WO2020122147A1 - Polarizing film provided with adhesive layer - Google Patents
Polarizing film provided with adhesive layer Download PDFInfo
- Publication number
- WO2020122147A1 WO2020122147A1 PCT/JP2019/048564 JP2019048564W WO2020122147A1 WO 2020122147 A1 WO2020122147 A1 WO 2020122147A1 JP 2019048564 W JP2019048564 W JP 2019048564W WO 2020122147 A1 WO2020122147 A1 WO 2020122147A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- weight
- adhesive layer
- monomer
- acrylate
- Prior art date
Links
- 239000012790 adhesive layer Substances 0.000 title claims abstract description 58
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- 230000001681 protective effect Effects 0.000 claims abstract description 49
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- 125000000524 functional group Chemical group 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims description 210
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 137
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 108
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- 238000002844 melting Methods 0.000 claims description 4
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000004417 polycarbonate Substances 0.000 description 1
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- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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- 239000003755 preservative agent Substances 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
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- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- YHPUTXNFABTCGG-UHFFFAOYSA-N propyl 2-sulfanylacetate Chemical compound CCCOC(=O)CS YHPUTXNFABTCGG-UHFFFAOYSA-N 0.000 description 1
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- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
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- 150000003505 terpenes Chemical class 0.000 description 1
- YXIMCNGUIIEJMO-UHFFFAOYSA-N tert-butyl 2-sulfanylacetate Chemical compound CC(C)(C)OC(=O)CS YXIMCNGUIIEJMO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Images
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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- 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
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- 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
- G02F1/133528—Polarisers
-
- 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
Definitions
- the present invention relates to a polarizing film with an adhesive layer. More specifically, the present invention relates to a pressure-sensitive adhesive layer-attached polarizing film having protective films on both sides of a polarizer.
- the image forming method it is essential for liquid crystal display devices to place polarizing films on both sides of the glass substrate that forms the surface of the liquid crystal panel.
- polarizing film generally, a polyvinyl alcohol-based film and a polarizer made of a dichroic material such as iodine having a protective film bonded to one or both surfaces thereof with a polyvinyl alcohol-based adhesive or the like are used. ..
- an adhesive When attaching the polarizing film to a liquid crystal cell etc., an adhesive is usually used.
- the pressure-sensitive adhesive is preliminarily provided as a pressure-sensitive adhesive layer on one surface of the polarizing film, since it has advantages such as being able to instantly fix the polarizing film and not requiring a drying step to fix the polarizing film. .. That is, a polarizing film with an adhesive layer is generally used for sticking a polarizing film (Patent Documents 1 and 2).
- a polarizing film or a polarizing film with a pressure-sensitive adhesive layer is attached to a glass substrate of a liquid crystal panel, durability is required, and for example, in a durability test such as heating and humidification that is usually performed as an environmental promotion test, adhesion It is required that problems such as peeling and floating due to the agent layer do not occur.
- the present inventors have found that the polarizing film with an adhesive layer of the present invention can solve the above problems, and have completed the present invention.
- the present invention includes the following embodiments.
- a polarizing film comprising a polarizer, a first protective film provided on the viewing side of the polarizer, and a second protective film provided on the opposite side of the viewing side of the polarizer.
- a pressure-sensitive adhesive layer-provided polarizing film comprising: a pressure-sensitive adhesive layer provided on the second protective film,
- the pressure-sensitive adhesive layer includes a base polymer and a silicone oligomer Ps,
- the silicone oligomer Ps is included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the base polymer,
- the silicone oligomer Ps has a Tg of ⁇ 50° C. or higher and 100° C. or lower, a side chain silicone functional group equivalent of 1000 to 20000 g/mol, and a weight average molecular weight of 10,000 or more and 300,000 or less.
- silicone oligomer Ps contains, as a monomer unit, a monomer S1 having a polyorganosiloxane skeleton and a homopolymer having a glass transition temperature of ⁇ 70° C. or higher and 180° C. or lower.
- Polarizing film with adhesive layer contains, as a monomer unit, a monomer S1 having a polyorganosiloxane skeleton and a homopolymer having a glass transition temperature of ⁇ 70° C. or higher and 180° C. or lower.
- the base polymer contains, as a monomer unit, 80% by weight or more of an alkyl (meth)acrylate (A) whose homopolymer has a glass transition temperature of ⁇ 80° C. or higher and 0° C. or lower, (1) or The polarizing film with an adhesive layer according to (2).
- A alkyl (meth)acrylate
- the base polymer further contains, as a monomer unit, at least one polar monomer (B) selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2) in an amount of 0 to 20% by weight.
- polar monomer (B) selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2) in an amount of 0 to 20% by weight.
- the adhesive force can increase after heating and durability can be given, and the adhesiveness (anchoring force) between a polarizing film and an adhesive is excellent.
- a polarizing film with an adhesive layer can be provided.
- FIG. 1 is an example of a schematic cross-sectional view of a polarizing film with an adhesive layer of the present invention.
- the polarizing film with a pressure-sensitive adhesive layer of the present invention includes a polarizing film and a pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer may be present on one side or both sides of the polarizing film.
- the structure of a polarizing film with an adhesive layer is schematically shown in FIG.
- the polarizing film with an adhesive layer 10 is configured as a polarizing film with an adhesive layer, which includes the polarizing film 3 and the adhesive layer 4 provided on one surface thereof.
- the polarizing film 3 includes a polarizer 1, a first protective film 2 provided on the viewing side of the polarizer 1, and a second protective film 2 provided on the opposite side of the viewing side of the polarizer 1. And the protective film 2'of.
- the pressure-sensitive adhesive layer 4 is provided fixedly on the second protective film 2 ′ forming the polarizing film 3, that is, without the intention of separating the pressure-sensitive adhesive layer 4 from the polarizing film 3.
- the polarizing film 10 with an adhesive layer is used by attaching the adhesive layer 4 to an adherend.
- a sheet-shaped base material liner base material which has a release layer provided with a release treatment agent on one surface so that the one surface serves as a release surface can be preferably used.
- the structure of the polarizing film with an adhesive layer is not limited to the embodiment schematically shown in FIG.
- the polarizer is not particularly limited, and various kinds can be used.
- the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene/vinyl acetate copolymer partially saponified film, and dichroism of iodine or dichroic dye.
- examples include polyene-oriented films such as those obtained by adsorbing a substance and uniaxially stretched, polyvinyl alcohol dehydrated products, polyvinyl chloride dehydrochlorinated products, and the like.
- a polarizer made of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable.
- the thickness of these polarizers is not particularly limited, but is generally 2 to 25 ⁇ m.
- a uniaxially stretched polarizer obtained by dyeing a polyvinyl alcohol film with iodine can be produced, for example, by dyeing a polyvinyl alcohol film by immersing it in an aqueous solution of iodine and stretching it to 3 to 7 times its original length. it can. If necessary, it can be immersed in an aqueous solution of potassium iodide or the like 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 with water before dyeing.
- Stretching may be performed after dyeing with iodine, stretching while dyeing, or stretching and then dyeing with iodine. Stretching can be performed in an aqueous solution of boric acid or potassium iodide or in a water bath.
- the material forming the protective film is preferably one having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like.
- polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate
- cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose
- acrylic-based polymers such as polymethyl methacrylate
- styrene such as polystyrene and acrylonitrile-styrene copolymer (AS resin).
- AS resin acrylonitrile-styrene copolymer
- polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure polyolefin polymers such as ethylene/propylene copolymer, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers.
- Polyether sulfone-based polymer, polyether ether ketone-based polymer, polyphenylene sulfide-based polymer, vinyl alcohol-based polymer, vinylidene chloride-based polymer, vinyl butyral-based polymer, arylate-based polymer, polyoxymethylene-based polymer, epoxy-based polymer, or the above Blends of polymers and the like are also mentioned as examples of the polymer forming the protective film. These protective films are usually attached to the polarizer with an adhesive layer.
- the protective film is made of a thermosetting resin such as a (meth)acrylic resin, a urethane resin, an acrylic urethane resin, an epoxy resin, or a silicone resin, or an ultraviolet curable resin, which is applied to the polarizer and cured. It can be formed by a thermosetting resin such as a (meth)acrylic resin, a urethane resin, an acrylic urethane resin, an epoxy resin, or a silicone resin, or an ultraviolet curable resin, which is applied to the polarizer and cured. It can be formed by a thermosetting resin such as a (meth)acrylic resin, a urethane resin, an acrylic urethane resin, an epoxy resin, or a silicone resin, or an ultraviolet curable resin, which is applied to the polarizer and cured. It can be formed by a thermosetting resin such as a (meth)acrylic resin, a urethane resin, an acrylic urethane resin, an epoxy resin, or a silicone resin, or an ultraviolet cur
- the protective film may contain one or more kinds of appropriate additives.
- 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 protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, further preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. When the content of the thermoplastic resin in the protective film is 50% by weight or less, the high transparency originally possessed by the thermoplastic resin may not be sufficiently exhibited.
- a retardation film As the protective film, a retardation film, a brightness enhancement film, a diffusion film, etc. can be used.
- the retardation film include those having a front surface retardation of 40 nm or more and/or a thickness direction retardation of 80 nm or more.
- the front retardation is usually controlled in the range of 40 to 200 nm
- the thickness direction retardation is usually controlled in the range of 80 to 300 nm.
- the retardation film also functions as a polarizer protective film, so that the thickness can be reduced.
- the retardation film may be a birefringent film obtained by uniaxially or biaxially stretching a thermoplastic resin film.
- the stretching temperature, the stretching ratio, and the like are appropriately set depending on the retardation value, the material of the film, and the thickness.
- the thickness of the protective film can be appropriately determined, but generally it is preferably 3 to 200 ⁇ m, more preferably 3 to 100 ⁇ m from the viewpoint of workability such as strength and handleability, and thin layer property. Is preferred.
- the thickness of the protective film (when the film is previously formed) is preferably 10 to 60 ⁇ m, more preferably 10 to 45 ⁇ m from the viewpoint of transportability.
- the thickness of the protective film (when formed by coating and curing) is preferably 3 to 25 ⁇ m, more preferably 3 to 20 ⁇ m from the viewpoint of transportability.
- the protective film may be used in plural sheets or in plural layers.
- a functional layer such as a hard coat layer, an antireflection layer, a sticking prevention layer, a diffusion layer or an antiglare layer can be provided on the surface of the protective film to which the polarizer is not adhered.
- the hard coat layer, the antireflection layer, the antisticking layer, the functional layer such as the diffusion layer and the antiglare layer may be provided on the protective film itself, or may be provided separately from the protective film. it can.
- the protective film and the polarizer are laminated via intervening layers such as an adhesive layer, a pressure-sensitive adhesive layer, and an undercoat layer (primer layer). At this time, it is desirable that both layers are laminated without an air gap by the intervening layer.
- the adhesive layer is formed by an adhesive.
- the type of adhesive is not particularly limited, and various types can be used.
- the adhesive layer is not particularly limited as long as it is optically transparent, and various types of adhesives such as water-based, solvent-based, hot melt-based and active energy ray-curable adhesives are used. Alternatively, an active energy ray-curable adhesive is suitable.
- water-based adhesives examples include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latex-based adhesives, and water-based polyesters.
- the water-based adhesive is usually used as an adhesive composed of an aqueous solution, and usually contains 0.5 to 60% by weight of solid content.
- the active energy ray-curable adhesive is an adhesive that is cured by active energy rays such as electron beams and ultraviolet rays (radical curable type, cation curable type), and is, for example, an electron beam curable type or an ultraviolet ray curable type. Can be used.
- active energy ray curable adhesive for example, a photo radical curable adhesive can be used.
- the photo-radical curable active energy ray curable adhesive is used as an ultraviolet curable adhesive, the adhesive contains a radical polymerizable compound and a photopolymerization initiator.
- the adhesive layer has a thickness of 30 to 300 nm.
- the thickness of the adhesive layer is more preferably 60 to 250 nm.
- an active energy ray-curable adhesive it is preferable that the adhesive layer has a thickness of 0.1 to 200 ⁇ m.
- the thickness is more preferably 0.5 to 50 ⁇ m, further preferably 0.5 to 10 ⁇ m.
- an easily adhesive layer can be provided between the protective film and the adhesive layer.
- a pressure-sensitive adhesive layer may be laminated on at least one surface of the polarizing film via a functional coating layer.
- the polarizing film with a pressure-sensitive adhesive layer may further include a functional coating layer between the second protective film and the pressure-sensitive adhesive layer.
- the terms “functional coating layer”, “anchor coat layer” and “anchor layer” are used interchangeably.
- the anchor coat layer may contain an aqueous resin.
- the anchor coat layer can be formed by applying a coating solution for forming an anchor layer (for example, an aqueous resin composition containing an aqueous resin) to the protective film.
- a coating solution for forming an anchor layer for example, an aqueous resin composition containing an aqueous resin
- the water-based resin for example, at least one selected from polyvinyl alcohol-based resins, polyurethane-based resins, polythiophene-based resins, polyoxyethylene group-containing polymers, and oxazoline group-containing polymers can be used.
- the water-based resin is a polyurethane-based resin from the viewpoint of coating film forming property and wettability with respect to the protective film. Polymers containing oxazoline groups are preferred.
- the functional coating layer may contain an oxazoline group-containing polymer.
- the anchor coat layer is disposed between the polarizing film and the pressure-sensitive adhesive, that is, between the second protective film and the pressure-sensitive adhesive layer, and the anchor coat layer-forming coating liquid is a polythiophene-based coating liquid. It may contain a polymer, a polyoxyalkylene group-containing polymer, and a mixed solvent containing 65 to 100% by weight of water and 0 to 35% by weight of alcohol.
- the alcohol is preferably hydrophilic at room temperature (25°C), and particularly preferably alcohol that can be mixed with water at an arbitrary ratio.
- an alcohol having 1 to 6 carbon atoms is preferable.
- an alcohol having 1 to 4 carbon atoms is preferable, and an alcohol having 1 to 3 carbon atoms is more preferable.
- Specific examples of such alcohols include, for example, methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol.
- Tert-amyl alcohol 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol and the like.
- ethanol and isopropyl alcohol are preferable, and isopropyl alcohol is more preferable.
- the alcohols may be used alone or in combination of two or more. Two or more alcohols can be mixed in any ratio. For example, a mixed alcohol in which ethanol and isopropanol are mixed at an arbitrary ratio can be used.
- polystyrene-equivalent weight average molecular weight of the polythiophene-based polymer is preferably 400000 or less, and more preferably 300000 or less.
- weight average molecular weight exceeds the above value, there is a tendency that the water solubility or water dispersibility is not satisfied, and when a coating solution is prepared using such a polymer, the solid content of the polymer in the coating solution is Tend to remain, or it becomes difficult to form an anchor layer having a uniform film thickness due to high viscosity.
- Water-soluble refers to the case where the solubility in 100 g of water is 5 g or more.
- the solubility of the water-soluble polythiophene polymer in 100 g of water is preferably 20 to 30 g.
- the water-dispersible polythiophene-based polymer is a polythiophene-based polymer in the form of fine particles dispersed in water.
- the water dispersion has a small liquid viscosity and is easy to apply in a thin film, and also has excellent coating layer uniformity. ing.
- the size of the fine particles is preferably 1 ⁇ m or less from the viewpoint of the uniformity of the anchor layer.
- the water-soluble or water-dispersible polythiophene polymer preferably has a hydrophilic functional group in the molecule.
- the hydrophilic functional group include a sulfone group, an amino group, an amide group, an imino group, a quaternary ammonium salt group, a hydroxyl group, a mercapto group, a hydrazino group, a carboxyl group, a sulfate ester group, a phosphate ester group, or a salt thereof.
- Etc By having a hydrophilic functional group in the molecule, it becomes easy to dissolve in water or easily dispersed in water in the form of fine particles, and thus the water-soluble or water-dispersible polythiophene polymer can be easily prepared.
- water-soluble or water-dispersible polythiophene-based polymer examples include Denatron series manufactured by Nagase Chemtex.
- the dispersibility of the polythiophene-based polymer in the anchor layer-forming coating liquid is further enhanced.
- the conductivity of the anchor layer obtained after coating and drying the anchor layer-forming coating liquid is further improved.
- the mixed solvent of water/alcohol at such a ratio, even if the pH value of the binder component becomes low, the liquid stability thereof can be maintained, so that the generation of foreign matter in the anchor layer can be suppressed.
- a water-rich mixed solvent is used, solvent cracks in the anchor layer can be more effectively prevented.
- the content of the polythiophene-based polymer in the anchor layer-forming coating liquid is preferably 0.005 to 5% by weight, and 0.01 to 3% by weight. Is more preferable, 0.01 to 1% by weight is further preferable, and 0.01 to 0.5% by weight is most preferable.
- the polyoxyalkylene group-containing polymer is contained in the anchor layer forming coating solution together with the mixed solvent and the polythiophene-based polymer.
- the polyoxyalkylene group-containing polymer for example, a polyoxyalkylene group whose main chain is a poly(meth)acrylate polymer and whose side chain contains a polyoxyalkylene group such as a polyoxyethylene group or a polyoxypropylene group Examples include contained poly(meth)acrylates.
- the content of the polyoxyalkylene group-containing polymer in the anchor layer-forming coating liquid is preferably 0.005 to 5% by weight, and 0.01 to 5% by weight. The amount is more preferably 3% by weight, further preferably 0.01 to 1% by weight, and most preferably 0.01 to 0.5% by weight.
- a binder component is contained in addition to the polythiophene-based polymer and the polyoxyalkylene group-containing polymer, in order to improve the anchoring property and the adhesion between the optical film and the pressure-sensitive adhesive layer.
- a binder component from the viewpoint of improving the anchoring force of the pressure-sensitive adhesive, for example, a polyurethane resin binder such as a water-soluble or water-dispersible polyurethane resin binder, an epoxy resin binder, an isocyanate resin binder, a polyester resin binder.
- Resins having organic reactive groups such as polymers containing an amino group in the molecule and various acrylic resin binders containing an oxazoline group can be used.
- a polyurethane resin binder is contained as a binder component, the adhesion between the optical film and the pressure-sensitive adhesive layer is improved through the anchor layer obtained from the anchor layer-forming coating liquid, which is preferable.
- the content of the binder resin in the anchor layer-forming coating liquid is preferably 0.005 to 5% by weight, more preferably 0.01 to 3% by weight, and 0.01 to 1% by weight. It is more preferable that the amount is 0.01 to 0.5% by weight.
- the above-mentioned polyurethane resin-based binder such as a water-soluble or water-dispersible polyurethane resin-based binder because the adhesion between the optical film and the pressure-sensitive adhesive layer is improved.
- a polyurethane resin-based binder when a polyurethane resin-based binder is used, if the pH value in the anchor layer-forming coating liquid decreases due to the generation of oxalic acid, the amount of foreign matter generated due to the polyurethane resin tends to increase.
- generation of foreign matter can be suppressed by setting the ratio of water and alcohol in the mixed solvent of the anchor layer forming coating liquid to a specific ratio.
- the mixed solvent (diluting solvent for the binder resin) in the anchor layer-forming coating liquid contains water and alcohol as main components, and specifically, the total amount of water and alcohol in the mixed solvent is 90% by weight or more. Is preferred.
- the total amount of water and alcohol in the mixed solvent is 95% by weight or more, further preferably, the total amount of water and alcohol in the mixed solvent is 99% by weight or more, and most preferably, the mixed solvent.
- the water and alcohol therein is substantially 100% by weight.
- the coating appearance and optical reliability of the anchor layer may be excellent, but the content of ammonia is as small as possible from the viewpoint of durability and prevention of solvent cracks.
- the content of ammonia in the anchor layer-forming coating liquid is preferably less than 0.05 parts by weight, and less than 0.03 parts by weight, based on 100 parts by weight of the binder resin (solid content). Is more preferable.
- the anchor layer forming coating liquid may contain additives.
- the additive include a leveling agent, a defoaming agent, a thickener, an antioxidant and the like.
- a leveling agent for example, one having an acetylene skeleton
- the ratio of these additives is usually about 0.01 to 500 parts by weight, preferably 0.1 to 300 parts by weight, and more preferably 1 to 100 parts by weight, relative to 100 parts by weight of the binder resin (solid content). More preferable.
- polyurethane resin an emulsion of polyurethane resin can be used. Further, as the polyurethane resin emulsion, a self-emulsified one can be used without using an emulsifier.
- the polyurethane resin for example, a one-pack type resin obtained by a polyaddition reaction of a polymer polyol and an isocyanate compound can be used.
- a one-pack type polyurethane resin for example, a polyether polyurethane resin, a polyester polyurethane resin or the like can be used.
- the polyurethane-based resin is preferably one in which a hydroxyl group remains.
- a lacquer type polyurethane resin can be used.
- the polyurethane resin can be formed into a film by simply removing the solvent and water by drying.
- Polyether polyurethane resin is generally obtained by polyaddition reaction of polyether polyol and isocyanate compound.
- the polyether polyol is obtained by adding an alkylene oxide to one or more polyhydric alcohols by ring-opening polymerization.
- the polyester-based polyurethane resin is generally obtained by a polyaddition reaction between a polyester polyol and an isocyanate compound.
