 (SEG) was prepared by laminating a saponified 80 ⁇ m thick triacetylcellulose film on both surfaces of the polarizer with a polyvinyl alcohol-based adhesive.
• polarizing film 2 (thin polarizing film)
• a laminated body in which a PVA layer having a thickness of 24 ⁇ m is formed on an amorphous PET substrate is produced by air-assisted stretching at a stretching temperature of 130 degrees, and then stretched.
• a colored laminate is produced by dyeing the laminate, and the colored laminate is further stretched integrally with an amorphous PET substrate so that the total draw ratio is 5.94 times by stretching in boric acid water at a stretching temperature of 65 degrees.
• An optical film laminate including a 3 ⁇ m thick PVA layer was produced.
• the PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex. It was possible to produce an optical film laminate including a PVA layer having a thickness of 10 ⁇ m and constituting a highly functional polarizing film. Furthermore, after applying a saponified 80 ⁇ m-thick triacetyl cellulose film while applying a polyvinyl alcohol adhesive on the surface of the polarizing film of the optical film laminate, the amorphous PET substrate was peeled off and polarized Film 2 (thin polarizing film) was produced.
• Example 1 (Preparation of adhesive composition) Based on 100 parts of the solid content of the acrylic polymer (A1) solution obtained in Production Example 1, 0.001 part of Silyl SAT10 manufactured by Kaneka Corporation as the polyether compound (B) and an isocyanate crosslinking agent (manufactured by Takeshi Mitsui Chemicals) Takenate D110N, 0.095 part of trimethylolpropane xylene diisocyanate) and 0.3 part of benzoyl peroxide (NIPPER BMT manufactured by NOF Corporation) were mixed to prepare a solution of an acrylic adhesive composition (solid content 15%) ) Was prepared.
• Silyl SAT10 manufactured by Kaneka Corporation
• an isocyanate crosslinking agent manufactured by Takeshi Mitsui Chemicals
• Takenate D110N, 0.095 part of trimethylolpropane xylene diisocyanate Takenate D110N, 0.095 part of trimethylolpropane xylene diisocyanate
• Example 2 the type of (meth) acrylic polymer (A), the type and amount of polyether compound (B), and the type and amount of silane coupling agent (C) were changed to those shown in Table 1. Except for the above, a polarizing film with an adhesive layer was produced in the same manner as in Example 1.
• a sample (polarizing film with an adhesive layer using polarizing film 1) was cut into a length of 420 mm ⁇ width of 320 mm, and a laminator was used on a non-alkali glass plate (EG-XG, manufactured by Corning) with a thickness of 0.7 mm. Then, it was autoclaved at 50 ° C. and 5 atm for 15 minutes for complete adhesion (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.
• EG-XG non-alkali glass plate
• Adhesive strength is the adhesive strength when peeling such a sample with a tensile tester (Autograph SHIMAZU AG-1 10OKN) at a peeling angle of 90 ° and a peeling speed of 300 mm / min (N / 25 mm, 80 m long when measured) It was calculated
• the sample similar to the object whose adhesive force was measured was peeled off from the alkali-free glass plate (manufactured by Corning, EG-XG) by human hands, and the reworkability was evaluated according to the following criteria. Evaluation of reworkability was carried out three times by preparing three sheets according to the above procedure. A: All three sheets can be peeled off satisfactorily without adhesive residue or film breakage. ⁇ : A part of the three films was broken, but was peeled off by peeling again. ⁇ : All three films were broken, but were peeled off by peeling again. X: Adhesive residue was generated on all three sheets, or the film was broken and could not be removed even if it was peeled many times.
• Sample polarizing film with adhesive layer using polarizing film 1 or polarizing film with adhesive layer using polarizing film 2 is 37 inches in size and 0.7 mm thick alkali-free glass (EG, manufactured by Corning, Inc. -XG) was attached 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 each atmosphere of 80 ° C. and 90 ° C. (heating test), and then 500 ° C. in each atmosphere of 60 ° C./90% RH and 65 ° C./95% RH.
• EG alkali-free glass
• the polarizing film with the pressure-sensitive adhesive layer using the polarizing film 1 or the polarizing film with the pressure-sensitive adhesive layer using the polarizing film 2 was stored for 12 months under the condition of 23 ° C./55% RH.
• the sample was attached to non-alkali glass (corning, EG-XG) having a size of 37 inches and 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 each atmosphere of 80 ° C. and 90 ° C. (heating test), and then 500 ° C.
• SAT10 in the polyether compound (B) is Silyl SAT10 manufactured by Kaneka Corporation.
• SAT350 is Kaneka's Silyl SAT350
• SAX220 is Kaneka's Silyl SAX220
• SAT400 is Kaneka's Silyl SAT400
• SIB82 is “SIB1824.82” manufactured by GELEST
• SIB84 represents “SIB1824.84” manufactured by GELEST
• both are polyether compounds (B) having a reactive silyl group.
• SAT10, SAT350 and SAX220 are all compounds represented by the general formula (4), A 2 is —C 3 H 6 —, Z 1 is —C 3 H 6 —Z 0 , and reactivity
• the silyl group (Z 0- ) is a dimethoxymethylsilyl group in which R 1 , R 2 and R 3 are all methyl groups, and AO is a linear oxypropylene group (particularly —CH 2 CH (CH 3 )). O-).
• SAT400 is a compound represented by the general formula (6), Z 3 is —C 3 H 6 —Z 0 , and the reactive silyl group (Z 0 —) is R 1 , R 2 and R 3.
• SIB82 is a compound represented by the general formula (5), A 2 is —C 3 H 8 —, Z 2 is —CONH—A 2 —Z 0 , and the reactive silyl group (Z 0 —) is , R 1 , R 2 and R 3 are all ethyl triethoxysilyl groups, and AO is a skeleton containing an oxyethylene group.
• SIB84 is a compound represented by the general formula (4), A 2 is —C 3 H 8 —, Z 1 is —C 3 H 8 —Z 0 , and a reactive silyl group (Z 0 — ) Is a triethoxysilyl group in which R 1 , R 2 and R 3 are all ethyl groups, and AO is a skeleton containing an oxyethylene group.

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