- Polyester polyol is obtained by polycondensing a polyhydric alcohol and a polybasic acid.
- the high molecular weight polyol such as polyether polyol or polyether polyol preferably has a number average molecular weight of 400 to 3,000, more preferably 500 to 2,000.
- Polymer polyols such as polyether polyols and polyester polyols may be used alone or as a copolymer using two or more kinds.
- an aromatic, araliphatic, aliphatic, or alicyclic isocyanate usually used in polyurethane can be appropriately used.
- an adduct, a dimer, a trimer of the above isocyanate compound, a polymer thereof, or the like may be used.
- a modified isocyanate obtained by urethanizing, uretidione-forming, carbodiimidizing a part of the above-mentioned isocyanate can also be used.
- the resin When dispersing the polyurethane resin in water, a method is known in which the resin is forcibly emulsified and dispersed using an emulsifier.
- a self-emulsified product obtained by introducing an anion group, a cation group or a nonion group of a water-dispersible hydrophilic group into the resin can be used.
- an ionic polymer complex can be used.
- polyurethane resin emulsion examples include the Adeka Bontiter HUX series manufactured by Asahi Denka Kogyo Co., Ltd., which is self-emulsified without using an emulsifier.
- specific examples of the water-based urethane resin include Superflex series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Takelac W-6020 manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., and the like.
- Examples of the oxazoline group-containing polymer include a polymer having a main chain composed of an acrylic skeleton or a styrene skeleton and having an oxazoline group on the side chain of the main chain.
- an oxazoline group-containing acrylic polymer having a main chain composed of an acrylic skeleton and having an oxazoline group on the side chain of the main chain is preferable.
- Examples of the oxazoline group include a 2-oxazoline group, a 3-oxazoline group, a 4-oxazoline group and the like, and among these, the 2-oxazoline group is preferable.
- the 2-oxazoline group is generally represented by the following general formula.
- R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, a phenyl group, or a substituted phenyl group.
- the oxazoline group-containing polymer may have a polyoxyalkylene group in addition to the oxazoline group.
- the number-average molecular weight of the oxazoline group-containing polymer is preferably 5,000 or more, more preferably 10,000 or more, and usually 1,000,000 or less. If the number average molecular weight is lower than 5,000, the strength of the anchor layer may be insufficient to cause cohesive failure and the anchoring force may not be improved. When the number average molecular weight is higher than 1,000,000, workability may be poor. Further, the oxazoline group-containing polymer has an oxazoline value of, for example, 1,500 g solid/eq. It is preferably not more than 1,200 g solid/eq. The following is more preferable. Oxazoline value is 1,500 g solid/eq. If it is larger, the amount of the oxazoline group contained in the molecule becomes small, and the anchoring force may not be improved in some cases.
- the oxazoline group-containing polymer reacts with the hydroxyl group contained in the pressure-sensitive adhesive composition at a relatively low temperature, if the oxazoline group-containing polymer is contained in the anchor coat layer, the functional group in the pressure-sensitive adhesive layer is reduced. It reacts with the like and can firmly adhere.
- oxazoline group-containing polymer examples include oxazoline group-containing acrylic polymers such as Epocros WS-300, Epocros WS-500, and Epocros WS-700 manufactured by Nippon Shokubai Co., Ltd., for example, manufactured by Nippon Shokubai Co., Ltd.
- the oxazoline group-containing acrylic/styrene-based polymers such as Epocros K-1000 series and Epocros K-2000 series can be used, and they can be used alone or in combination of two or more.
- the thickness of the anchor coat layer is preferably 0.05 ⁇ m, more preferably 0.2 ⁇ m or more, and the thickness of the anchor coat layer is preferably 0.5 ⁇ m or more, more preferably 0.1 ⁇ m or more. It is preferably 7 ⁇ m or more. If the anchor coat layer becomes too thick, the optical reliability and water resistance will decrease, so the thickness of the anchor coat layer is preferably 6 ⁇ m or less, more preferably 5 ⁇ m or less, further 3 ⁇ m or less, and further 2 ⁇ m or less. Is preferred.
- the anchor coat layer can be formed by applying the water-based resin composition to a protective film and drying.
- the aqueous resin composition is applied so as to have a thickness after drying (preferably 0.2 ⁇ m or more and 6 ⁇ m or less).
- the coating operation is not particularly limited, and any appropriate method can be adopted. For example, various methods such as a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method and a knife coating method (comma coating method) can be adopted.
- the pressure-sensitive adhesive layer used in the present invention contains a base polymer and a silicone oligomer Ps.
- the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer used in the present invention is not particularly limited, and it is a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a vinyl alkyl ether-based pressure-sensitive adhesive, a polyvinyl alcohol-based pressure-sensitive adhesive.
- Adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives and the like can be used.
- Various base polymers can be used depending on the adhesive used.
- a (meth)acrylic polymer is used as the base polymer of the acrylic pressure-sensitive adhesive.
- the (meth)acrylate contains acrylate and/or methacrylate.
- a (meth)acrylic polymer is usually used as the base polymer.
- Alkyl (meth)acrylate (A) The (meth)acrylic polymer usually contains, as a monomer unit, an alkyl (meth)acrylate as a main component.
- an alkyl (meth)acrylate (A) constituting the main skeleton of the (meth)acrylic polymer a linear or branched C1 to C20 (meth)acrylic acid alkyl ester can be used.
- the C1 to C20 (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate.
- N-butyl (meth)acrylate N-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, ( Hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, Decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (me
- the (meth)acrylic polymer may preferably contain one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA) as a monomer unit.
- BA n-butyl acrylate
- 2EHA 2-ethylhexyl acrylate
- examples of other (meth)acrylic acid alkyl esters that can be preferably used as the monomer unit of the (meth)acrylic polymer include methyl acrylate, methyl methacrylate (MMA), n-butyl methacrylate (BMA), and methacrylic acid.
- 2-ethylhexyl (2EHMA) and the like can be mentioned.
- the alkyl (meth)acrylate (A) used as a monomer unit of the base polymer has a homopolymer glass transition temperature of ⁇ 80° C. or higher and 0° C. or lower.
- the glass transition temperature of the homopolymer of alkyl (meth)acrylate (A) is preferably ⁇ 70° C. to ⁇ 5° C., more preferably ⁇ 60° C. to ⁇ 10° C.
- the alkyl (meth)acrylate (A) used as a monomer unit of the base polymer can be contained in an amount of 80% by weight or more based on the weight of the base polymer.
- the alkyl (meth)acrylate (A) is preferably 85% by weight or more, more preferably 90% by weight or more, based on the weight of the base polymer.
- an alkyl (meth)acrylate (A) having a glass transition temperature of a homopolymer of ⁇ 80° C. or higher and 0° C. or lower can be contained as a monomer unit of a base polymer. ..
- the (meth)acrylic polymer is, in addition to the alkyl (meth)acrylate (A) as a main component, other monomer that is copolymerizable with the alkyl (meth)acrylate, if necessary. It may further contain (copolymerizable monomer).
- a monomer having a polar group for example, a carboxy group, a hydroxyl group, a nitrogen atom-containing ring, etc.
- the monomer having a polar group can be useful for introducing a cross-linking point in the acrylic polymer and for enhancing the cohesive force of the (meth)acrylic polymer.
- the copolymerizable monomer may be used alone or in combination of two or more.
- Non-limiting specific examples of the copolymerizable monomer include a carboxy group-containing monomer, an acid anhydride group-containing monomer, a hydroxyl group-containing monomer, a sulfonic acid group- or phosphoric acid group-containing monomer, an epoxy group-containing monomer, and a cyano group-containing monomer.
- Examples of the carboxy group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like;
- Examples of the acid anhydride group-containing monomer include maleic anhydride and itaconic anhydride;
- Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylate.
- Examples of the monomer having a sulfonic acid group or a phosphoric acid group include styrenesulfonic acid, allylsulfonic acid, sodium vinylsulfonate, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid.
- epoxy group-containing monomer examples include epoxy group-containing acrylates such as (meth)acrylic acid glycidyl and (meth)acrylic acid-2-ethylglycidyl ether, allyl glycidyl ether, and (meth)acrylic acid glycidyl ether;
- the cyano group-containing monomer examples include acrylonitrile and methacrylonitrile.
- Examples of the isocyanate group-containing monomer include 2-isocyanatoethyl (meth)acrylate and the like;
- Examples of the amide group-containing monomer include (meth)acrylamide; N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl( N,N-dialkyl(meth)acrylamides such as (meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl)(meth)acrylamide; N-ethyl (meth ) N-alkyl(meth)acrylamides such as acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, Nn-butyl(meth)acrylamide; N-vinylcarboxylic amides such
- Examples of the maleimides include N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide, N-phenyl maleimide and the like;
- Examples of itaconimides include N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide, N -Lauryl itaconimide and the like;
- Examples of aminoalkyl (meth)acrylates include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and (meth)acrylic.
- alkoxyalkyl (meth)acrylates examples include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and (meth)acrylic acid.
- Ethoxypropyl and the like can be mentioned;
- vinyl esters include vinyl acetate, vinyl propionate and the like;
- vinyl ethers include vinyl alkyl ethers such as methyl vinyl ether and ethyl vinyl ether;
- aromatic vinyl compound include styrene, ⁇ -methylstyrene, vinyltoluene and the like;
- olefins include ethylene, butadiene, isoprene, and isobutylene;
- Examples of the (meth)acrylic acid ester having an alicyclic hydrocarbon group include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate and the like;
- Examples of the (meth)acrylic acid ester having an aromatic hydrocarbon group include phenyl(meth)acrylate, phenoxyethyl(meth)acrylate, and benz
- the amount thereof is not particularly limited, but it is usually suitable to be 0.01% by weight or more of the total amount of the monomer components. From the viewpoint of better exerting the effect of using the copolymerizable monomer, the amount of the copolymerizable monomer used may be 0.1% by weight or more, or 1% by weight or more based on the total amount of the monomer components.
- the amount of the copolymerizable monomer used can be 50% by weight or less, and preferably 40% by weight or less, based on the total amount of the monomer components. This can prevent the cohesive force of the pressure-sensitive adhesive from becoming too high, and improve the tackiness at room temperature (25° C.).
- the (meth)acrylic polymer is, in addition to the alkyl (meth)acrylate as a main component, optionally a hydroxyl group-containing monomer (typically, as described above) as a monomer unit.
- a (meth)acrylic monomer containing a hydroxyl group examples include, as described above, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxy (meth)acrylate.
- hydroxyalkyl (meth)acrylate such as hydroxylauryl, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, and the like, 2-hydroxyethyl (meth)acrylate, 4-hydroxy (meth)acrylate.
- Butyl, 6-hydroxyhexyl (meth)acrylate and the like can be preferably used.
- preferable examples include 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA).
- HSA 2-hydroxyethyl acrylate
- 4HBA 4-hydroxybutyl acrylate
- the hydroxyl group-containing monomer can also serve to suppress the decrease in transparency due to moisture by increasing the hydrophilicity of the pressure-sensitive adhesive layer.
- the amount of the hydroxyl group-containing monomer to be used is not particularly limited, but usually 0.01% by weight or more, 0.1% by weight or more, based on the total amount of the monomer unit for preparing the (meth)acrylic polymer.
- the pressure-sensitive adhesive layer-attached polarizing film can contain the hydroxyl group-containing monomer in an amount of 0.01 to 5% by weight as the monomer unit of the (meth)acrylic polymer as the base polymer.
- the (meth)acrylic polymer is, in addition to the alkyl (meth)acrylate as the main component, a polyfunctional polymer for the purpose of adjusting the cohesive force of the pressure-sensitive adhesive layer, if necessary. It may contain a polymerizable monomer.
- polyfunctional monomer examples include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecane Diol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate,
- trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate and dipentaerythritol hexa(meth)acrylate can be preferably used.
- the polyfunctional monomers may be used alone or in combination of two or more.
- the amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, etc., but is usually 0.01% by weight to 3.0% by weight based on the total amount of the monomer components for preparing the alkyl (meth)acrylate (A). It is suitable to set it in the range of wt%, and it may be 0.02 wt% to 2.0 wt% or 0.03 wt% to 1.0 wt%.
- the base polymer contains, as a copolymerizable monomer unit, at least one polar monomer (B) selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2). It can also be included.
- the polar monomer (B) may be included in an amount of 0 to 20% by weight based on the weight of the base polymer.
- the polar monomer (B) is preferably 0.1 to 17.5% by weight, more preferably 1 to 15% by weight, based on the weight of the base polymer.
- the base polymer may contain a carboxyl group-containing monomer (b1) as a copolymerizable monomer unit.
- the carboxy group-containing monomer (b1) include, but are not limited to, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like. ..
- the carboxyl group-containing monomer (b1) may be acrylic acid or methacrylic acid.
- the carboxyl group-containing monomer (b1) may be acrylic acid (AA).
- the base polymer may include a nitrogen-containing monomer (b2) as a copolymerizable monomer unit.
- the nitrogen-containing monomer (b2) include vinyl monomers having a lactam ring (for example, vinylpyrrolidone monomers such as N-vinylpyrrolidone and methylvinylpyrrolidone, ⁇ -lactam ring, ⁇ -lactam ring, and ⁇ -).
- Maleimide-based monomers such as maleimide, N-cyclohexylmaleimide, N-phenylmaleimide;
- the nitrogen-containing monomer (b2) may be N-vinylpyrrolidone, methylvinylpyrrolidone, N,N-dimethyl(meth)acrylamide. In a more preferred embodiment of the present invention, the nitrogen-containing monomer (b2) may be N-vinylpyrrolidone.
- the method for obtaining the (meth)acrylic polymer is not particularly limited, and various known methods for synthesizing acrylic polymers, such as solution polymerization method, emulsion polymerization method, bulk polymerization method, suspension polymerization method, and photopolymerization method.
- the above-mentioned polymerization method can be appropriately adopted.
- the solution polymerization method may be preferably adopted.
- the polymerization temperature at the time of performing solution polymerization can be appropriately selected according to the type of monomer and solvent used, the type of polymerization initiator, etc., and is, for example, about 20°C to 170°C (typically 40°C to 140°C). C.).
- the initiator used for the polymerization can be appropriately selected from conventionally known thermal polymerization initiators, photopolymerization initiators, etc. according to the polymerization method.
- the polymerization initiators may be used alone or in combination of two or more.
- thermal polymerization initiator examples include azo polymerization initiators (eg, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis( 2-methylpropionic acid)dimethyl, 4,4′-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 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'-dimethylene Isobutylamidine) dihydrochloride, etc.); Persulfate such as potassium persulfate; Peroxide type polymerization initiator (eg, dibenzoyl peroxide, t-butyl permaleate, lau
- the amount of the thermal polymerization initiator used is not particularly limited, but is, for example, 0.01 parts by weight to 5 parts by weight, preferably 0.05 parts by weight to 100 parts by weight of the monomer component used for preparing the acrylic polymer.
- the amount can be within the range of 3 parts by weight.
- the photopolymerization initiator is not particularly limited, and examples thereof include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, ⁇ -ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactivators.
- Oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone photopolymerization initiator, acylphosphine oxide photopolymerization initiator Agents and the like can be used.
- the amount of the photopolymerization initiator used is not particularly limited, but for example, 0.01 part by weight to 5 parts by weight, preferably 0.05 part by weight to 100 parts by weight of the monomer component used for the preparation of the acrylic polymer.
- the amount can be within the range of 3 parts by weight.
- the (meth)acrylic polymer is solution-polymerized by using, for example, ethyl acetate, toluene or the like as a polymerization solvent in a mixture of the above-mentioned monomer component and a polymerization initiator.
- a (meth)acrylic polymer can be obtained.
- the reaction is usually carried out under a stream of an inert gas such as nitrogen with a polymerization initiator at about 50 to 70° C. for about 5 to 30 hours.
- the pressure-sensitive adhesive layer disclosed in the present specification can be formed using, for example, a pressure-sensitive adhesive composition containing the (meth)acrylic polymer, the silicone oligomer Ps described below, and other additives.
- the weight average molecular weight Mw of the above-mentioned base polymer may be 500,000 to 2,500,000. In one embodiment of the present invention, the weight average molecular weight Mw of the base polymer may be preferably 700,000 to 2.7 million, more preferably 800,000 to 2.5 million.
- the pressure-sensitive adhesive layer contains silicone oligomer Ps.
- Silicone oligomer Ps can function as a tackiness increase retarder that contributes to suppression of initial tackiness and improvement of tackiness increase ratio due to the low polarity and mobility of the siloxane structure.
- a polymer having a siloxane structure in its side chain can be preferably used.
- the silicone oligomer Ps used in the present invention has a glass transition temperature (Tg) in the range of -50°C to 100°C.
- Tg glass transition temperature
- the Tg of the silicone oligomer Ps may preferably be -30°C or higher and 70°C or lower, and more preferably -20°C or higher and 60°C or lower.
- the silicone oligomer Ps used in the present invention has a weight average molecular weight Mw of 10,000 or more and 300,000 or less.
- the weight average molecular weight Mw of the silicone oligomer Ps may be preferably 12,500 or more and 2500000 or less, more preferably 15000 or more and 2000000 or less.
- the weight average molecular weight Mw of the silicone oligomer Ps is within the above range, it is easy to adjust the compatibility and mobility in the pressure-sensitive adhesive layer to an appropriate range, and the initial low tackiness and strong tackiness during use are high. It becomes easier to realize a pressure-sensitive adhesive sheet that is compatible at both levels.
- the silicone oligomer Ps has a Tg of ⁇ 50° C. or higher and 100° C. or lower, a side chain silicone functional group equivalent of 1000 to 20000 g/mol, and a weight average molecular weight Mw of 10,000 or more and 300,000 or less. May be
- the silicone oligomer Ps may include a monomer S1 having a polyorganosiloxane skeleton and a monomer having a homopolymer glass transition temperature of ⁇ 70° C. or higher and 180° C. or lower as monomer units.
- Monomer S1 having a polyorganosiloxane skeleton The monomer S1 having a polyorganosiloxane skeleton that can be used in the silicone oligomer Ps of the present invention is not particularly limited, and any monomer having a polyorganosiloxane skeleton can be used.
- the polyorganosiloxane skeleton include, but are not limited to, trimethylsiloxane (TM), dimethylsiloxane (DM), polyoxyethylmethylsiloxane (EOM), and the like.
- the monomer S1 having a polyorganosiloxane skeleton for example, a compound represented by the following general formula (1) or (2) can be used. More specifically, as one-end reactive silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., X-22-174ASX, X-22-2426, X-22-2475, KF-2012, X-22-174BX, X -22-2404 and the like.
- the monomer S1 having a polyorganosiloxane skeleton may be used alone or in combination of two or more.
- R 3 in the general formulas (1) and (2) is hydrogen or methyl
- R 4 is a methyl group or a monovalent organic group
- m and n are integers of 0 or more.
- the silicone oligomer Ps used in the present invention has a silicone functional group equivalent of its side chain of 1000 to 20000 g/mol.
- the silicone functional group equivalent of the side chain of the silicone oligomer Ps may be preferably 1200 to 18000 g/mol, more preferably 1500 to 15000 g/mol.
- the silicone functional group equivalent of the side chain of the silicone oligomer Ps is within the above range, it is easy to adjust the compatibility (for example, the compatibility with the base polymer) and the mobility in the pressure-sensitive adhesive layer to an appropriate range and It becomes easy to realize a pressure-sensitive adhesive sheet that achieves both low tackiness and strong tackiness during use at a high level.
- the “functional group equivalent” means the weight of the main skeleton (for example, polydimethylsiloxane) bonded to each functional group.
- the unit of g/mol is converted to 1 mol of the functional group.
- the functional group equivalent of the monomer S1 having a polyorganosiloxane skeleton can be calculated from the spectrum intensity of 1 H-NMR (proton NMR) based on nuclear magnetic resonance (NMR), for example. Calculation of the functional group equivalent (g/mol) of the monomer S1 having a polyorganosiloxane skeleton based on the 1 H-NMR spectrum intensity is required based on a general structural analysis method related to 1 H-NMR spectrum analysis. In that case, it can be performed by referring to the description of Japanese Patent No. 5915153.
- an arithmetic average value can be used as the functional group equivalent of the monomer S1. That is, the functional group equivalent of the monomer S1 composed of n kinds of monomers (monomer S1 1 , monomer S1 2 ... Monomer S1 n ) having different functional group equivalents can be calculated by the following formula.
- Functional group equivalent of the monomer S1 (g / mol) (monomer S1 1 functional group equivalent ⁇ monomer S1 1 of the amount + monomer S1 2 functional group equivalent ⁇ monomer S1 2 of the amount + ... + monomer S1 n
- the content of the monomer S1 having a polyorganosiloxane skeleton may be, for example, 5% by weight or more based on the total monomer components for preparing the silicone oligomer Ps, and the effect as a tackiness increase retarder can be better exhibited. From the viewpoint of the above, the amount is preferably 10% by weight or more, and may be 15% by weight or more. In some embodiments, the content of the monomer S1 may be, for example, 20% by weight or more. From the viewpoint of polymerization reactivity and compatibility, the content of the monomer S1 having a polyorganosiloxane skeleton is appropriately 60% by weight or less based on the total monomer components for preparing the silicone oligomer Ps.
- the content of the monomer S1 having a polyorganosiloxane skeleton is within the above range, it is easy to realize a pressure-sensitive adhesive sheet that achieves a high level of both low initial tackiness and increase in tackiness (strong tackiness) during use. Become.
- the silicone oligomer Ps of the present invention is a (meth)acryl-based monomer or another monomer copolymerizable with the monomer S1 having the polyorganosiloxane skeleton. It contains a copolymerizable monomer.
- a homopolymer having a glass transition temperature of ⁇ 70° C. to 180° C. is used as the copolymerizable (meth)acrylic monomer or other copolymerizable monomer that can be used in the silicone oligomer Ps of the present invention.
- Examples thereof include, but are not limited to, (meth)acrylic acid alkyl ester and (meth)acrylic acid ester having an alicyclic hydrocarbon group.
- the (meth)acrylic acid alkyl ester include methyl methacrylate (MMA), butyl methacrylate (BMA), 2-ethylhexyl methacrylate (2-EHMA), butyl acrylate (BA), and 2-ethylhexyl acrylate (2-EHA).
- Examples of the (meth)acrylic acid ester having an alicyclic hydrocarbon group include 2-((3-hydroxymethyl)-adamantan-1-yl)methoxy-2-oxoethyl methacrylate (2EHAMA), cyclopentyl (meth)acrylate, Examples thereof include, but are not limited to, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, and the like.
- At least one selected from 2-((3-hydroxymethyl)-adamantan-1-yl)methoxy-2-oxoethyl methacrylate (2EHAMA) and isobornyl methacrylate (IBXMA) is a monomer unit.
- it may contain at least one selected from dicyclopentanyl methacrylate, isobornyl methacrylate and cyclohexyl methacrylate as a monomer unit. These monomers may be used alone or in combination of two or more.
- the amount of the above-mentioned (meth)acrylic acid alkyl ester and the above-mentioned (meth)acrylic acid ester having an alicyclic hydrocarbon group used is, for example, 10% by weight or more and 95% by weight or more based on all the monomer components for preparing the silicone oligomer Ps. May be 20% by weight or more, 95% by weight or less, 30% by weight or more and 90% by weight or less, or 40% by weight or more and 90% by weight or less, It may be 50% by weight or more and 85% by weight or less.
- a carboxyl group-containing monomer and an acid anhydride group-containing monomer exemplified above as the monomer that can be used in the alkyl (meth)acrylate (A) are included.
- the total amount of the monomer S1 and the (meth)acrylic monomer in the entire monomer component is, for example, 50% by weight.
- the amount may be 70% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, or substantially 100% by weight.
- the composition of the (meth)acrylic monomer contained in the monomer component can be set such that the glass transition temperature T m1 based on the composition of the (meth)acrylic monomer is higher than 0° C., for example.
- the glass transition temperature T m1 based on the composition of the (meth)acrylic monomer is based on the composition of only the (meth)acrylic monomer among the monomer components used for the preparation of the silicone oligomer Ps, and according to the Fox equation. Refers to the required Tg.
- T m1 is the glass transition temperature of the homopolymer of each (meth)acrylic monomer, which is obtained by applying the above-described Fox equation to only the (meth)acrylic monomer among the monomer components used for the preparation of the silicone oligomer Ps. And the weight fraction of each (meth)acrylic monomer in the total amount of the (meth)acrylic monomer.
- the silicone oligomer Ps having a glass transition temperature T m1 higher than 0° C. the initial adhesive force is easily suppressed. Further, by using the silicone oligomer Ps having a glass transition temperature T m1 higher than 0° C., it is easy to obtain a pressure-sensitive adhesive sheet having a large adhesive force increase ratio.
- T m1 may be ⁇ 20° C. or higher, ⁇ 10° C. or higher, 0° C. or higher, or 10° C. or higher. At higher T m1, the adhesive strength in the early stage of application generally tends to be better suppressed. Further, T m1 may be, for example, 90° C. or lower, 80° C. or lower, 70° C. or lower, or lower than 70° C. When T m1 is low, increase in adhesive strength due to heating tends to be facilitated.
- the technique disclosed herein can be preferably carried out using a silicone oligomer Ps having T m1 in the range of, for example, ⁇ 20° C. to 90° C., or ⁇ 10° C. to 80° C., and 0° C. to 70° C.
- the silicone oligomer Ps can be produced, for example, by polymerizing the above-mentioned monomer by a known method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or a photopolymerization method.
- a chain transfer agent can be used to adjust the molecular weight of the silicone oligomer Ps.
- the chain transfer agent to be used include compounds having a mercapto group such as octyl mercaptan, lauryl mercaptan, t-nonyl mercaptan, t-dodecyl mercaptan, mercaptoethanol and ⁇ -thioglycerol; thioglycolic acid, methyl thioglycolate, Ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, ethylene Examples thereof include
- the amount of the chain transfer agent used is not particularly limited, but is usually 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the monomer. And more preferably 0.2 to 10 parts by weight.
- the chain transfer agents may be used alone or in combination of two or more.
- the silicone oligomer Ps may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the above-mentioned (meth)acrylic polymer that is the base polymer.
- the silicone oligomer Ps is preferably contained in an amount of 0.25 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the above-mentioned (meth)acrylic polymer. May be included in the section.
- the content of the silicone oligomer Ps contained in the adhesive layer is within the above range, the initial adhesive force can be suppressed and a higher adhesive force after heating can be obtained.
- the silicone oligomer Ps as described above can function favorably as an agent for increasing the adhesive strength by being mixed in the adhesive layer.
- the pressure-sensitive adhesive sheet disclosed herein can be preferably implemented in a mode in which the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer contains a base polymer and a pressure-sensitive adhesive force increase retarder, and the pressure-sensitive adhesive force increase retarder contains a silicone oligomer Ps.
- the silicone oligomer Ps functions as an adhesive force increase retarder because the initial adhesive force is suppressed by the silicone oligomer Ps existing on the surface of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet from before attachment to the adherend and in the initial stage of attachment.
- the amount of the silicone oligomer Ps present on the surface of the pressure-sensitive adhesive layer decreases due to the pressure-sensitive adhesive flowing due to the passage of time after application, heating, etc., and the silicone oligomer Ps is compatible with the pressure-sensitive adhesive, increasing the adhesive strength. Conceivable. Therefore, as the above-mentioned adhesive force increase retarder in the technology disclosed herein, other materials capable of exhibiting the same kind of function may be used instead of the silicone oligomer Ps or in combination with the silicone oligomer Ps.
- a non-limiting example of such a material is a polymer having a polyoxyalkylene structure in the molecule (hereinafter, also referred to as “polymer Po”).
- the polymer Po can be, for example, a polymer including a monomer unit derived from a monomer having a polyoxyalkylene skeleton. Specific examples thereof include homopolymers or copolymers of any one of the above-mentioned monomers having a polyoxyalkylene skeleton, and one or more of monomers having a polyoxyalkylene skeleton and others.
- a copolymer with the monomer (eg, a (meth)acrylic monomer) or the like can be used as the polymer Po.
- the amount of the monomer having a polyoxyalkylene skeleton is not particularly limited, but for example, the amount of the monomer S1 used in the silicone oligomer Ps described above may be applied to the amount of the monomer having a polyoxyalkylene skeleton in the polymer Po. You can The amount of the polymer Po used in the pressure-sensitive adhesive layer is not particularly limited. For example, the amount of the silicone oligomer Ps used for the base polymer described above can be applied to the amount of the polymer Po used for the base polymer.
- a part of the amount of the silicone oligomer Ps used with respect to the above-mentioned base polymer may be replaced with the polymer Po.
- the melting temperature of the silicone oligomer Ps may be -20 to 120°C. In another embodiment of the present invention, the melting temperature of the silicone oligomer Ps may be ⁇ 10 to 90° C., 0 to 80° C.
- a crosslinking agent may be used in the pressure-sensitive adhesive layer disclosed in the present specification for the purpose of adjusting cohesive force and the like.
- a commonly used cross-linking agent can be used, and examples thereof include epoxy cross-linking agents, isocyanate cross-linking agents, silicone cross-linking agents, oxazoline cross-linking agents, aziridine cross-linking agents, silane cross-linking agents, alkyl etherifications. Examples thereof include a melamine-based crosslinking agent and a metal chelate-based crosslinking agent.
- an isocyanate cross-linking agent, an epoxy cross-linking agent, and a metal chelate cross-linking agent can be preferably used.
- the cross-linking agents can be used alone or in combination of two or more.
- examples of the isocyanate cross-linking agent include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene.
- examples thereof include diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, and adducts of these with polyols such as trimethylolpropane.
- a compound having at least one or more isocyanate group and one or more unsaturated bond in one molecule should also be used as an isocyanate cross-linking agent. You can These may be used alone or in combination of two or more.
- Epoxy crosslinking agents include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane tri Glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N,N,N',N'-tetraglycidyl-m-xylylenediamine and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane You can These may be used alone or in combination of two or more.
- metal chelate compound examples include aluminum, iron, tin, titanium and nickel as metal components, and acetylene, methyl acetoacetate and ethyl lactate as chelate components. These may be used alone or in combination of two or more.
- the amount of the crosslinking agent used can be, for example, 0.01 part by weight or more, and preferably 0.05 part by weight or more, based on 100 parts by weight of the base polymer. A higher cohesive force tends to be obtained by increasing the amount of the crosslinking agent used.
- the amount of the cross-linking agent used may be 0.1 part by weight or more, 100 parts by weight or more, 0.5 parts by weight or more, and 1 part by weight or more. Good.
- the amount of the cross-linking agent to be used is usually 15 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the base polymer. It may be 5 parts by weight or less.
- the use amount of the crosslinking agent is not too large. It may be advantageous from the viewpoint of good expression.
- the technique disclosed in the present specification can be preferably carried out in a mode in which at least an isocyanate cross-linking agent is used as the cross-linking agent.
- the amount of the isocyanate-based cross-linking agent based on 100 parts by weight of the base polymer is, for example, 5 parts by weight or less. It may be 3 parts by weight or less, 1 part by weight or less, 0.7 parts by weight or less, and 0.5 parts by weight or less.
- a cross-linking catalyst may be used in order to more effectively promote any of the above-mentioned cross-linking reactions.
- a crosslinking catalyst for example, a tin-based catalyst (particularly dioctyltin dilaurate) can be preferably used.
- the amount of the crosslinking catalyst used is not particularly limited, but can be, for example, approximately 0.0001 parts by weight to 1 part by weight with respect to 100 parts by weight of the base polymer.
- the pressure-sensitive adhesive layer disclosed in the present specification may further contain a silane coupling agent.
- the durability can be improved by using the silane coupling agent.
- the silane coupling agent one having any appropriate functional group can be used. Specific examples of the functional group include a vinyl group, an epoxy group, an amino group, a mercapto group, a (meth)acryloxy group, an acetoacetyl group, an isocyanate group, a styryl group, and a polysulfide group.
- vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, and vinyltributoxysilane; ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycine Epoxy group-containing silane coupling agents such as cidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; ⁇ -aminopropyltrimethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, ⁇ -triethoxysilyl-N-(1,3-dimethylbutylidene) Amino group-
- silane coupling agent for example, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane and ⁇ -mercaptopropylmethyldimethoxysilane are preferably used. You can
- the silane coupling agent may be used alone or in combination of two or more kinds, but the total content is 100 parts by weight of the base polymer and the silane coupling agent.
- the amount is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, further preferably 0.02 to 1 part by weight, further preferably 0.05 to 0.6 part by weight.
- the pressure-sensitive adhesive layer in the technique disclosed herein is a tackifier, a leveling agent, a plasticizer, a softening agent, a colorant (a dye, a pigment, etc.), a filler, etc. within a range that does not significantly impair the effects of the present invention.
- known additives such as antistatic agents, antiaging agents, ultraviolet absorbers, antioxidants, light stabilizers and preservatives that can be used for pressure-sensitive adhesives may be included.
- a method for forming a pressure-sensitive adhesive layer for example, a method in which the pressure-sensitive adhesive composition is applied to a release-treated separator or the like, and a polymerization solvent or the like is dried and removed to form a pressure-sensitive adhesive layer, and then transferred to a polarizing film, or It is prepared by a method of applying the above-mentioned pressure-sensitive adhesive composition to a polarizing film, drying and removing a polymerization solvent and the like to form an adhesive layer on the polarizing film.
- one or more solvents other than the polymerization solvent may be newly added as appropriate.
- a silicone release liner is preferably used as the release-treated separator.
- the step of forming the pressure-sensitive adhesive layer by applying the adhesive composition of the present invention on such a liner, and drying the pressure-sensitive adhesive layer as a method for drying the pressure-sensitive adhesive, an appropriate method is appropriately adopted depending on the purpose. obtain.
- a method of heating and drying the above coating film is used.
- the heat 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.
- an anchor layer can be formed on the surface of the polarizing film, or an adhesive layer can be formed after various types of easy adhesion treatment such as corona treatment and plasma treatment. Further, the surface of the pressure-sensitive adhesive layer may be subjected to easy adhesion treatment.
- Various methods are used to form the 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 of the method include an extrusion coating method.
- the thickness of the 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 further 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 release-treated sheet (separator) until practical use.
- a constituent material of the separator for example, polyethylene, polypropylene, polyethylene terephthalate, a plastic film such as a polyester film, a porous material such as paper, cloth, non-woven fabric, a net, a foamed sheet, a metal foil, and a laminated body thereof are appropriately used.
- a plastic film such as a polyester film
- a porous material such as paper, cloth, non-woven fabric, a net, a foamed sheet, a metal foil, and a laminated body thereof
- plastic thin films and plastic films are preferably used because they have excellent surface smoothness.
- the plastic film is not particularly limited as long as it is a film capable of protecting the pressure-sensitive adhesive layer, and examples thereof include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film and vinyl chloride. Examples thereof include polymer films, polyethylene terephthalate films, polybutylene terephthalate films, polyurethane films, ethylene-vinyl acetate copolymer films and the like.
- the thickness of the separator is usually 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
- a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, release and antifouling treatment with silica powder or the like, coating type, kneading type, vapor deposition type It is also possible to perform antistatic treatment such as. Particularly, by appropriately performing a peeling treatment such as a silicone treatment, a long-chain alkyl treatment, or a fluorine treatment on the surface of the separator, the peelability from the pressure-sensitive adhesive layer can be further enhanced.
- the release-treated sheet used in the production of the pressure-sensitive adhesive layer-attached polarizing film can be used as it is as a separator for the pressure-sensitive adhesive layer-attached polarizing film, which simplifies the process.
- the present invention will be described below with reference to examples, but the present invention is not limited to the examples shown below. In addition, all parts and% in each example are based on weight. Unless otherwise specified below, the room temperature standing condition is 23° C. and 65% RH.
- the weight average molecular weight Mw of each of the following polymers was determined by using a GPC device (manufactured by Tosoh Corporation, HLC-8220GPC) under the following conditions, and calculated in terms of polystyrene.
- THF tetrahydrofuran
- Eluent THF
- Flow rate 0.6 ml/min
- Measuring temperature 40°C
- SP value 32.8 thickness 23 ⁇ m
- ⁇ Active energy ray> As active energy rays, ⁇ Ultraviolet irradiation device (gallium-encapsulated metal halide lamp): Fusion UV Systems, Inc. Light HAMMER10 ⁇ Valve: V valve ⁇ Peak illuminance: 1600 mW/cm 2 , An integrated dose of 1000/mJ/cm 2 (wavelength 380 to 440 nm) was used. The illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell.
- radically polymerizable compound (A) N-hydroxyethyl acrylamide (SP value 2 9.6, homopolymer Tg123° C., manufactured by Kojin Co., Ltd., 38.3 parts
- radically polymerizable compound (B) tripropylene glycol diacrylate (trade name: Aronix M-220, SP value 19.0, Homopolymer Tg 69° C., manufactured by Toagosei Co., Ltd. 19.1 parts, and acryloylmorpholine (SP value 22.9, homopolymer Tg 150° C., manufactured by Kojin Co., Ltd.) 38.3 as the radically polymerizable compound (C).
- the active energy ray-curable adhesive was applied to the easy-adhesive layer by an MCD coater (manufactured by Fuji Machine Co., Ltd.). (Cell shape: honeycomb, gravure roll number of lines: 1000/inch, rotation speed 140%/vs line speed) was used to coat the adhesive layer to a thickness of 0.5 ⁇ m.
- MCD coater manufactured by Fuji Machine Co., Ltd.
- the acrylic resin film was bonded to both sides of the above-mentioned polarizer by a roll machine as a transparent protective film on the viewing side and the panel side via the adhesive.
- the both sides of the bonded acrylic resin film were heated to 50° C. using an IR heater, and both sides were irradiated with the above-mentioned ultraviolet rays to cure the active energy ray-curable adhesive. Further, it was dried with hot air at 70° C. for 3 minutes to obtain a polarizing film A having transparent protective films on both sides of the polarizer (Table 1).
- the bonding line speed was 25 m/min.
- Preparation of anchor coat layer> (Preparation of anchor layer coating liquid A and formation of anchor coat layer A) A solution containing 30 to 90% by weight of a urethane-based polymer and 10 to 50% by weight of a polythiophene-based polymer in terms of solid content [Nagase Chemtex's trade name "Denatron P-580W” and oxazoline group-containing acrylic polymer in terms of solid content A solution containing 10 to 70% by weight and a polyoxyethylene group-containing methacrylate of 10 to 70% by weight [Nippon Shokubai Co., Ltd.
- Epocros WS-700 was added to a 100% by weight water (mixed) solution, The solid content concentration (base concentration) was adjusted to 0.4% by weight.
- the prepared solution was applied to the acrylic film side opposite to the visible side of the polarizing film by using Meyer bar #5, and the time until the oven was placed in a drying oven (the time until the drying was started) was 5 seconds. After providing, it was dried at 50° C. for 25 seconds to form an anchor coat layer A having a thickness of 48 nm. The coating thickness before drying calculated from the dry thickness was about 12 ⁇ m.
- the work was performed in a 23° C. 55% RH atmosphere. Plasma treatment or corona treatment may be performed as dry treatment for improving wettability.
- the prepared solution was applied to the acrylic film side opposite to the visible side of the polarizing film by using Meyer bar #5, and the time until the oven was placed in a drying oven (the time until the drying was started) was 5 seconds. After being provided, it was dried at 50° C. for 25 seconds to form an anchor coat layer B having a thickness of 48 nm. The coating thickness before drying calculated from the dry thickness was about 12 ⁇ m. The work was performed in a 23° C. 55% RH atmosphere. Plasma treatment or corona treatment may be performed as dry treatment for improving wettability.
- composition of the anchor coat layer is shown in Table 2 below.
- cross-linking agent based on 100 parts of the solid content of the acrylic polymer solution A, a cross-linking agent containing 0.6 part of a compound having an isocyanate group as a main component (manufactured by Nippon Polyurethane Co., Ltd., trade name “Coronate L”) ) And 0.075 part of ⁇ -glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”) as a silane coupling agent in this order, and the adhesive agent Polymer solution A was prepared.
- cross-linking agent a cross-linking agent containing 0.6 part of a compound having an isocyanate group as a main component based on 100 parts of the solid content of the acrylic polymer solution (B) (manufactured by Nippon Polyurethane Co., Ltd., trade name “Coronate”) L”) and 0.075 part of ⁇ -glycidoxypropyltrimethoxysilane (trade name “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent in this order, An adhesive polymer solution B was prepared.
- compositions of the acrylic polymer solution (A) (polymer A), the acrylic polymer solution (B) (polymer B), and the acrylic polymer solution (C) (polymer C) are shown in Table 3 below.
- Silicone oligomers B to F were prepared in the same manner as silicone oligomer A, except that the monomer composition and parts by weight were changed to the constituent components shown in Table 4.
- Comparative Example 1 A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the silicone oligomer A was removed in Comparative Example 1.
- the measurement was performed 200 times at intervals of 1 time/0.5 s, and the average value was used as the measured value.
- the number of samples was three.
- the average value thereof is shown in the column of "2 kg roller" in Table 5 as the initial adhesive strength.
- the reworkability was judged based on the level of adhesive strength according to the following criteria.
- C More than 5N/25mm and 6N/25mm or less, and rework succeeds 70% or more.
- D More than 6 N/25 mm and 7 N/25 mm or less, and rework succeeds 60% or more.
- E Over 7 N/25 mm, rework fails more than 40%.
- the produced polarizing film with an adhesive layer was cut into a length of 120 mm and a width of 25 mm to obtain a sample.
- the sample was attached to a 0.7 mm-thick non-alkali glass plate (EG-XG, manufactured by Corning Incorporated) using a laminator, and then autoclaved at 50° C. and 5 atm for 15 minutes for complete adhesion.
- the adhesive strength of the sample was measured.
- the adhesive force is measured by a tensile tester (Autograph SHIMAZU AG-1 1OKN) at a peeling angle of 90° and a peeling speed of 300 mm/min. (N/25 mm, measuring length 80 mm) was obtained by doing.
- ⁇ Measuring method of anchoring force of pressure-sensitive adhesive layer> A polyethylene terephthalate film [Oike Industry Co., Ltd., trade name "125 Tetraite OES" (thickness 125 ⁇ m)] having a 25 mm width, which was vapor-deposited with indium tin oxide, was used.
- the polarizing film with the pressure-sensitive adhesive layer was pressure-bonded back and forth once with a 2 kg roller and cured at 23° C. for 1 minute, and the adhesive strength was measured when the polyethylene terephthalate film was peeled together with the pressure-sensitive adhesive layer in the 180° direction at 300 mm/min. .. Then, the anchoring power was judged according to the following criteria.
- a polarizing film with an adhesive layer which has both high durability and reworkability and is excellent in the adhesiveness (anchoring force) between the polarizing film and the adhesive.
- Polarizer 2 1st protective film 2'2nd protective film 3 Polarizing film 4 Adhesive layer 5 Separator 10 Polarizing film with an adhesive layer
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Abstract
Provided is a polarizing film provided with an adhesive layer, provided with high durability and reworkability, and having excellent adhesion (anchoring power) between the polarizing film and the adhesive. Provided is a polarizing film provided with an adhesive layer, comprising: a polarizing film provided with a polarizer, a first protective film provided on a visible side of the polarizer, and a second protective film provided on the reverse side of the polarizer from the visible side thereof; and an adhesive layer provided on the second protective film; wherein the adhesive layer includes a base polymer and a silicone oligomer Ps, the silicone oligomer Ps is included in the amount of 0.1-20 parts by weight with respect to 100 parts by weight of the base polymer, and the silicone oligomer Ps has a Tg of -50°C to 100°C, a side-chain silicone functional group equivalent weight of 1,000-20,000 g/mol, and a weight-average molecular weight of 10,000 to 300,000.
Description
本発明は、粘着剤層付偏光フィルムに関する。より詳細には、本発明は、偏光子の両側に保護フィルムを備える粘着剤層付偏光フィルムに関する。
The present invention relates to a polarizing film with an adhesive layer. More specifically, the present invention relates to a pressure-sensitive adhesive layer-attached polarizing film having protective films on both sides of a polarizer.
液晶表示装置には、その画像形成方式から液晶パネル表面を形成するガラス基板の両側に偏光フィルムを配置することが必要不可欠である。偏光フィルムは、一般的には、ポリビニルアルコール系フィルムとヨウ素等の二色性材料からなる偏光子の片面または両面に、保護フィルムをポリビニルアルコール系接着剤等により貼り合わせたものが用いられている。
According to the image forming method, it is essential for liquid crystal display devices to place polarizing films on both sides of the glass substrate that forms the surface of the liquid crystal panel. As the polarizing film, generally, a polyvinyl alcohol-based film and a polarizer made of a dichroic material such as iodine having a protective film bonded to one or both surfaces thereof with a polyvinyl alcohol-based adhesive or the like are used. ..
前記偏光フィルムを液晶セル等に貼着する際には、通常、粘着剤が使用される。また、偏光フィルムを瞬時に固定できること、偏光フィルムを固着させるのに乾燥工程を必要としないこと等のメリットを有することから、粘着剤は、偏光フィルムの片面に予め粘着剤層として設けられている。即ち、偏光フィルムの貼着には粘着剤層付偏光フィルムが一般的に用いられる(特許文献1および2)。
When attaching the polarizing film to a liquid crystal cell etc., an adhesive is usually used. In addition, the pressure-sensitive adhesive is preliminarily provided as a pressure-sensitive adhesive layer on one surface of the polarizing film, since it has advantages such as being able to instantly fix the polarizing film and not requiring a drying step to fix the polarizing film. .. That is, a polarizing film with an adhesive layer is generally used for sticking a polarizing film (Patent Documents 1 and 2).
また、偏光フィルムや粘着剤層付き偏光フィルムを液晶パネルのガラス基板に貼り合わせた場合、耐久性が求められており、例えば、環境促進試験として通常行われる加熱および加湿等による耐久試験において、粘着剤層に起因する剥がれや浮き等の不具合が発生しないことが求められる。
Further, when a polarizing film or a polarizing film with a pressure-sensitive adhesive layer is attached to a glass substrate of a liquid crystal panel, durability is required, and for example, in a durability test such as heating and humidification that is usually performed as an environmental promotion test, adhesion It is required that problems such as peeling and floating due to the agent layer do not occur.
このように偏光フィルムに使用する粘着剤は、高耐久性が求められる反面、偏光板を貼り合わせる際の工程不良で発生した欠点や貼りミスをリカバリーするために、リワーク性の要望も高まっている。近年パネルの薄型化や大型化のトレンドにより、パネルの再活要望が高くなっているため、リワーク性は重要な項目である。しかしながら、高耐久性とリワーク性はトレードオフの関係にあり、両立が非常に難しい特性である。
As described above, while the pressure-sensitive adhesive used for the polarizing film is required to have high durability, there is an increasing demand for reworkability in order to recover a defect or a bonding error caused by a process defect in bonding the polarizing plate. .. Due to the trend of thinner and larger panels in recent years, the demand for re-activating panels is increasing, and reworkability is an important item. However, there is a trade-off relationship between high durability and reworkability, and it is very difficult to achieve both at the same time.
さらに、偏光フィルムと粘着剤層との密着性が悪いと、リワーク時に粘着剤のみがパネルに残る不良が発生する。また、ロール状の偏光フィルムについて打ち抜き等の加工をした時に、糊欠けが発生し、視認性に影響を与える可能性があるため、偏光フィルムと粘着剤との密着性(投錨力)も重要な特性である。
Furthermore, if the adhesion between the polarizing film and the adhesive layer is poor, there will be defects in which only the adhesive remains on the panel during rework. In addition, adhesiveness (anchoring force) between the polarizing film and the adhesive is important because adhesive cracks may occur when punching the rolled polarizing film, which may affect visibility. It is a characteristic.
上記の背景技術に鑑み、トレードオフの関係にある高耐久性とリワーク性とを両立して備えることができ、かつ偏光フィルムと粘着剤との密着性(投錨力)に優れる、粘着剤層付き偏光フィルムが強く望まれている。
In view of the above background art, with a pressure-sensitive adhesive layer, it is possible to provide both high durability and reworkability that are in a trade-off relationship, and excellent in adhesion (anchoring force) between the polarizing film and the pressure-sensitive adhesive. A polarizing film is strongly desired.
本発明者らは、鋭意検討の結果、本発明の粘着剤層付き偏光フィルムにより上記の課題を解決し得ることを見出し、本発明を完成するに至った。
As a result of intensive studies, the present inventors have found that the polarizing film with an adhesive layer of the present invention can solve the above problems, and have completed the present invention.
すなわち、本発明は、下記の実施形態を含む。
That is, the present invention includes the following embodiments.
(1)偏光子と、前記偏光子の視認側に設けられた第1の保護フィルムと、前記偏光子の視認側とは反対側に設けられた第2の保護フィルムと、を備える偏光フィルムと、
前記第2の保護フィルム上に設けられる粘着剤層と、を備える粘着剤層付き偏光フィルムであって、
前記粘着剤層は、ベースポリマーと、シリコーンオリゴマーPsとを含み、
前記シリコーンオリゴマーPsは、前記ベースポリマー100重量部に対し、0.1~20重量部で含まれ、
前記シリコーンオリゴマーPsは、Tgが-50℃以上100℃以下、側鎖のシリコーン官能基当量が1000~20000g/molであり、重量平均分子量が10000以上300000以下である、粘着剤層付き偏光フィルム。 (1) A polarizing film comprising a polarizer, a first protective film provided on the viewing side of the polarizer, and a second protective film provided on the opposite side of the viewing side of the polarizer. ,
A pressure-sensitive adhesive layer-provided polarizing film comprising: a pressure-sensitive adhesive layer provided on the second protective film,
The pressure-sensitive adhesive layer includes a base polymer and a silicone oligomer Ps,
The silicone oligomer Ps is included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the base polymer,
The silicone oligomer Ps has a Tg of −50° C. or higher and 100° C. or lower, a side chain silicone functional group equivalent of 1000 to 20000 g/mol, and a weight average molecular weight of 10,000 or more and 300,000 or less.
前記第2の保護フィルム上に設けられる粘着剤層と、を備える粘着剤層付き偏光フィルムであって、
前記粘着剤層は、ベースポリマーと、シリコーンオリゴマーPsとを含み、
前記シリコーンオリゴマーPsは、前記ベースポリマー100重量部に対し、0.1~20重量部で含まれ、
前記シリコーンオリゴマーPsは、Tgが-50℃以上100℃以下、側鎖のシリコーン官能基当量が1000~20000g/molであり、重量平均分子量が10000以上300000以下である、粘着剤層付き偏光フィルム。 (1) A polarizing film comprising a polarizer, a first protective film provided on the viewing side of the polarizer, and a second protective film provided on the opposite side of the viewing side of the polarizer. ,
A pressure-sensitive adhesive layer-provided polarizing film comprising: a pressure-sensitive adhesive layer provided on the second protective film,
The pressure-sensitive adhesive layer includes a base polymer and a silicone oligomer Ps,
The silicone oligomer Ps is included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the base polymer,
The silicone oligomer Ps has a Tg of −50° C. or higher and 100° C. or lower, a side chain silicone functional group equivalent of 1000 to 20000 g/mol, and a weight average molecular weight of 10,000 or more and 300,000 or less.
(2)前記シリコーンオリゴマーPsが、モノマー単位として、ポリオルガノシロキサン骨格を有するモノマーS1と、ホモポリマーのガラス転移温度が-70℃以上180℃以下のモノマーとを含む、上記(1)に記載の粘着剤層付き偏光フィルム。
(2) The above-mentioned (1), wherein the silicone oligomer Ps contains, as a monomer unit, a monomer S1 having a polyorganosiloxane skeleton and a homopolymer having a glass transition temperature of −70° C. or higher and 180° C. or lower. Polarizing film with adhesive layer.
(3)前記ベースポリマーが、モノマー単位として、ホモポリマーのガラス転移温度が-80℃以上0℃以下であるアルキル(メタ)アクリレート(A)を80重量%以上で含有する、上記(1)または(2)に記載の粘着剤層付き偏光フィルム。
(3) The base polymer contains, as a monomer unit, 80% by weight or more of an alkyl (meth)acrylate (A) whose homopolymer has a glass transition temperature of −80° C. or higher and 0° C. or lower, (1) or The polarizing film with an adhesive layer according to (2).
(4)前記ベースポリマーが、モノマー単位として、カルボキシル基含有モノマー(b1)および窒素含有モノマー(b2)からなる群より選択される少なくとも1種の極性モノマー(B)を0~20重量%で更に含有する、上記(3)に記載の粘着剤層付き偏光フィルム。
(4) The base polymer further contains, as a monomer unit, at least one polar monomer (B) selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2) in an amount of 0 to 20% by weight. The polarizing film with a pressure-sensitive adhesive layer according to the above (3), which is contained.
(5)前記ベースポリマーが、モノマー単位として、水酸基含有モノマーを0.01~5重量%で含有する、上記(4)に記載の粘着剤層付き偏光フィルム。
(5) The polarizing film with a pressure-sensitive adhesive layer as described in (4) above, wherein the base polymer contains 0.01 to 5% by weight of a hydroxyl group-containing monomer as a monomer unit.
(6)前記ベースポリマーの重量平均分子量が50万~250万である、上記(1)~(5)のいずれかに記載の粘着剤層付き偏光フィルム。
(6) The polarizing film with a pressure-sensitive adhesive layer according to any one of (1) to (5) above, wherein the base polymer has a weight average molecular weight of 500,000 to 2,500,000.
(7)前記第2の保護フィルムと前記粘着剤層との間に機能性コーティング層を更に備える、上記(1)~(6)のいずれかに記載の粘着剤層付き偏光フィルム。
(7) The polarizing film with a pressure-sensitive adhesive layer according to any one of (1) to (6) above, further including a functional coating layer between the second protective film and the pressure-sensitive adhesive layer.
(8)前記機能性コーティング層が、オキサゾリン基含有ポリマーを含有する、上記(7)に記載の粘着剤層付き偏光フィルム。
(8) The polarizing film with a pressure-sensitive adhesive layer according to (7) above, wherein the functional coating layer contains an oxazoline group-containing polymer.
(9)前記シリコーンオリゴマーPsの溶融温度が、-20℃~120℃である、上記(1)~(8)のいずれかに記載の粘着剤層付き偏光フィルム。
(9) The polarizing film with a pressure-sensitive adhesive layer according to any one of (1) to (8) above, wherein the melting temperature of the silicone oligomer Ps is −20° C. to 120° C.
本発明によれば、貼り合わせ直後のリワーク性を付与しながら、加熱後に粘着力が上昇して耐久性を付与することができ、かつ偏光フィルムと粘着剤との密着性(投錨力)に優れる、粘着剤層付き偏光フィルムを提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, while giving the reworkability immediately after bonding, the adhesive force can increase after heating and durability can be given, and the adhesiveness (anchoring force) between a polarizing film and an adhesive is excellent. A polarizing film with an adhesive layer can be provided.
以下、本発明の好適な実施形態について説明する。本明細書において特に言及している事項以外の事柄であって本発明の実施に必要な事柄は、本明細書に記載された発明の実施についての教示と出願時の技術常識とに基づいて当業者に理解され得る。本発明は、本明細書に開示されている内容と当該分野における技術常識とに基づいて実施することができる。
A preferred embodiment of the present invention will be described below. Matters other than the matters particularly referred to in the present specification and necessary for the implementation of the present invention should be determined based on the teaching about the implementation of the invention described in the present specification and the common general knowledge as of the filing. It can be understood by those skilled in the art. The present invention can be carried out based on the contents disclosed in this specification and the common general technical knowledge in the field.
<粘着剤層付き偏光フィルム>
本発明の粘着剤層付き偏光フィルムは、偏光フィルムと、粘着剤層とを備える。本発明において、粘着剤層は、偏光フィルムの片面に存在してもよいし、両面に存在してもよい。 <Polarizing film with adhesive layer>
The polarizing film with a pressure-sensitive adhesive layer of the present invention includes a polarizing film and a pressure-sensitive adhesive layer. In the present invention, the pressure-sensitive adhesive layer may be present on one side or both sides of the polarizing film.
本発明の粘着剤層付き偏光フィルムは、偏光フィルムと、粘着剤層とを備える。本発明において、粘着剤層は、偏光フィルムの片面に存在してもよいし、両面に存在してもよい。 <Polarizing film with adhesive layer>
The polarizing film with a pressure-sensitive adhesive layer of the present invention includes a polarizing film and a pressure-sensitive adhesive layer. In the present invention, the pressure-sensitive adhesive layer may be present on one side or both sides of the polarizing film.
一実施形態に係る粘着剤層付き偏光フィルムの構造を図1に模式的に示す。この粘着剤層付き偏光フィルム10は、偏光フィルム3と、その片面に設けられた粘着剤層4とを備える粘着剤層付き偏光フィルムとして構成されている。図1において、偏光フィルム3は、偏光子1と、前記偏光子1の視認側に設けられた第1の保護フィルム2と、前記偏光子1の視認側とは反対側に設けられた第2の保護フィルム2’とから構成されている。粘着剤層4は、偏光フィルム3を構成する第2の保護フィルム2’上に固定的に、すなわち当該偏光フィルム3から粘着剤層4を分離する意図なく、設けられている。粘着剤層付き偏光フィルム10は、粘着剤層4を被着体に貼り付けて用いられる。セパレータ5としては、例えば、シート状の基材(ライナー基材)の片面に剥離処理剤による剥離層を設けることで当該片面が剥離面となるように構成されたものを好ましく使用し得る。粘着剤層付き偏光フィルムの構造は、図1に模式的に示された実施形態には限定されない。
The structure of a polarizing film with an adhesive layer according to one embodiment is schematically shown in FIG. The polarizing film with an adhesive layer 10 is configured as a polarizing film with an adhesive layer, which includes the polarizing film 3 and the adhesive layer 4 provided on one surface thereof. In FIG. 1, the polarizing film 3 includes a polarizer 1, a first protective film 2 provided on the viewing side of the polarizer 1, and a second protective film 2 provided on the opposite side of the viewing side of the polarizer 1. And the protective film 2'of. The pressure-sensitive adhesive layer 4 is provided fixedly on the second protective film 2 ′ forming the polarizing film 3, that is, without the intention of separating the pressure-sensitive adhesive layer 4 from the polarizing film 3. The polarizing film 10 with an adhesive layer is used by attaching the adhesive layer 4 to an adherend. As the separator 5, for example, a sheet-shaped base material (liner base material) which has a release layer provided with a release treatment agent on one surface so that the one surface serves as a release surface can be preferably used. The structure of the polarizing film with an adhesive layer is not limited to the embodiment schematically shown in FIG.
<偏光子>
偏光子は、特に限定されず、各種のものを使用できる。偏光子としては、例えば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料の二色性物質を吸着させて一軸延伸したもの、ポリビニルアルコールの脱水処理物やポリ塩化ビニルの脱塩酸処理物等ポリエン系配向フィルム等が挙げられる。これらの中でも、ポリビニルアルコール系フィルムとヨウ素などの二色性物質からなる偏光子が好適である。これらの偏光子の厚さは特に制限されないが、一般的には2~25μmである。 <Polarizer>
The polarizer is not particularly limited, and various kinds can be used. Examples of the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene/vinyl acetate copolymer partially saponified film, and dichroism of iodine or dichroic dye. Examples include polyene-oriented films such as those obtained by adsorbing a substance and uniaxially stretched, polyvinyl alcohol dehydrated products, polyvinyl chloride dehydrochlorinated products, and the like. Among these, a polarizer made of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally 2 to 25 μm.
偏光子は、特に限定されず、各種のものを使用できる。偏光子としては、例えば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料の二色性物質を吸着させて一軸延伸したもの、ポリビニルアルコールの脱水処理物やポリ塩化ビニルの脱塩酸処理物等ポリエン系配向フィルム等が挙げられる。これらの中でも、ポリビニルアルコール系フィルムとヨウ素などの二色性物質からなる偏光子が好適である。これらの偏光子の厚さは特に制限されないが、一般的には2~25μmである。 <Polarizer>
The polarizer is not particularly limited, and various kinds can be used. Examples of the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene/vinyl acetate copolymer partially saponified film, and dichroism of iodine or dichroic dye. Examples include polyene-oriented films such as those obtained by adsorbing a substance and uniaxially stretched, polyvinyl alcohol dehydrated products, polyvinyl chloride dehydrochlorinated products, and the like. Among these, a polarizer made of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally 2 to 25 μm.
ポリビニルアルコール系フィルムをヨウ素で染色し一軸延伸した偏光子は、例えば、ポリビニルアルコール系フィルムをヨウ素の水溶液に浸漬することによって染色し、元長の3~7倍に延伸することで作製することができる。必要に応じてホウ酸や硫酸亜鉛、塩化亜鉛等を含んでいても良いヨウ化カリウムなどの水溶液に浸漬することもできる。さらに必要に応じて染色前にポリビニルアルコール系フィルムを水に浸漬して水洗してもよい。ポリビニルアルコール系フィルムを水洗することでポリビニルアルコール系フィルム表面の汚れやブロッキング防止剤を洗浄することができるほかに、ポリビニルアルコール系フィルムを膨潤させることで染色のムラなどの不均一を防止する効果もある。延伸はヨウ素で染色した後に行っても良いし、染色しながら延伸しても良いし、また延伸してからヨウ素で染色しても良い。ホウ酸やヨウ化カリウムなどの水溶液や水浴中でも延伸することができる。
A uniaxially stretched polarizer obtained by dyeing a polyvinyl alcohol film with iodine can be produced, for example, by dyeing a polyvinyl alcohol film by immersing it in an aqueous solution of iodine and stretching it to 3 to 7 times its original length. it can. If necessary, it can be immersed in an aqueous solution of potassium iodide or the like 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 with water before dyeing. By washing the polyvinyl alcohol-based film with water, it is possible to wash the stains and anti-blocking agent on the surface of the polyvinyl alcohol-based film, and by swelling the polyvinyl alcohol-based film, the effect of preventing unevenness such as uneven dyeing is also obtained. is there. Stretching may be performed after dyeing with iodine, stretching while dyeing, or stretching and then dyeing with iodine. Stretching can be performed in an aqueous solution of boric acid or potassium iodide or in a water bath.
<保護フィルム>
前記保護フィルムを構成する材料としては、透明性、機械的強度、熱安定性、水分遮断性、等方性などに優れるものが好ましい。例えば、ポリエチレンテレフタレートやポリエチレンナフタレートなどのポリエステル系ポリマー、ジアセチルセルロースやトリアセチルセルロースなどのセルロース系ポリマー、ポリメチルメタクリレートなどのアクリル系ポリマー、ポリスチレンやアクリロニトリル・スチレン共重合体(AS樹脂)などのスチレン系ポリマー、ポリカーボネート系ポリマー等が挙げられる。また、ポリエチレン、ポリプロピレン、シクロ系ないしはノルボルネン構造を有するポリオレフィン、エチレン・プロピレン共重合体の如きポリオレフィン系ポリマー、塩化ビニル系ポリマー、ナイロンや芳香族ポリアミドなどのアミド系ポリマー、イミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマー、または上記ポリマーのブレンド物なども上記保護フィルムを形成するポリマーの例として挙げられる。これら保護フィルムは、通常、接着剤層により、偏光子に貼り合わせられる。また、前記保護フィルムは、(メタ)アクリル系、ウレタン系、アクリルウレタン系、エポキシ系、シリコーン系等の熱硬化性樹脂または紫外線硬化型樹脂を用いて、これらを偏光子に塗布し、硬化させることにより形成することができる。 <Protective film>
The material forming the protective film is preferably one having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like. For example, polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose, acrylic-based polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile-styrene copolymer (AS resin). Examples thereof include a polymer and a polycarbonate polymer. Further, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene/propylene copolymer, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers. , Polyether sulfone-based polymer, polyether ether ketone-based polymer, polyphenylene sulfide-based polymer, vinyl alcohol-based polymer, vinylidene chloride-based polymer, vinyl butyral-based polymer, arylate-based polymer, polyoxymethylene-based polymer, epoxy-based polymer, or the above Blends of polymers and the like are also mentioned as examples of the polymer forming the protective film. These protective films are usually attached to the polarizer with an adhesive layer. The protective film is made of a thermosetting resin such as a (meth)acrylic resin, a urethane resin, an acrylic urethane resin, an epoxy resin, or a silicone resin, or an ultraviolet curable resin, which is applied to the polarizer and cured. It can be formed by
前記保護フィルムを構成する材料としては、透明性、機械的強度、熱安定性、水分遮断性、等方性などに優れるものが好ましい。例えば、ポリエチレンテレフタレートやポリエチレンナフタレートなどのポリエステル系ポリマー、ジアセチルセルロースやトリアセチルセルロースなどのセルロース系ポリマー、ポリメチルメタクリレートなどのアクリル系ポリマー、ポリスチレンやアクリロニトリル・スチレン共重合体(AS樹脂)などのスチレン系ポリマー、ポリカーボネート系ポリマー等が挙げられる。また、ポリエチレン、ポリプロピレン、シクロ系ないしはノルボルネン構造を有するポリオレフィン、エチレン・プロピレン共重合体の如きポリオレフィン系ポリマー、塩化ビニル系ポリマー、ナイロンや芳香族ポリアミドなどのアミド系ポリマー、イミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマー、または上記ポリマーのブレンド物なども上記保護フィルムを形成するポリマーの例として挙げられる。これら保護フィルムは、通常、接着剤層により、偏光子に貼り合わせられる。また、前記保護フィルムは、(メタ)アクリル系、ウレタン系、アクリルウレタン系、エポキシ系、シリコーン系等の熱硬化性樹脂または紫外線硬化型樹脂を用いて、これらを偏光子に塗布し、硬化させることにより形成することができる。 <Protective film>
The material forming the protective film is preferably one having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like. For example, polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose, acrylic-based polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile-styrene copolymer (AS resin). Examples thereof include a polymer and a polycarbonate polymer. Further, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene/propylene copolymer, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers. , Polyether sulfone-based polymer, polyether ether ketone-based polymer, polyphenylene sulfide-based polymer, vinyl alcohol-based polymer, vinylidene chloride-based polymer, vinyl butyral-based polymer, arylate-based polymer, polyoxymethylene-based polymer, epoxy-based polymer, or the above Blends of polymers and the like are also mentioned as examples of the polymer forming the protective film. These protective films are usually attached to the polarizer with an adhesive layer. The protective film is made of a thermosetting resin such as a (meth)acrylic resin, a urethane resin, an acrylic urethane resin, an epoxy resin, or a silicone resin, or an ultraviolet curable resin, which is applied to the polarizer and cured. It can be formed by
なお、保護フィルム中には任意の適切な添加剤が1種類以上含まれていてもよい。添加剤としては、例えば、紫外線吸収剤、酸化防止剤、滑剤、可塑剤、離型剤、着色防止剤、難燃剤、核剤、帯電防止剤、顔料、着色剤などがあげられる。保護フィルム中の上記熱可塑性樹脂の含有量は、好ましくは50~100重量%、より好ましくは50~99重量%、さらに好ましくは60~98重量%、特に好ましくは70~97重量%である。保護フィルム中の上記熱可塑性樹脂の含有量が50重量%以下の場合、熱可塑性樹脂が本来有する高透明性等が十分に発現できないおそれがある。
Incidentally, the protective film may contain one or more kinds of appropriate additives. Examples of 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 protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, further preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. When the content of the thermoplastic resin in the protective film is 50% by weight or less, the high transparency originally possessed by the thermoplastic resin may not be sufficiently exhibited.
前記保護フィルムとしては、位相差フィルム、輝度向上フィルム、拡散フィルム等を用いることができる。位相差フィルムとしては、正面位相差が40nm以上および/または、厚み方向位相差が80nm以上の位相差を有するものが挙げられる。正面位相差は、通常、40~200nmの範囲に、厚み方向位相差は、通常、80~300nmの範囲に制御される。保護フィルムとして位相差フィルムを用いる場合には、当該位相差フィルムが偏光子保護フィルムとしても機能するため、薄型化を図ることができる。
As the protective film, a retardation film, a brightness enhancement film, a diffusion film, etc. can be used. Examples of the retardation film include those having a front surface retardation of 40 nm or more and/or a thickness direction retardation of 80 nm or more. The front retardation is usually controlled in the range of 40 to 200 nm, and the thickness direction retardation is usually controlled in the range of 80 to 300 nm. When a retardation film is used as the protective film, the retardation film also functions as a polarizer protective film, so that the thickness can be reduced.
位相差フィルムとしては、熱可塑性樹脂フィルムを一軸または二軸延伸処理してなる複屈折性フィルムが挙げられる。上記延伸の温度、延伸倍率等は、位相差値、フィルムの材料、厚みにより適宜に設定される。
The retardation film may be a birefringent film obtained by uniaxially or biaxially stretching a thermoplastic resin film. The stretching temperature, the stretching ratio, and the like are appropriately set depending on the retardation value, the material of the film, and the thickness.
前記保護フィルムの厚さは、適宜に決定しうるが、一般には強度や取扱性等の作業性、薄層性などの点より3~200μmであるのが好ましく、さらには3~100μmであるのが好ましい。特に、前記保護フィルム(予めフィルムが形成されている場合)の厚みは、搬送性の点から10~60μmが好ましく、さらには10~45μmが好ましい。一方、前記保護フィルム(塗布、硬化により形成する場合)の厚みは搬送性の点から、3~25μmが好ましく、さらには3~20μmが好ましい。前記保護フィルムは、複数枚または複数層で用いることもできる。
The thickness of the protective film can be appropriately determined, but generally it is preferably 3 to 200 μm, more preferably 3 to 100 μm from the viewpoint of workability such as strength and handleability, and thin layer property. Is preferred. In particular, the thickness of the protective film (when the film is previously formed) is preferably 10 to 60 μm, more preferably 10 to 45 μm from the viewpoint of transportability. On the other hand, the thickness of the protective film (when formed by coating and curing) is preferably 3 to 25 μm, more preferably 3 to 20 μm from the viewpoint of transportability. The protective film may be used in plural sheets or in plural layers.
前記保護フィルムの偏光子を接着させない面には、ハードコート層、反射防止層、スティッキング防止層、拡散層ないしアンチグレア層などの機能層を設けることができる。なお、上記ハードコート層、反射防止層、スティッキング防止層、拡散層やアンチグレア層などの機能層は、保護フィルムそのものに設けることができるほか、別途、保護フィルムとは別体のものとして設けることもできる。
A functional layer such as a hard coat layer, an antireflection layer, a sticking prevention layer, a diffusion layer or an antiglare layer can be provided on the surface of the protective film to which the polarizer is not adhered. The hard coat layer, the antireflection layer, the antisticking layer, the functional layer such as the diffusion layer and the antiglare layer may be provided on the protective film itself, or may be provided separately from the protective film. it can.
<介在層>
前記保護フィルムと偏光子は接着剤層、粘着剤層、下塗り層(プライマー層)などの介在層を介して積層される。この際、介在層により両者を空気間隙なく積層することが望ましい。 <Intervening layer>
The protective film and the polarizer are laminated via intervening layers such as an adhesive layer, a pressure-sensitive adhesive layer, and an undercoat layer (primer layer). At this time, it is desirable that both layers are laminated without an air gap by the intervening layer.
前記保護フィルムと偏光子は接着剤層、粘着剤層、下塗り層(プライマー層)などの介在層を介して積層される。この際、介在層により両者を空気間隙なく積層することが望ましい。 <Intervening layer>
The protective film and the polarizer are laminated via intervening layers such as an adhesive layer, a pressure-sensitive adhesive layer, and an undercoat layer (primer layer). At this time, it is desirable that both layers are laminated without an air gap by the intervening layer.
接着剤層は接着剤により形成される。接着剤の種類は特に制限されず、種々のものを用いることができる。前記接着剤層は光学的に透明であれば特に制限されず、接着剤としては、水系、溶剤系、ホットメルト系、活性エネルギー線硬化型等の各種形態のものが用いられるが、水系接着剤または活性エネルギー線硬化型接着剤が好適である。
The adhesive layer is formed by an adhesive. The type of adhesive is not particularly limited, and various types can be used. The adhesive layer is not particularly limited as long as it is optically transparent, and various types of adhesives such as water-based, solvent-based, hot melt-based and active energy ray-curable adhesives are used. Alternatively, an active energy ray-curable adhesive is suitable.
水系接着剤としては、イソシアネート系接着剤、ポリビニルアルコール系接着剤、ゼラチン系接着剤、ビニル系ラテックス系、水系ポリエステル等を例示できる。水系接着剤は、通常、水溶液からなる接着剤として用いられ、通常、0.5~60重量%の固形分を含有してなる。
Examples of water-based adhesives include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latex-based adhesives, and water-based polyesters. The water-based adhesive is usually used as an adhesive composed of an aqueous solution, and usually contains 0.5 to 60% by weight of solid content.
活性エネルギー線硬化型接着剤は、電子線、紫外線(ラジカル硬化型、カチオン硬化型)等の活性エネルギー線により硬化が進行する接着剤であり、例えば、電子線硬化型、紫外線硬化型の態様で用いることができる。活性エネルギー線硬化型接着剤は、例えば、光ラジカル硬化型接着剤を用いることができる。光ラジカル硬化型の活性エネルギー線硬化型接着剤を、紫外線硬化型として用いる場合には、当該接着剤は、ラジカル重合性化合物および光重合開始剤を含有する。
The active energy ray-curable adhesive is an adhesive that is cured by active energy rays such as electron beams and ultraviolet rays (radical curable type, cation curable type), and is, for example, an electron beam curable type or an ultraviolet ray curable type. Can be used. As the active energy ray curable adhesive, for example, a photo radical curable adhesive can be used. When the photo-radical curable active energy ray curable adhesive is used as an ultraviolet curable adhesive, the adhesive contains a radical polymerizable compound and a photopolymerization initiator.
また、前記接着剤の塗工は、水系接着剤等を用いる場合には、最終的に形成される接着剤層の厚みが30~300nmになるように行うのが好ましい。前記接着剤層の厚さは、さらに好ましくは60~250nmである。一方、活性エネルギー線硬化型接着剤を用いる場合には、前記接着剤層の厚みは、0.1~200μmになるよう行うのが好ましい。より好ましくは、0.5~50μm、さらに好ましくは0.5~10μmである。
Further, when the water-based adhesive or the like is used, it is preferable to apply the adhesive so that the finally formed adhesive layer has a thickness of 30 to 300 nm. The thickness of the adhesive layer is more preferably 60 to 250 nm. On the other hand, when an active energy ray-curable adhesive is used, it is preferable that the adhesive layer has a thickness of 0.1 to 200 μm. The thickness is more preferably 0.5 to 50 μm, further preferably 0.5 to 10 μm.
なお、偏光子と保護フィルムの積層にあたって、保護フィルムと接着剤層の間には、易接着層を設けることができる。
In addition, when laminating the polarizer and the protective film, an easily adhesive layer can be provided between the protective film and the adhesive layer.
<機能性コーティング層(アンカーコート層)>
本発明の一実施形態において、偏光フィルムの少なくとも片面に機能性コーティング層を介して粘着剤層が積層されていてよい。本発明の好ましい実施形態において、粘着剤層付き偏光フィルムは、第2の保護フィルムと粘着剤層との間に機能性コーティング層を更に備えることができる。本発明において、用語「機能性コーティング層」、「アンカーコート層」、「アンカー層」は互換的に用いられる。 <Functional coating layer (anchor coat layer)>
In one embodiment of the present invention, a pressure-sensitive adhesive layer may be laminated on at least one surface of the polarizing film via a functional coating layer. In a preferred embodiment of the present invention, the polarizing film with a pressure-sensitive adhesive layer may further include a functional coating layer between the second protective film and the pressure-sensitive adhesive layer. In the present invention, the terms "functional coating layer", "anchor coat layer" and "anchor layer" are used interchangeably.
本発明の一実施形態において、偏光フィルムの少なくとも片面に機能性コーティング層を介して粘着剤層が積層されていてよい。本発明の好ましい実施形態において、粘着剤層付き偏光フィルムは、第2の保護フィルムと粘着剤層との間に機能性コーティング層を更に備えることができる。本発明において、用語「機能性コーティング層」、「アンカーコート層」、「アンカー層」は互換的に用いられる。 <Functional coating layer (anchor coat layer)>
In one embodiment of the present invention, a pressure-sensitive adhesive layer may be laminated on at least one surface of the polarizing film via a functional coating layer. In a preferred embodiment of the present invention, the polarizing film with a pressure-sensitive adhesive layer may further include a functional coating layer between the second protective film and the pressure-sensitive adhesive layer. In the present invention, the terms "functional coating layer", "anchor coat layer" and "anchor layer" are used interchangeably.
アンカーコート層は、水系樹脂を含有し得る。アンカーコート層は、アンカー層形成用塗布液(例えば、水系樹脂を含有する水系樹脂組成物)を、保護フィルムに塗布することにより形成することができる。前記水系樹脂としては、例えば、ポリビニルアルコール系樹脂、ポリウレタン系樹脂、ポリチオフェン系樹脂、ポリオキシエチレン基含有ポリマー、およびオキサゾリン基含有ポリマーから選ばれるいずれ少なくとも1つを用いることができる。これらのなかでも、第2の保護フィルムと粘着剤層との間にアンカーコート層を形成する場合には、保護フィルムに対する塗膜形成性や濡れ性の観点から前記水系樹脂としては、ポリウレタン系樹脂、オキサゾリン基含有ポリマーが好ましい。
The anchor coat layer may contain an aqueous resin. The anchor coat layer can be formed by applying a coating solution for forming an anchor layer (for example, an aqueous resin composition containing an aqueous resin) to the protective film. As the water-based resin, for example, at least one selected from polyvinyl alcohol-based resins, polyurethane-based resins, polythiophene-based resins, polyoxyethylene group-containing polymers, and oxazoline group-containing polymers can be used. Among these, when the anchor coat layer is formed between the second protective film and the pressure-sensitive adhesive layer, the water-based resin is a polyurethane-based resin from the viewpoint of coating film forming property and wettability with respect to the protective film. Polymers containing oxazoline groups are preferred.
本発明の一実施形態において、上記機能性コーティング層は、オキサゾリン基含有ポリマーを含有し得る。
In an embodiment of the present invention, the functional coating layer may contain an oxazoline group-containing polymer.
本発明の一実施形態において、アンカーコート層は、偏光フィルムと粘着剤との間、すなわち第2の保護フィルムと粘着剤層との間に配され、アンカーコート層形成用塗布液は、ポリチオフェン系ポリマーと、ポリオキシアルキレン基含有ポリマーと、水65~100重量%とアルコール0~35重量%とを含む混合溶媒とを含有するものであってよい。
In one embodiment of the present invention, the anchor coat layer is disposed between the polarizing film and the pressure-sensitive adhesive, that is, between the second protective film and the pressure-sensitive adhesive layer, and the anchor coat layer-forming coating liquid is a polythiophene-based coating liquid. It may contain a polymer, a polyoxyalkylene group-containing polymer, and a mixed solvent containing 65 to 100% by weight of water and 0 to 35% by weight of alcohol.
アルコールとしては、常温(25℃)において、親水性のもの、特に水と任意の割合で混合可能なものが好ましい。このようなアルコールとしては、炭素数1~6のアルコールが好ましい。さらには炭素数1~4のアルコールが好ましく、さらには炭素数1~3のアルコールが好ましい。このようなアルコールの具体例としては、たとえば、メタノール、エタノール、n‐プロパノール、イソプロピルアルコール、n‐ブタノール、イソブタノール、sec‐ブタノール、tert‐ブタノール、n-アミルアルコール、イソアミルアルコール、sec-アミルアルコール、tert-アミルアルコール、1-エチル-1-プロパノール、2-メチル-1-ブタノール、n-ヘキサノール、及びシクロヘキサノール等があげられる。これらのなかでも、エタノール、イソプロピルアルコールが好ましく、より好ましくはイソプロピルアルコールである。アルコールは、1種を単独で、または2種以上を混合して用いることができる。2種以上のアルコールは任意の割合で混合することができる。例えば、エタノールとイソプロパノールを任意の割合で混合した混合アルコールを使用することができる。
The alcohol is preferably hydrophilic at room temperature (25°C), and particularly preferably alcohol that can be mixed with water at an arbitrary ratio. As such an alcohol, an alcohol having 1 to 6 carbon atoms is preferable. Further, an alcohol having 1 to 4 carbon atoms is preferable, and an alcohol having 1 to 3 carbon atoms is more preferable. Specific examples of such alcohols include, for example, methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol. , Tert-amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol and the like. Among these, ethanol and isopropyl alcohol are preferable, and isopropyl alcohol is more preferable. The alcohols may be used alone or in combination of two or more. Two or more alcohols can be mixed in any ratio. For example, a mixed alcohol in which ethanol and isopropanol are mixed at an arbitrary ratio can be used.
ポリチオフェン系ポリマーとしては、各種形態のもの用いることができるが、水溶性または水分散性のものを好適に用いることができる。ポリチオフェン系ポリマーのポリスチレン換算による重量平均分子量は400000以下であることが好ましく、さらに好ましくは300000以下である。重量平均分子量が前記値を超える場合には前記水溶性または水分散性を満たさなくなる傾向にあり、そのようなポリマーを用いて塗布液を調製した場合には、当該塗布液中にポリマーの固形分が残存し、あるいは高粘度化して膜厚の均一なアンカー層を形成することが困難になる傾向にある。
As the polythiophene-based polymer, various forms can be used, but water-soluble or water-dispersible ones can be preferably used. The polystyrene-equivalent weight average molecular weight of the polythiophene-based polymer is preferably 400000 or less, and more preferably 300000 or less. When the weight average molecular weight exceeds the above value, there is a tendency that the water solubility or water dispersibility is not satisfied, and when a coating solution is prepared using such a polymer, the solid content of the polymer in the coating solution is Tend to remain, or it becomes difficult to form an anchor layer having a uniform film thickness due to high viscosity.
前記水溶性とは、水100gに対する溶解度が5g以上の場合をいう。前記水溶性ポリチオフェン系ポリマーの水100gに対する溶解度は20~30gであることが好ましい。水分散性ポリチオフェン系ポリマーは、ポリチオフェン系ポリマーが微粒子状で水中に分散しているものであり、水分散液は液粘度が小さく薄膜塗工が容易であるばかりか、塗布層の均一性に優れている。ここで微粒子のサイズとしては1μm以下のものがアンカー層の均一性という点から好ましい。
“Water-soluble” refers to the case where the solubility in 100 g of water is 5 g or more. The solubility of the water-soluble polythiophene polymer in 100 g of water is preferably 20 to 30 g. The water-dispersible polythiophene-based polymer is a polythiophene-based polymer in the form of fine particles dispersed in water.The water dispersion has a small liquid viscosity and is easy to apply in a thin film, and also has excellent coating layer uniformity. ing. Here, the size of the fine particles is preferably 1 μm or less from the viewpoint of the uniformity of the anchor layer.
また、前記水溶性または水分散性のポリチオフェン系ポリマーは、分子中に親水性官能基を有することが好ましい。親水性官能基としては、例えばスルホン基、アミノ基、アミド基、イミノ基、四級アンモニウム塩基、ヒドロキシル基、メルカプト基、ヒドラジノ基、カルボキシル基、硫酸エステル基、リン酸エステル基、またはそれらの塩などがあげられる。分子内に親水性官能基を有することにより水に溶けやすくなったり、水に微粒子状で分散しやすくなり、前記水溶性または水分散性のポリチオフェン系ポリマーを容易に調製することができる。
The water-soluble or water-dispersible polythiophene polymer preferably has a hydrophilic functional group in the molecule. Examples of the hydrophilic functional group include a sulfone group, an amino group, an amide group, an imino group, a quaternary ammonium salt group, a hydroxyl group, a mercapto group, a hydrazino group, a carboxyl group, a sulfate ester group, a phosphate ester group, or a salt thereof. Etc. By having a hydrophilic functional group in the molecule, it becomes easy to dissolve in water or easily dispersed in water in the form of fine particles, and thus the water-soluble or water-dispersible polythiophene polymer can be easily prepared.
前記水溶性または水分散性のポリチオフェン系ポリマーとしては、ナガセケムテックス社製のデナトロンシリーズなどがあげられる。
Examples of the water-soluble or water-dispersible polythiophene-based polymer include Denatron series manufactured by Nagase Chemtex.
混合溶媒の水/アルコールをかかる比率とし、バインダー成分として導電性を有するポリチオフェン系ポリマーを使用することにより、アンカー層形成用塗布液中のポリチオフェン系ポリマーの分散性がより高まる。その結果、アンカー層形成用塗布液を塗布・乾燥後に得られるアンカー層の導電性能がより向上する。また、混合溶媒の水/アルコールをかかる比率とすることで、バインダー成分のpH値が低くなっても、その液安定性を維持できるため、アンカー層中の異物発生が抑制できる。加えて、水リッチ混合溶媒を使用した場合、アンカー層のソルベントクラックをより効果的に防止することができる。特にアンカー層の導電性能を向上する観点からは、水80~100重量%およびアルコール0~20重量%を含む混合溶媒を使用することが好ましい。
By using water/alcohol as a mixed solvent at such a ratio and using a conductive polythiophene-based polymer as a binder component, the dispersibility of the polythiophene-based polymer in the anchor layer-forming coating liquid is further enhanced. As a result, the conductivity of the anchor layer obtained after coating and drying the anchor layer-forming coating liquid is further improved. Further, by setting the mixed solvent of water/alcohol at such a ratio, even if the pH value of the binder component becomes low, the liquid stability thereof can be maintained, so that the generation of foreign matter in the anchor layer can be suppressed. In addition, when a water-rich mixed solvent is used, solvent cracks in the anchor layer can be more effectively prevented. In particular, from the viewpoint of improving the conductive performance of the anchor layer, it is preferable to use a mixed solvent containing 80 to 100% by weight of water and 0 to 20% by weight of alcohol.
アンカー層の導電性能を向上する観点から、アンカー層形成用塗布液中のポリチオフェン系ポリマーの含有量は、0.005~5重量%であることが好ましく、0.01~3重量%であることがより好ましく、0.01~1重量%であることがさらに好ましく、0.01~0.5重量%であることが最も好ましい。
From the viewpoint of improving the conductive performance of the anchor layer, the content of the polythiophene-based polymer in the anchor layer-forming coating liquid is preferably 0.005 to 5% by weight, and 0.01 to 3% by weight. Is more preferable, 0.01 to 1% by weight is further preferable, and 0.01 to 0.5% by weight is most preferable.
本発明では、アンカー層形成用塗布液中に、前記混合溶媒およびポリチオフェン系ポリマーと共に、ポリオキシアルキレン基含有ポリマーを含有する。ポリオキシアルキレン基含有ポリマーとしては、例えば主鎖がポリ(メタ)アクリレート重合体であって、側鎖にポリオキシエチレン基やポリオキシプロピレン基などのポリオキシアルキレン基を含有する、ポリオキシアルキレン基含有ポリ(メタ)アクリレートなどが挙げられる。アンカー層と光学フィルムとの濡れ性を考慮した場合、アンカー層形成用塗布液中のポリオキシアルキレン基含有ポリマーの含有量は、0.005~5重量%であることが好ましく、0.01~3重量%であることがより好ましく、0.01~1重量%であることがさらに好ましく、0.01~0.5重量%であることが最も好ましい。
In the present invention, the polyoxyalkylene group-containing polymer is contained in the anchor layer forming coating solution together with the mixed solvent and the polythiophene-based polymer. As the polyoxyalkylene group-containing polymer, for example, a polyoxyalkylene group whose main chain is a poly(meth)acrylate polymer and whose side chain contains a polyoxyalkylene group such as a polyoxyethylene group or a polyoxypropylene group Examples include contained poly(meth)acrylates. In consideration of the wettability between the anchor layer and the optical film, the content of the polyoxyalkylene group-containing polymer in the anchor layer-forming coating liquid is preferably 0.005 to 5% by weight, and 0.01 to 5% by weight. The amount is more preferably 3% by weight, further preferably 0.01 to 1% by weight, and most preferably 0.01 to 0.5% by weight.
本発明に係るアンカー層形成用塗布液においては、ポリチオフェン系ポリマーおよびポリオキシアルキレン基含有ポリマーに加えて、投錨性および光学フィルムと粘着剤層との密着性を向上するために、バインダー成分を含有しても良い。バインダー成分としては、粘着剤の投錨力を向上する観点からは、例えば、水溶性または水分散性ポリウレタン樹脂系バインダーなどのポリウレタン樹脂系バインダー、エポキシ樹脂系バインダー、イソシアネート樹脂系バインダー、ポリエステル樹脂系バインダー、分子中にアミノ基を含むポリマー類、オキサゾリン基などを含有する各種アクリル樹脂系バインダーなどの有機反応性基を有する樹脂(ポリマー)を用いることができる。特にバインダー成分としてポリウレタン樹脂系バインダーを含有する場合、該アンカー層形成用塗布液から得られるアンカー層を介して、光学フィルムと粘着剤層との密着性が向上するため好ましい。アンカー層形成用塗布液中のバインダー樹脂の含有量は、0.005~5重量%であることが好ましく、0.01~3重量%であることがより好ましく、0.01~1重量%であることがさらに好ましく、0.01~0.5重量%であることが最も好ましい。
In the anchor layer-forming coating liquid according to the present invention, in addition to the polythiophene-based polymer and the polyoxyalkylene group-containing polymer, in order to improve the anchoring property and the adhesion between the optical film and the pressure-sensitive adhesive layer, a binder component is contained. You may. As the binder component, from the viewpoint of improving the anchoring force of the pressure-sensitive adhesive, for example, a polyurethane resin binder such as a water-soluble or water-dispersible polyurethane resin binder, an epoxy resin binder, an isocyanate resin binder, a polyester resin binder. Resins (polymers) having organic reactive groups such as polymers containing an amino group in the molecule and various acrylic resin binders containing an oxazoline group can be used. In particular, when a polyurethane resin binder is contained as a binder component, the adhesion between the optical film and the pressure-sensitive adhesive layer is improved through the anchor layer obtained from the anchor layer-forming coating liquid, which is preferable. The content of the binder resin in the anchor layer-forming coating liquid is preferably 0.005 to 5% by weight, more preferably 0.01 to 3% by weight, and 0.01 to 1% by weight. It is more preferable that the amount is 0.01 to 0.5% by weight.
水溶性または水分散性ポリウレタン樹脂系バインダーなどの前記ポリウレタン樹脂系バインダーを使用した場合、特に光学フィルムと粘着剤層との密着性が向上するため好ましい。一方、ポリウレタン樹脂系バインダーを使用した場合、シュウ酸の発生などでアンカー層形成用塗布液中のpH値が低下すると、ポリウレタン樹脂に起因した異物発生量が増大する傾向にある。しかしながら、本願発明ではアンカー層形成用塗布液の混合溶媒中の水およびアルコールの比率を特定の割合とすることで、異物の発生を抑制することができる。
It is preferable to use the above-mentioned polyurethane resin-based binder such as a water-soluble or water-dispersible polyurethane resin-based binder because the adhesion between the optical film and the pressure-sensitive adhesive layer is improved. On the other hand, when a polyurethane resin-based binder is used, if the pH value in the anchor layer-forming coating liquid decreases due to the generation of oxalic acid, the amount of foreign matter generated due to the polyurethane resin tends to increase. However, in the present invention, generation of foreign matter can be suppressed by setting the ratio of water and alcohol in the mixed solvent of the anchor layer forming coating liquid to a specific ratio.
また、アンカー層形成用塗布液中に、水およびアルコール以外の成分、例えば、アンモニアの割合が多くなると、高熱、高湿度環境下において、例えば、光学フィルムとして偏光フィルムを用いる場合、偏光フィルムの偏光特性が変化し、これにより、光学特性に影響を及ぼし、高熱、高湿度環境下における高耐久性を満足できなくなる場合がある。したがって、アンカー層形成用塗布液中の混合溶媒(バインダー樹脂の希釈溶媒)は、水およびアルコールを主成分とすること、具体的には混合溶媒中の水およびアルコールの合計量が90重量%以上であることが好ましい。より好ましくは、混合溶媒中の水およびアルコールの合計量が95重量%以上であり、さらに好ましくは、混合溶媒中の水およびアルコールの合計量が99重量%以上であり、最も好ましくは、混合溶媒中の水およびアルコールが実質的に100重量%である。
In the anchor layer-forming coating liquid, components other than water and alcohol, for example, when the proportion of ammonia is high, under high heat and high humidity environment, for example, when using a polarizing film as an optical film, the polarization of the polarizing film. The characteristics may change, which may affect the optical characteristics and make it impossible to satisfy the high durability in a high heat and high humidity environment. Therefore, the mixed solvent (diluting solvent for the binder resin) in the anchor layer-forming coating liquid contains water and alcohol as main components, and specifically, the total amount of water and alcohol in the mixed solvent is 90% by weight or more. Is preferred. More preferably, the total amount of water and alcohol in the mixed solvent is 95% by weight or more, further preferably, the total amount of water and alcohol in the mixed solvent is 99% by weight or more, and most preferably, the mixed solvent. The water and alcohol therein is substantially 100% by weight.
なお、アンカー層形成用塗布液中にアンモニアを含有する場合、アンカー層の塗布外観性や光学信頼性に優れる場合はあるが、耐久性やソルベントクラック防止の観点からはアンモニアを含有量ができるだけ少ないことが好ましい。具体的には、アンカー層形成用塗布液中のアンモニアの含有量は、バインダー樹脂(固形分)100重量部に対して、0.05重量部未満が好ましく、0.03重量部未満であることがより好ましい。
When the coating liquid for forming the anchor layer contains ammonia, the coating appearance and optical reliability of the anchor layer may be excellent, but the content of ammonia is as small as possible from the viewpoint of durability and prevention of solvent cracks. Preferably. Specifically, the content of ammonia in the anchor layer-forming coating liquid is preferably less than 0.05 parts by weight, and less than 0.03 parts by weight, based on 100 parts by weight of the binder resin (solid content). Is more preferable.
アンカー層形成用塗布液には、必要に応じて、添加剤を配合することができる。添加剤としては、レベリング剤、消泡剤、増粘剤、酸化防止剤などが挙げられる。これら添加剤のなかでも、レベリング剤(例えば、アセチレン骨格を有するものなど)が好ましい。これら添加剤の割合は、通常、バインダー樹脂(固形分)100重量部に対して、0.01~500重量部程度が好ましく、0.1~300重量部がより好ましく、1~100重量部がさらに好ましい。
If necessary, the anchor layer forming coating liquid may contain additives. Examples of the additive include a leveling agent, a defoaming agent, a thickener, an antioxidant and the like. Among these additives, a leveling agent (for example, one having an acetylene skeleton) is preferable. The ratio of these additives is usually about 0.01 to 500 parts by weight, preferably 0.1 to 300 parts by weight, and more preferably 1 to 100 parts by weight, relative to 100 parts by weight of the binder resin (solid content). More preferable.
ポリウレタン系樹脂としては、ポリウレタン系樹脂のエマルションを用いることができる。また、ポリウレタンの樹脂エマルションとしては、乳化剤を用いず、自己乳化したものを用いることができる。
As the polyurethane resin, an emulsion of polyurethane resin can be used. Further, as the polyurethane resin emulsion, a self-emulsified one can be used without using an emulsifier.
ポリウレタン系樹脂としては、例えば、高分子ポリオールとイソシアネート化合物の重付加反応により得られる一液型のものを用いることができる。前記一液型のポリウレタン系樹脂としては、例えば、ポリエーテル系ポリウレタン樹脂、ポリエステル系ポリウレタン樹脂等を用いることができる。前記ポリウレタン系樹脂としては、水酸基が残存しているものが好ましい。具体的には、例えば、ラッカータイプのポリウレタン系樹脂が挙げられる。前記ポリウレタン系樹脂は溶剤や水を乾燥除去させるだけで皮膜形成できる。
As the polyurethane resin, for example, a one-pack type resin obtained by a polyaddition reaction of a polymer polyol and an isocyanate compound can be used. As the one-pack type polyurethane resin, for example, a polyether polyurethane resin, a polyester polyurethane resin or the like can be used. The polyurethane-based resin is preferably one in which a hydroxyl group remains. Specifically, for example, a lacquer type polyurethane resin can be used. The polyurethane resin can be formed into a film by simply removing the solvent and water by drying.
ポリエーテル系ポリウレタン樹脂は、一般にポリエーテルポリオールとイソシアネート化合物の重付加反応により得られる。ポリエーテルポリオールは、多価アルコールの1種または2種以上にアルキレンオキサイドを開環重合により付加して得られるものである。ポリエステル系ポリウレタン樹脂は、一般にポリエステルポリオールとイソシアネート化合物の重付加反応により得られる。ポリエステルルポリオールは、多価アルコールと多塩基酸を重縮合して得られるものである。また、ポリエーテルポリオールまたはポリエーテルポリオール等の高分子ポリオールは、数平均分子量が400~3000であるのが好ましく、500~2000であるのがより好ましい。ポリエーテルポリオール、ポリエステルポリオール等の高分子ポリオールは1種を単独に用いてもよく、2種以上を使用した共重合体でもよい。
Polyether polyurethane resin is generally obtained by polyaddition reaction of polyether polyol and isocyanate compound. The polyether polyol is obtained by adding an alkylene oxide to one or more polyhydric alcohols by ring-opening polymerization. The polyester-based polyurethane resin is generally obtained by a polyaddition reaction between a polyester polyol and an isocyanate compound. Polyester polyol is obtained by polycondensing a polyhydric alcohol and a polybasic acid. The high molecular weight polyol such as polyether polyol or polyether polyol preferably has a number average molecular weight of 400 to 3,000, more preferably 500 to 2,000. Polymer polyols such as polyether polyols and polyester polyols may be used alone or as a copolymer using two or more kinds.
イソシアネート化合物としては、通常、ポリウレタンに使用されている芳香族、芳香脂肪族、脂肪族、または脂環族等のイソシアネートが適宜使用できる。また、イソシアネート化合物として、上記イソシアネート化合物のアダクト体、二量体、三量体、およびこれらの重合体等を使用してもよい。さらに、イソシアネート化合物は、上記イソシアネートの一部をウレタン化、ウレチジオン化、カルボジイミド化等した変性イソシアネートも使用可能である。
As the isocyanate compound, an aromatic, araliphatic, aliphatic, or alicyclic isocyanate usually used in polyurethane can be appropriately used. Further, as the isocyanate compound, an adduct, a dimer, a trimer of the above isocyanate compound, a polymer thereof, or the like may be used. Further, as the isocyanate compound, a modified isocyanate obtained by urethanizing, uretidione-forming, carbodiimidizing a part of the above-mentioned isocyanate can also be used.
前記ポリウレタン系樹脂を水に分散する場合は、当該樹脂を、乳化剤を用いて強制的に乳化分散して調整する方法が知られている。また前記樹脂中に、水分散性親水基のアニオン基、カチオン基またはノニオン基を導入して自己乳化物としたもの等を用いることができる。またイオン高分子錯体を用いることができる。
When dispersing the polyurethane resin in water, a method is known in which the resin is forcibly emulsified and dispersed using an emulsifier. In addition, a self-emulsified product obtained by introducing an anion group, a cation group or a nonion group of a water-dispersible hydrophilic group into the resin can be used. Further, an ionic polymer complex can be used.
ポリウレタンの樹脂エマルションとしては、乳化剤を用いず、自己乳化した、旭電化工業株式会社製のアデカボンタイターHUXシリーズ等を例示できる。また、水系ウレタン樹脂の具体例として,第一工業製薬社製のスーパーフレックスシリーズ、三井化学ポリウレタン(株)製のタケラックW-6020等が挙げられる。
Examples of the polyurethane resin emulsion include the Adeka Bontiter HUX series manufactured by Asahi Denka Kogyo Co., Ltd., which is self-emulsified without using an emulsifier. In addition, specific examples of the water-based urethane resin include Superflex series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Takelac W-6020 manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., and the like.
オキサゾリン基含有ポリマーとしては、例えば、アクリル骨格またはスチレン骨格からなる主鎖を含み、その主鎖の側鎖にオキサゾリン基を有するポリマーが挙げられる。前記のなかでもアクリル骨格からなる主鎖を含み、その主鎖の側鎖にオキサゾリン基を有しているオキサゾリン基含有アクリル系ポリマーが好ましい。
Examples of the oxazoline group-containing polymer include a polymer having a main chain composed of an acrylic skeleton or a styrene skeleton and having an oxazoline group on the side chain of the main chain. Among these, an oxazoline group-containing acrylic polymer having a main chain composed of an acrylic skeleton and having an oxazoline group on the side chain of the main chain is preferable.
オキサゾリン基としては、例えば、2-オキサゾリン基、3-オキサゾリン基、4-オキサゾリン基などが挙げられ、これらの中でも、2-オキサゾリン基が好ましい。2-オキサゾリン基としては、一般に、下記一般式で表される。
Examples of the oxazoline group include a 2-oxazoline group, a 3-oxazoline group, a 4-oxazoline group and the like, and among these, the 2-oxazoline group is preferable. The 2-oxazoline group is generally represented by the following general formula.
また、前記オキサゾリン基含有ポリマーは、オキサゾリン基以外に、ポリオキシアルキレン基を有していてもよい。
The oxazoline group-containing polymer may have a polyoxyalkylene group in addition to the oxazoline group.
オキサゾリン基含有ポリマーは、その数平均分子量が5,000以上であることが好ましく、10,000以上であることがより好ましく、通常、1,000,000以下が好ましい。数平均分子量が5,000より低いと、アンカー層の強度が不足して凝集破壊を起こし、投錨力を向上できない場合がある。数平均分子量が1,000,000より高いと、作業性に劣る場合がある。また、オキサゾリン基含有ポリマーは、そのオキサゾリン価が、例えば、1,500gsolid/eq.以下であることが好ましく、1,200g solid/eq.以下であることがより好ましい。オキサゾリン価が1,500g solid/eq.より大きいと、分子中に含まれるオキサゾリン基の量が少なくなり、投錨力を向上できない場合がある。
The number-average molecular weight of the oxazoline group-containing polymer is preferably 5,000 or more, more preferably 10,000 or more, and usually 1,000,000 or less. If the number average molecular weight is lower than 5,000, the strength of the anchor layer may be insufficient to cause cohesive failure and the anchoring force may not be improved. When the number average molecular weight is higher than 1,000,000, workability may be poor. Further, the oxazoline group-containing polymer has an oxazoline value of, for example, 1,500 g solid/eq. It is preferably not more than 1,200 g solid/eq. The following is more preferable. Oxazoline value is 1,500 g solid/eq. If it is larger, the amount of the oxazoline group contained in the molecule becomes small, and the anchoring force may not be improved in some cases.
オキサゾリン基含有ポリマーは、オキサゾリン基が、粘着剤組成物に含まれているヒドロキシル基と比較的低温で反応するため、オキサゾリン基含有ポリマーをアンカーコート層に含ませれば、粘着剤層中の官能基などと反応し、強固に密着することができる。
Since the oxazoline group-containing polymer reacts with the hydroxyl group contained in the pressure-sensitive adhesive composition at a relatively low temperature, if the oxazoline group-containing polymer is contained in the anchor coat layer, the functional group in the pressure-sensitive adhesive layer is reduced. It reacts with the like and can firmly adhere.
オキサゾリン基含有ポリマーとしては、具体的には、(株)日本触媒製のエポクロスWS-300、エポクロスWS-500、エポクロスWS-700などのオキサゾリン基含有アクリル系ポリマー、例えば、(株)日本触媒製のエポクロスK-1000シリーズ、エポクロスK-2000シリーズなどのオキサゾリン基含有アクリル/スチレン系ポリマーなどが挙げられ、1種単独で、又は、2種以上を併用して用いることができる。
Specific examples of the oxazoline group-containing polymer include oxazoline group-containing acrylic polymers such as Epocros WS-300, Epocros WS-500, and Epocros WS-700 manufactured by Nippon Shokubai Co., Ltd., for example, manufactured by Nippon Shokubai Co., Ltd. The oxazoline group-containing acrylic/styrene-based polymers such as Epocros K-1000 series and Epocros K-2000 series can be used, and they can be used alone or in combination of two or more.
アンカーコート層の厚さは0.05μmであるのが好ましく、さらには0.2μm以上であるのが好ましく、前記アンカーコート層の厚さは0.5μm以上であるのが好ましく、さらには0.7μm以上であるのが好ましい。アンカーコート層が厚くなりすぎると光学信頼性と耐水性が低下するため、アンカーコート層の厚さは6μm以下であるのが好ましく、さらには5μm以下、さらには3μm以下、さらには2μm以下であるのが好ましい。
The thickness of the anchor coat layer is preferably 0.05 μm, more preferably 0.2 μm or more, and the thickness of the anchor coat layer is preferably 0.5 μm or more, more preferably 0.1 μm or more. It is preferably 7 μm or more. If the anchor coat layer becomes too thick, the optical reliability and water resistance will decrease, so the thickness of the anchor coat layer is preferably 6 μm or less, more preferably 5 μm or less, further 3 μm or less, and further 2 μm or less. Is preferred.
前記アンカーコート層は、前記水系樹脂組成物を、保護フィルムに塗布して乾燥することにより形成することができる。前記水系樹脂組成物の塗布は、乾燥後の厚み(好ましくは0.2μm以上6μm以下)になるように行なう。塗布操作は特に制限されず、任意の適切な方法を採用することができる。例えば、ロールコート法、スピンコート法、ワイヤーバーコート法、ディップコート法、ダイコート法、カーテンコート法、スプレーコート法、ナイフコート法(コンマコート法等)等各種手段を採用できる。
The anchor coat layer can be formed by applying the water-based resin composition to a protective film and drying. The aqueous resin composition is applied so as to have a thickness after drying (preferably 0.2 μm or more and 6 μm or less). The coating operation is not particularly limited, and any appropriate method can be adopted. For example, various methods such as a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method and a knife coating method (comma coating method) can be adopted.
<粘着剤層>
本発明において用いられる粘着剤層は、ベースポリマーと、シリコーンオリゴマーPsとを含む。 <Adhesive layer>
The pressure-sensitive adhesive layer used in the present invention contains a base polymer and a silicone oligomer Ps.
本発明において用いられる粘着剤層は、ベースポリマーと、シリコーンオリゴマーPsとを含む。 <Adhesive layer>
The pressure-sensitive adhesive layer used in the present invention contains a base polymer and a silicone oligomer Ps.
本発明において用いられる粘着剤層を構成する粘着剤は、特に限定されず、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、ビニルアルキルエーテル系粘着剤、ポリビニルアルコール系粘着剤、ポリビニルピロリドン系粘着剤、ポリアクリルアミド系粘着剤、セルロース系粘着剤などを用いることができる。使用される粘着剤に応じて各種のベースポリマーを用いることができる。
The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer used in the present invention is not particularly limited, and it is a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a vinyl alkyl ether-based pressure-sensitive adhesive, a polyvinyl alcohol-based pressure-sensitive adhesive. Adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives and the like can be used. Various base polymers can be used depending on the adhesive used.
上記の粘着剤の中でも、光学的透明性に優れ、適宜な濡れ性と凝集性と接着性の粘着特性を示して、耐候性や耐熱性などに優れるものが好ましく使用される。このような特徴を示すものとしてアクリル系粘着剤が好ましく使用される。アクリル系粘着剤のベースポリマーとしては(メタ)アクリル系ポリマーが用いられる。なお、(メタ)アクリレートはアクリレートおよび/またはメタクリレートを含む。
Among the above-mentioned pressure-sensitive adhesives, those having excellent optical transparency, exhibiting appropriate wettability, cohesiveness and adhesiveness, and excellent weather resistance and heat resistance are preferably used. Acrylic pressure-sensitive adhesives are preferably used as those exhibiting such characteristics. A (meth)acrylic polymer is used as the base polymer of the acrylic pressure-sensitive adhesive. The (meth)acrylate contains acrylate and/or methacrylate.
<ベースポリマー>
本発明において、ベースポリマーとしては通常、(メタ)アクリル系ポリマーが用いられる。 <Base polymer>
In the present invention, a (meth)acrylic polymer is usually used as the base polymer.
本発明において、ベースポリマーとしては通常、(メタ)アクリル系ポリマーが用いられる。 <Base polymer>
In the present invention, a (meth)acrylic polymer is usually used as the base polymer.
(1)アルキル(メタ)アクリレート(A)
(メタ)アクリル系ポリマーは、通常、モノマー単位として、アルキル(メタ)アクリレートを主成分として含有する。(メタ)アクリル系ポリマーの主骨格を構成する、アルキル(メタ)アクリレート(A)としては、直鎖状または分岐鎖状のC1~C20の(メタ)アクリル酸アルキルエステルを用いることができる。C1~C20の(メタ)アクリル酸アルキルエステルとしては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸s-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸イソペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸ウンデシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸トリデシル、(メタ)アクリル酸テトラデシル、(メタ)アクリル酸ペンタデシル、(メタ)アクリル酸ヘキサデシル、(メタ)アクリル酸ヘプタデシル、(メタ)アクリル酸オクタデシル、(メタ)アクリル酸イソオクタデシル、(メタ)アクリル酸ノナデシル、(メタ)アクリル酸エイコシル等が挙げられるが、これらに限定されない。これらの(メタ)アクリル酸アルキルエステルは単独であるいは組み合わせて使用することができる。 (1) Alkyl (meth)acrylate (A)
The (meth)acrylic polymer usually contains, as a monomer unit, an alkyl (meth)acrylate as a main component. As the alkyl (meth)acrylate (A) constituting the main skeleton of the (meth)acrylic polymer, a linear or branched C1 to C20 (meth)acrylic acid alkyl ester can be used. Examples of the C1 to C20 (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. , N-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, ( Hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, Decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, ( Examples include, but are not limited to, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, isooctadecyl (meth)acrylate, nonadecyl (meth)acrylate, and eicosyl (meth)acrylate. Not done. These (meth)acrylic acid alkyl esters can be used alone or in combination.
(メタ)アクリル系ポリマーは、通常、モノマー単位として、アルキル(メタ)アクリレートを主成分として含有する。(メタ)アクリル系ポリマーの主骨格を構成する、アルキル(メタ)アクリレート(A)としては、直鎖状または分岐鎖状のC1~C20の(メタ)アクリル酸アルキルエステルを用いることができる。C1~C20の(メタ)アクリル酸アルキルエステルとしては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸s-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸イソペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸ウンデシル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸トリデシル、(メタ)アクリル酸テトラデシル、(メタ)アクリル酸ペンタデシル、(メタ)アクリル酸ヘキサデシル、(メタ)アクリル酸ヘプタデシル、(メタ)アクリル酸オクタデシル、(メタ)アクリル酸イソオクタデシル、(メタ)アクリル酸ノナデシル、(メタ)アクリル酸エイコシル等が挙げられるが、これらに限定されない。これらの(メタ)アクリル酸アルキルエステルは単独であるいは組み合わせて使用することができる。 (1) Alkyl (meth)acrylate (A)
The (meth)acrylic polymer usually contains, as a monomer unit, an alkyl (meth)acrylate as a main component. As the alkyl (meth)acrylate (A) constituting the main skeleton of the (meth)acrylic polymer, a linear or branched C1 to C20 (meth)acrylic acid alkyl ester can be used. Examples of the C1 to C20 (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. , N-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, ( Hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, Decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, ( Examples include, but are not limited to, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, isooctadecyl (meth)acrylate, nonadecyl (meth)acrylate, and eicosyl (meth)acrylate. Not done. These (meth)acrylic acid alkyl esters can be used alone or in combination.
本発明の一実施形態において、(メタ)アクリル系ポリマーは、好ましくは、アクリル酸n-ブチル(BA)およびアクリル酸2-エチルヘキシル(2EHA)の一方または両方をモノマー単位として含み得る。(メタ)アクリル系ポリマーのモノマー単位として好ましく用いられ得る他の(メタ)アクリル酸アルキルエステルの例としては、アクリル酸メチル、メタクリル酸メチル(MMA)、メタクリル酸n-ブチル(BMA)、メタクリル酸2-エチルヘキシル(2EHMA)等が挙げられる。
In one embodiment of the present invention, the (meth)acrylic polymer may preferably contain one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA) as a monomer unit. Examples of other (meth)acrylic acid alkyl esters that can be preferably used as the monomer unit of the (meth)acrylic polymer include methyl acrylate, methyl methacrylate (MMA), n-butyl methacrylate (BMA), and methacrylic acid. 2-ethylhexyl (2EHMA) and the like can be mentioned.
本発明の一実施形態において、ベースポリマーのモノマー単位として用いられるアルキル(メタ)アクリレート(A)は、そのホモポリマーのガラス転移温度が-80℃以上0℃以下である。アルキル(メタ)アクリレート(A)のホモポリマーのガラス転移温度は、好ましくは、-70℃~-5℃であり、より好ましくは、-60℃~-10℃である。
In one embodiment of the present invention, the alkyl (meth)acrylate (A) used as a monomer unit of the base polymer has a homopolymer glass transition temperature of −80° C. or higher and 0° C. or lower. The glass transition temperature of the homopolymer of alkyl (meth)acrylate (A) is preferably −70° C. to −5° C., more preferably −60° C. to −10° C.
本発明の一実施形態において、ベースポリマーのモノマー単位として用いられるアルキル(メタ)アクリレート(A)は、ベースポリマーの重量を基準として80重量%以上で含有することができる。アルキル(メタ)アクリレート(A)は、ベースポリマーの重量を基準として、好ましくは85重量%以上であり、より好ましくは90重量%以上である。
In one embodiment of the present invention, the alkyl (meth)acrylate (A) used as a monomer unit of the base polymer can be contained in an amount of 80% by weight or more based on the weight of the base polymer. The alkyl (meth)acrylate (A) is preferably 85% by weight or more, more preferably 90% by weight or more, based on the weight of the base polymer.
本発明の好ましい実施形態において、ベースポリマーのモノマー単位として、ホモポリマーのガラス転移温度が-80℃以上0℃以下であるアルキル(メタ)アクリレート(A)を80重量%以上で含有することができる。
In a preferred embodiment of the present invention, 80% by weight or more of an alkyl (meth)acrylate (A) having a glass transition temperature of a homopolymer of −80° C. or higher and 0° C. or lower can be contained as a monomer unit of a base polymer. ..
本発明の一実施形態において、(メタ)アクリル系ポリマーは、主成分としてのアルキル(メタ)アクリレート(A)に加えて、必要に応じて、アルキル(メタ)アクリレートと共重合可能な他のモノマー(共重合性モノマー)を更に含んでいてもよい。共重合性モノマーとしては、極性基(例えば、カルボキシ基、水酸基、窒素原子含有環等)を有するモノマーを好適に使用することができる。極性基を有するモノマーは、アクリル系ポリマーに架橋点を導入したり、(メタ)アクリル系ポリマーの凝集力を高めたりするために役立ち得る。共重合性モノマーは、1種を単独でまたは2種以上を組み合わせて用いることができる。
In one embodiment of the present invention, the (meth)acrylic polymer is, in addition to the alkyl (meth)acrylate (A) as a main component, other monomer that is copolymerizable with the alkyl (meth)acrylate, if necessary. It may further contain (copolymerizable monomer). As the copolymerizable monomer, a monomer having a polar group (for example, a carboxy group, a hydroxyl group, a nitrogen atom-containing ring, etc.) can be preferably used. The monomer having a polar group can be useful for introducing a cross-linking point in the acrylic polymer and for enhancing the cohesive force of the (meth)acrylic polymer. The copolymerizable monomer may be used alone or in combination of two or more.
共重合性モノマーの非限定的な具体例としては、カルボキシ基含有モノマー、酸無水物基含有モノマー、水酸基含有モノマー、スルホン酸基またはリン酸基を含有するモノマー、エポキシ基含有モノマー、シアノ基含有モノマー、イソシアネート基含有モノマー、アミド基含有モノマー、窒素原子含有環を有するモノマー、スクシンイミド骨格を有するモノマー、マレイミド類、イタコンイミド類、(メタ)アクリル酸アミノアルキル類、(メタ)アクリル酸アルコキシアルキル類、ビニルエステル類、ビニルエーテル類、芳香族ビニル化合物、オレフィン類、脂環式炭化水素基を有する(メタ)アクリル酸エステル、芳香族炭化水素基を有する(メタ)アクリル酸エステル、その他、(メタ)アクリル酸テトラヒドロフルフリル等の複素環含有(メタ)アクリレート、塩化ビニルやフッ素原子含有(メタ)アクリレート等のハロゲン原子含有(メタ)アクリレート、シリコーン(メタ)アクリレート等のケイ素原子含有(メタ)アクリレート、テルペン化合物誘導体アルコールから得られる(メタ)アクリル酸エステル等が挙げられる。
Non-limiting specific examples of the copolymerizable monomer include a carboxy group-containing monomer, an acid anhydride group-containing monomer, a hydroxyl group-containing monomer, a sulfonic acid group- or phosphoric acid group-containing monomer, an epoxy group-containing monomer, and a cyano group-containing monomer. Monomers, isocyanate group-containing monomers, amide group-containing monomers, nitrogen atom-containing ring-containing monomers, succinimide skeleton-containing monomers, maleimides, itaconic imides, (meth)acrylic acid aminoalkyls, (meth)acrylic acid alkoxyalkyls, Vinyl esters, vinyl ethers, aromatic vinyl compounds, olefins, (meth)acrylic acid esters having an alicyclic hydrocarbon group, (meth)acrylic acid esters having an aromatic hydrocarbon group, other, (meth)acrylic Heterocycle-containing (meth)acrylates such as acid tetrahydrofurfuryl, halogen atom-containing (meth)acrylates such as vinyl chloride and fluorine atom-containing (meth)acrylate, silicon atom-containing (meth)acrylates such as silicone (meth)acrylate, terpenes Examples thereof include (meth)acrylic acid ester obtained from a compound derivative alcohol.
カルボキシ基含有モノマーとしては、例えば、アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸等が挙げられ;
酸無水物基含有モノマーとしては、例えば、無水マレイン酸、無水イタコン酸が挙げられ;
水酸基含有モノマーとしては、例えば、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸2-ヒドロキシブチル、(メタ)アクリル酸3-ヒドロキシプロピル、(メタ)アクリル酸4-ヒドロキシブチル、(メタ)アクリル酸6-ヒドロキシヘキシル、(メタ)アクリル酸8-ヒドロキシオクチル、(メタ)アクリル酸10-ヒドロキシデシル、(メタ)アクリル酸12-ヒドロキシラウリル、(4-ヒドロキシメチルシクロへキシル)メチル(メタ)アクリレート等の(メタ)アクリル酸ヒドロキシアルキル等が挙げられ;
スルホン酸基またはリン酸基を含有するモノマーとしては、例えば、スチレンスルホン酸、アリルスルホン酸、ビニルスルホン酸ナトリウム、2-(メタ)アクリルアミド-2-メチルプロパンスルホン酸、(メタ)アクリルアミドプロパンスルホン酸、スルホプロピル(メタ)アクリレート、(メタ)アクリロイルオキシナフタレンスルホン酸、2-ヒドロキシエチルアクリロイルホスフェート等が挙げられ;
エポキシ基含有モノマーとしては、例えば、(メタ)アクリル酸グリシジルや(メタ)アクリル酸-2-エチルグリシジルエーテル等のエポキシ基含有アクリレート、アリルグリシジルエーテル、(メタ)アクリル酸グリシジルエーテル等が挙げられ;
シアノ基含有モノマーとしては、例えば、アクリロニトリル、メタクリロニトリル等が挙げられ;
イソシアネート基含有モノマーとしては、例えば、2-イソシアナートエチル(メタ)アクリレート等が挙げられ;
アミド基含有モノマーとしては、例えば、(メタ)アクリルアミド;N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N,N-ジプロピル(メタ)アクリルアミド、N,N-ジイソプロピル(メタ)アクリルアミド、N,N-ジ(n-ブチル)(メタ)アクリルアミド、N,N-ジ(t-ブチル)(メタ)アクリルアミド等のN,N-ジアルキル(メタ)アクリルアミド;N-エチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N-n-ブチル(メタ)アクリルアミド等のN-アルキル(メタ)アクリルアミド;N-ビニルアセトアミド等のN-ビニルカルボン酸アミド類;その他、N,N-ジメチルアミノプロピル(メタ)アクリルアミド、ヒドロキシエチルアクリルアミド、N-メチロール(メタ)アクリルアミド、N-エチロール(メタ)アクリルアミド、N-メチロールプロパン(メタ)アクリルアミド、N-メトキシメチル(メタ)アクリルアミド、N-メトキシエチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド、N-(メタ)アクリロイルモルホリン等が挙げられ;
窒素原子含有環を有するモノマーとしては、例えば、N-ビニル-2-ピロリドン、N-メチルビニルピロリドン、N-ビニルピリジン、N-ビニルピペリドン、N-ビニルピリミジン、N-ビニルピペラジン、N-ビニルピラジン、N-ビニルピロール、N-ビニルイミダゾール、N-ビニルオキサゾール、N-(メタ)アクリロイル-2-ピロリドン、N-(メタ)アクリロイルピペリジン、N-(メタ)アクリロイルピロリジン、N-ビニルモルホリン、N-ビニル-3-モルホリノン、N-ビニル-2-カプロラクタム、N-ビニル-1,3-オキサジン-2-オン、N-ビニル-3,5-モルホリンジオン、N-ビニルピラゾール、N-ビニルイソオキサゾール、N-ビニルチアゾール、N-ビニルイソチアゾール、N-ビニルピリダジン等(例えば、N-ビニル-2-カプロラクタム等のラクタム類)が挙げられ;
スクシンイミド骨格を有するモノマーとしては、例えば、N-(メタ)アクリロイルオキシメチレンスクシンイミド、N-(メタ)アクリロイル-6-オキシヘキサメチレンスクシンイミド、N-(メタ)アクリロイル-8-オキシヘキサメチレンスクシンイミド等が挙げられ;
マレイミド類としては、例えば、N-シクロヘキシルマレイミド、N-イソプロピルマレイミド、N-ラウリルマレイミド、N-フェニルマレイミド等が挙げられ;
イタコンイミド類としては、例えば、N-メチルイタコンイミド、N-エチルイタコンイミド、N-ブチルイタコンイミド、N-オクチルイタコンイミド、N-2-エチルへキシルイタコンイミド、N-シクロへキシルイタコンイミド、N-ラウリルイタコンイミド等が挙げられ;
(メタ)アクリル酸アミノアルキル類としては、例えば、(メタ)アクリル酸アミノエチル、(メタ)アクリル酸N,N-ジメチルアミノエチル、(メタ)アクリル酸N,N-ジエチルアミノエチル、(メタ)アクリル酸t-ブチルアミノエチルが挙げられ;
(メタ)アクリル酸アルコキシアルキル類としては、例えば、(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸エトキシエチル、(メタ)アクリル酸プロポキシエチル、(メタ)アクリル酸ブトキシエチル、(メタ)アクリル酸エトキシプロピル等が挙げられ;
ビニルエステル類としては、例えば、酢酸ビニル、プロピオン酸ビニル等が挙げられ;
ビニルエーテル類としては、例えば、例えば、メチルビニルエーテルやエチルビニルエーテル等のビニルアルキルエーテルが挙げられ;
芳香族ビニル化合物としては、例えば、スチレン、α-メチルスチレン、ビニルトルエン等が挙げられ;
オレフィン類としては、例えば、エチレン、ブタジエン、イソプレン、イソブチレン等が挙げられ;
脂環式炭化水素基を有する(メタ)アクリル酸エステルとしては、例えば、シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート等が挙げられ;
芳香族炭化水素基を有する(メタ)アクリル酸エステルとしては、例えば、フェニル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレート等が挙げられる。 Examples of the carboxy group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like;
Examples of the acid anhydride group-containing monomer include maleic anhydride and itaconic anhydride;
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylate. ) 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4 -Hydroxymethylcyclohexyl)methyl (meth)acrylate and the like hydroxyalkyl (meth)acrylate and the like;
Examples of the monomer having a sulfonic acid group or a phosphoric acid group include styrenesulfonic acid, allylsulfonic acid, sodium vinylsulfonate, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid. , Sulfopropyl (meth)acrylate, (meth)acryloyloxynaphthalene sulfonic acid, 2-hydroxyethyl acryloyl phosphate and the like;
Examples of the epoxy group-containing monomer include epoxy group-containing acrylates such as (meth)acrylic acid glycidyl and (meth)acrylic acid-2-ethylglycidyl ether, allyl glycidyl ether, and (meth)acrylic acid glycidyl ether;
Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
Examples of the isocyanate group-containing monomer include 2-isocyanatoethyl (meth)acrylate and the like;
Examples of the amide group-containing monomer include (meth)acrylamide; N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl( N,N-dialkyl(meth)acrylamides such as (meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl)(meth)acrylamide; N-ethyl (meth ) N-alkyl(meth)acrylamides such as acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, Nn-butyl(meth)acrylamide; N-vinylcarboxylic amides such as N-vinylacetamide Others: N,N-dimethylaminopropyl(meth)acrylamide, hydroxyethylacrylamide, N-methylol(meth)acrylamide, N-ethylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, N-methoxymethyl( (Meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-(meth)acryloylmorpholine and the like;
Examples of the monomer having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, N-vinyl -3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N -Vinylthiazole, N-vinylisothiazole, N-vinylpyridazine and the like (for example, lactams such as N-vinyl-2-caprolactam);
Examples of the monomer having a succinimide skeleton include N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, N-(meth)acryloyl-8-oxyhexamethylenesuccinimide and the like. Given;
Examples of the maleimides include N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide, N-phenyl maleimide and the like;
Examples of itaconimides include N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide, N -Lauryl itaconimide and the like;
Examples of aminoalkyl (meth)acrylates include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and (meth)acrylic. T-butylaminoethyl acid acid;
Examples of the alkoxyalkyl (meth)acrylates include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and (meth)acrylic acid. Ethoxypropyl and the like can be mentioned;
Examples of vinyl esters include vinyl acetate, vinyl propionate and the like;
Examples of vinyl ethers include vinyl alkyl ethers such as methyl vinyl ether and ethyl vinyl ether;
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene and the like;
Examples of olefins include ethylene, butadiene, isoprene, and isobutylene;
Examples of the (meth)acrylic acid ester having an alicyclic hydrocarbon group include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate and the like;
Examples of the (meth)acrylic acid ester having an aromatic hydrocarbon group include phenyl(meth)acrylate, phenoxyethyl(meth)acrylate, and benzyl(meth)acrylate.
酸無水物基含有モノマーとしては、例えば、無水マレイン酸、無水イタコン酸が挙げられ;
水酸基含有モノマーとしては、例えば、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸2-ヒドロキシブチル、(メタ)アクリル酸3-ヒドロキシプロピル、(メタ)アクリル酸4-ヒドロキシブチル、(メタ)アクリル酸6-ヒドロキシヘキシル、(メタ)アクリル酸8-ヒドロキシオクチル、(メタ)アクリル酸10-ヒドロキシデシル、(メタ)アクリル酸12-ヒドロキシラウリル、(4-ヒドロキシメチルシクロへキシル)メチル(メタ)アクリレート等の(メタ)アクリル酸ヒドロキシアルキル等が挙げられ;
スルホン酸基またはリン酸基を含有するモノマーとしては、例えば、スチレンスルホン酸、アリルスルホン酸、ビニルスルホン酸ナトリウム、2-(メタ)アクリルアミド-2-メチルプロパンスルホン酸、(メタ)アクリルアミドプロパンスルホン酸、スルホプロピル(メタ)アクリレート、(メタ)アクリロイルオキシナフタレンスルホン酸、2-ヒドロキシエチルアクリロイルホスフェート等が挙げられ;
エポキシ基含有モノマーとしては、例えば、(メタ)アクリル酸グリシジルや(メタ)アクリル酸-2-エチルグリシジルエーテル等のエポキシ基含有アクリレート、アリルグリシジルエーテル、(メタ)アクリル酸グリシジルエーテル等が挙げられ;
シアノ基含有モノマーとしては、例えば、アクリロニトリル、メタクリロニトリル等が挙げられ;
イソシアネート基含有モノマーとしては、例えば、2-イソシアナートエチル(メタ)アクリレート等が挙げられ;
アミド基含有モノマーとしては、例えば、(メタ)アクリルアミド;N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N,N-ジプロピル(メタ)アクリルアミド、N,N-ジイソプロピル(メタ)アクリルアミド、N,N-ジ(n-ブチル)(メタ)アクリルアミド、N,N-ジ(t-ブチル)(メタ)アクリルアミド等のN,N-ジアルキル(メタ)アクリルアミド;N-エチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N-n-ブチル(メタ)アクリルアミド等のN-アルキル(メタ)アクリルアミド;N-ビニルアセトアミド等のN-ビニルカルボン酸アミド類;その他、N,N-ジメチルアミノプロピル(メタ)アクリルアミド、ヒドロキシエチルアクリルアミド、N-メチロール(メタ)アクリルアミド、N-エチロール(メタ)アクリルアミド、N-メチロールプロパン(メタ)アクリルアミド、N-メトキシメチル(メタ)アクリルアミド、N-メトキシエチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド、N-(メタ)アクリロイルモルホリン等が挙げられ;
窒素原子含有環を有するモノマーとしては、例えば、N-ビニル-2-ピロリドン、N-メチルビニルピロリドン、N-ビニルピリジン、N-ビニルピペリドン、N-ビニルピリミジン、N-ビニルピペラジン、N-ビニルピラジン、N-ビニルピロール、N-ビニルイミダゾール、N-ビニルオキサゾール、N-(メタ)アクリロイル-2-ピロリドン、N-(メタ)アクリロイルピペリジン、N-(メタ)アクリロイルピロリジン、N-ビニルモルホリン、N-ビニル-3-モルホリノン、N-ビニル-2-カプロラクタム、N-ビニル-1,3-オキサジン-2-オン、N-ビニル-3,5-モルホリンジオン、N-ビニルピラゾール、N-ビニルイソオキサゾール、N-ビニルチアゾール、N-ビニルイソチアゾール、N-ビニルピリダジン等(例えば、N-ビニル-2-カプロラクタム等のラクタム類)が挙げられ;
スクシンイミド骨格を有するモノマーとしては、例えば、N-(メタ)アクリロイルオキシメチレンスクシンイミド、N-(メタ)アクリロイル-6-オキシヘキサメチレンスクシンイミド、N-(メタ)アクリロイル-8-オキシヘキサメチレンスクシンイミド等が挙げられ;
マレイミド類としては、例えば、N-シクロヘキシルマレイミド、N-イソプロピルマレイミド、N-ラウリルマレイミド、N-フェニルマレイミド等が挙げられ;
イタコンイミド類としては、例えば、N-メチルイタコンイミド、N-エチルイタコンイミド、N-ブチルイタコンイミド、N-オクチルイタコンイミド、N-2-エチルへキシルイタコンイミド、N-シクロへキシルイタコンイミド、N-ラウリルイタコンイミド等が挙げられ;
(メタ)アクリル酸アミノアルキル類としては、例えば、(メタ)アクリル酸アミノエチル、(メタ)アクリル酸N,N-ジメチルアミノエチル、(メタ)アクリル酸N,N-ジエチルアミノエチル、(メタ)アクリル酸t-ブチルアミノエチルが挙げられ;
(メタ)アクリル酸アルコキシアルキル類としては、例えば、(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸エトキシエチル、(メタ)アクリル酸プロポキシエチル、(メタ)アクリル酸ブトキシエチル、(メタ)アクリル酸エトキシプロピル等が挙げられ;
ビニルエステル類としては、例えば、酢酸ビニル、プロピオン酸ビニル等が挙げられ;
ビニルエーテル類としては、例えば、例えば、メチルビニルエーテルやエチルビニルエーテル等のビニルアルキルエーテルが挙げられ;
芳香族ビニル化合物としては、例えば、スチレン、α-メチルスチレン、ビニルトルエン等が挙げられ;
オレフィン類としては、例えば、エチレン、ブタジエン、イソプレン、イソブチレン等が挙げられ;
脂環式炭化水素基を有する(メタ)アクリル酸エステルとしては、例えば、シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート等が挙げられ;
芳香族炭化水素基を有する(メタ)アクリル酸エステルとしては、例えば、フェニル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレート等が挙げられる。 Examples of the carboxy group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like;
Examples of the acid anhydride group-containing monomer include maleic anhydride and itaconic anhydride;
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylate. ) 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4 -Hydroxymethylcyclohexyl)methyl (meth)acrylate and the like hydroxyalkyl (meth)acrylate and the like;
Examples of the monomer having a sulfonic acid group or a phosphoric acid group include styrenesulfonic acid, allylsulfonic acid, sodium vinylsulfonate, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid. , Sulfopropyl (meth)acrylate, (meth)acryloyloxynaphthalene sulfonic acid, 2-hydroxyethyl acryloyl phosphate and the like;
Examples of the epoxy group-containing monomer include epoxy group-containing acrylates such as (meth)acrylic acid glycidyl and (meth)acrylic acid-2-ethylglycidyl ether, allyl glycidyl ether, and (meth)acrylic acid glycidyl ether;
Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
Examples of the isocyanate group-containing monomer include 2-isocyanatoethyl (meth)acrylate and the like;
Examples of the amide group-containing monomer include (meth)acrylamide; N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl( N,N-dialkyl(meth)acrylamides such as (meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl)(meth)acrylamide; N-ethyl (meth ) N-alkyl(meth)acrylamides such as acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, Nn-butyl(meth)acrylamide; N-vinylcarboxylic amides such as N-vinylacetamide Others: N,N-dimethylaminopropyl(meth)acrylamide, hydroxyethylacrylamide, N-methylol(meth)acrylamide, N-ethylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, N-methoxymethyl( (Meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-(meth)acryloylmorpholine and the like;
Examples of the monomer having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, N-vinyl -3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N -Vinylthiazole, N-vinylisothiazole, N-vinylpyridazine and the like (for example, lactams such as N-vinyl-2-caprolactam);
Examples of the monomer having a succinimide skeleton include N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, N-(meth)acryloyl-8-oxyhexamethylenesuccinimide and the like. Given;
Examples of the maleimides include N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide, N-phenyl maleimide and the like;
Examples of itaconimides include N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide, N -Lauryl itaconimide and the like;
Examples of aminoalkyl (meth)acrylates include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and (meth)acrylic. T-butylaminoethyl acid acid;
Examples of the alkoxyalkyl (meth)acrylates include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and (meth)acrylic acid. Ethoxypropyl and the like can be mentioned;
Examples of vinyl esters include vinyl acetate, vinyl propionate and the like;
Examples of vinyl ethers include vinyl alkyl ethers such as methyl vinyl ether and ethyl vinyl ether;
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene and the like;
Examples of olefins include ethylene, butadiene, isoprene, and isobutylene;
Examples of the (meth)acrylic acid ester having an alicyclic hydrocarbon group include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate and the like;
Examples of the (meth)acrylic acid ester having an aromatic hydrocarbon group include phenyl(meth)acrylate, phenoxyethyl(meth)acrylate, and benzyl(meth)acrylate.
このような共重合性モノマーを使用する場合、その使用量は特に限定されないが、通常はモノマー成分全量の0.01重量%以上とすることが適当である。共重合性モノマーの使用による効果をよりよく発揮する観点から、共重合性モノマーの使用量をモノマー成分全量の0.1重量%以上としてもよく、1重量%以上としてもよい。また、共重合性モノマーの使用量は、モノマー成分全量の50重量%以下とすることができ、40重量%以下とすることが好ましい。これにより、粘着剤の凝集力が高くなり過ぎることを防ぎ、常温(25℃)でのタック感を向上させ得る。
When such a copolymerizable monomer is used, the amount thereof is not particularly limited, but it is usually suitable to be 0.01% by weight or more of the total amount of the monomer components. From the viewpoint of better exerting the effect of using the copolymerizable monomer, the amount of the copolymerizable monomer used may be 0.1% by weight or more, or 1% by weight or more based on the total amount of the monomer components. The amount of the copolymerizable monomer used can be 50% by weight or less, and preferably 40% by weight or less, based on the total amount of the monomer components. This can prevent the cohesive force of the pressure-sensitive adhesive from becoming too high, and improve the tackiness at room temperature (25° C.).
本発明の一実施形態において、(メタ)アクリル系ポリマーは、主成分としてのアルキル(メタ)アクリレートに加えて、必要に応じて、モノマー単位として、上述のような水酸基含有モノマー(典型的には、水酸基を含有する(メタ)アクリル系モノマー)を含み得る。水酸基含有モノマーとしては、上述のように、例えば、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸2-ヒドロキシブチル、(メタ)アクリル酸3-ヒドロキシプロピル、(メタ)アクリル酸4-ヒドロキシブチル、(メタ)アクリル酸6-ヒドロキシヘキシル、(メタ)アクリル酸8-ヒドロキシオクチル、(メタ)アクリル酸10-ヒドロキシデシル、(メタ)アクリル酸12-ヒドロキシラウリル、(4-ヒドロキシメチルシクロへキシル)メチル(メタ)アクリレート等の(メタ)アクリル酸ヒドロキシアルキル等が挙げられるが、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸4-ヒドロキシブチル、(メタ)アクリル酸6-ヒドロキシヘキシル等を好適に使用することができる。なかでも好ましい例として、アクリル酸2-ヒドロキシエチル(HEA)、アクリル酸4-ヒドロキシブチル(4HBA)が挙げられる。水酸基含有モノマーの使用により、粘着剤の凝集力や極性を調整し、加熱後粘着力を向上させることができる。また、水酸基含有モノマーは、粘着剤層の親水性を高めることで、湿気による透明性低下を抑制するためにも役立ち得る。水酸基含有モノマーを含める場合、水酸基含有モノマーの使用量は、特に制限されないが、通常、(メタ)アクリル系ポリマーを調製するためのモノマー単位全量を基準として、例えば0.01重量%以上、0.1重量%以上、0.5重量%以上などとすることができる。本発明の好ましい実施形態において、粘着剤層付き偏光フィルムは、ベースポリマーである(メタ)アクリル系ポリマーが、モノマー単位として、水酸基含有モノマーを0.01~5重量%で含有することができる。
In one embodiment of the present invention, the (meth)acrylic polymer is, in addition to the alkyl (meth)acrylate as a main component, optionally a hydroxyl group-containing monomer (typically, as described above) as a monomer unit. , A (meth)acrylic monomer containing a hydroxyl group). Examples of the hydroxyl group-containing monomer include, as described above, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxy (meth)acrylate. Hydroxypropyl, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-(meth)acrylic acid Examples thereof include hydroxyalkyl (meth)acrylate such as hydroxylauryl, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, and the like, 2-hydroxyethyl (meth)acrylate, 4-hydroxy (meth)acrylate. Butyl, 6-hydroxyhexyl (meth)acrylate and the like can be preferably used. Among these, preferable examples include 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA). By using the hydroxyl group-containing monomer, the cohesive force and polarity of the pressure-sensitive adhesive can be adjusted and the pressure-sensitive adhesive force after heating can be improved. Further, the hydroxyl group-containing monomer can also serve to suppress the decrease in transparency due to moisture by increasing the hydrophilicity of the pressure-sensitive adhesive layer. When the hydroxyl group-containing monomer is included, the amount of the hydroxyl group-containing monomer to be used is not particularly limited, but usually 0.01% by weight or more, 0.1% by weight or more, based on the total amount of the monomer unit for preparing the (meth)acrylic polymer. It can be 1% by weight or more, 0.5% by weight or more. In a preferred embodiment of the present invention, the pressure-sensitive adhesive layer-attached polarizing film can contain the hydroxyl group-containing monomer in an amount of 0.01 to 5% by weight as the monomer unit of the (meth)acrylic polymer as the base polymer.
また、本発明の一実施形態において、(メタ)アクリル系ポリマーは、主成分としてのアルキル(メタ)アクリレートに加えて、必要に応じて、粘着剤層の凝集力調整等の目的で、多官能性モノマーを含有してもよい。多官能性モノマーとしては、例えば、エチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、1,12-ドデカンジオールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、テトラメチロールメタントリ(メタ)アクリレート、アリル(メタ)アクリレート、ビニル(メタ)アクリレート、ジビニルベンゼン、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート、ブチルジオール(メタ)アクリレート、ヘキシルジオールジ(メタ)アクリレート等が挙げられる。なかでも、トリメチロールプロパントリ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレートを好適に使用することができる。多官能性モノマーは、1種を単独でまたは2種以上を組み合わせて使用することができる。多官能性モノマーの使用量は、その分子量や官能基数等により異なるが、通常は、アルキル(メタ)アクリレート(A)を調製するためのモノマー成分全量に対して0.01重量%~3.0重量%の範囲とすることが適当であり、0.02重量%~2.0重量%としてもよく、0.03重量%~1.0重量%としてもよい。
In addition, in one embodiment of the present invention, the (meth)acrylic polymer is, in addition to the alkyl (meth)acrylate as the main component, a polyfunctional polymer for the purpose of adjusting the cohesive force of the pressure-sensitive adhesive layer, if necessary. It may contain a polymerizable monomer. Examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecane Diol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl Examples thereof include diol (meth)acrylate and hexyl diol di(meth)acrylate. Among them, trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate and dipentaerythritol hexa(meth)acrylate can be preferably used. The polyfunctional monomers may be used alone or in combination of two or more. The amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, etc., but is usually 0.01% by weight to 3.0% by weight based on the total amount of the monomer components for preparing the alkyl (meth)acrylate (A). It is suitable to set it in the range of wt%, and it may be 0.02 wt% to 2.0 wt% or 0.03 wt% to 1.0 wt%.
(2)極性モノマー(B)
本発明の一実施形態において、ベースポリマーは、共重合性モノマー単位として、カルボキシル基含有モノマー(b1)および窒素含有モノマー(b2)からなる群より選択される少なくとも1種の極性モノマー(B)を更に含むことができる。 (2) Polar monomer (B)
In one embodiment of the present invention, the base polymer contains, as a copolymerizable monomer unit, at least one polar monomer (B) selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2). It can also be included.
本発明の一実施形態において、ベースポリマーは、共重合性モノマー単位として、カルボキシル基含有モノマー(b1)および窒素含有モノマー(b2)からなる群より選択される少なくとも1種の極性モノマー(B)を更に含むことができる。 (2) Polar monomer (B)
In one embodiment of the present invention, the base polymer contains, as a copolymerizable monomer unit, at least one polar monomer (B) selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2). It can also be included.
本発明の一実施形態において、上記極性モノマー(B)は、ベースポリマーの重量を基準として、0~20重量%で含まれ得る。極性モノマー(B)は、ベースポリマーの重量を基準として、好ましくは0.1~17.5重量%であり、より好ましくは1~15重量%である。
In an embodiment of the present invention, the polar monomer (B) may be included in an amount of 0 to 20% by weight based on the weight of the base polymer. The polar monomer (B) is preferably 0.1 to 17.5% by weight, more preferably 1 to 15% by weight, based on the weight of the base polymer.
(2-1)カルボキシル基含有モノマー(b1)
本発明において、ベースポリマーは、共重合性モノマー単位として、カルボキシル基含有モノマー(b1)を含むことができる。カルボキシ基含有モノマー(b1)としては、例えば、アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸等が挙げられるが、これらに限定されない。本発明の好ましい実施形態において、カルボキシル基含有モノマー(b1)は、アクリル酸、メタクリル酸であってよい。本発明のより好ましい実施形態において、カルボキシル基含有モノマー(b1)は、アクリル酸(AA)であってよい。 (2-1) Carboxyl group-containing monomer (b1)
In the present invention, the base polymer may contain a carboxyl group-containing monomer (b1) as a copolymerizable monomer unit. Examples of the carboxy group-containing monomer (b1) include, but are not limited to, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like. .. In a preferred embodiment of the present invention, the carboxyl group-containing monomer (b1) may be acrylic acid or methacrylic acid. In a more preferred embodiment of the present invention, the carboxyl group-containing monomer (b1) may be acrylic acid (AA).
本発明において、ベースポリマーは、共重合性モノマー単位として、カルボキシル基含有モノマー(b1)を含むことができる。カルボキシ基含有モノマー(b1)としては、例えば、アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸等が挙げられるが、これらに限定されない。本発明の好ましい実施形態において、カルボキシル基含有モノマー(b1)は、アクリル酸、メタクリル酸であってよい。本発明のより好ましい実施形態において、カルボキシル基含有モノマー(b1)は、アクリル酸(AA)であってよい。 (2-1) Carboxyl group-containing monomer (b1)
In the present invention, the base polymer may contain a carboxyl group-containing monomer (b1) as a copolymerizable monomer unit. Examples of the carboxy group-containing monomer (b1) include, but are not limited to, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like. .. In a preferred embodiment of the present invention, the carboxyl group-containing monomer (b1) may be acrylic acid or methacrylic acid. In a more preferred embodiment of the present invention, the carboxyl group-containing monomer (b1) may be acrylic acid (AA).
(2-2)窒素含有モノマー(b2)
本発明において、ベースポリマーは、共重合性モノマー単位として、窒素含有モノマー(b2)を含むことができる。窒素含有モノマー(b2)としては、例えば、ラクタム環を有するビニル系モノマー(例えば、N-ビニルピロリドン、メチルビニルピロリドンなどのビニルピロリドン系モノマー、及びβ-ラクタム環、δ-ラクタム環、及びε-ラクタム環などのラクタム環を有するビニルラクタム系モノマーなど);マレイミド、N-シクロへキシルマレイミド、N-フェニルマレイミドなどのマレイミド系モノマー;(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N-ヘキシル(メタ)アクリルアミド、N-メチル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-メチロールプロパン(メタ)アクリルアミドなどの(N-置換)アミド系モノマー;(メタ)アクリル酸アミノエチル、(メタ)アクリル酸アミノプロピル、(メタ)アクリル酸N,N-ジメチルアミノエチル、(メタ)アクリル酸t-ブチルアミノエチル、3-(3-ピリニジル)プロピル(メタ)アクリレートなどの(メタ)アクリル酸アミノアルキル系モノマー;N-(メタ)アクリロイルオキシメチレンスクシンイミド、N-(メタ)アクリロイル-6-オキシヘキサメチレンスクシンイミド、N-(メタ)アクリロイル-8-オキシオクタメチレンスクシンイミドなどのスクシンイミド系モノマー;アクリロニトリル、メタクリロニトリルなどのシアノ(メタ)アクリレート系モノマー;ビニルピリジン、ビニルピペリドン、ビニルピリミジン、ビニルピペラジン、ビニルピラジン、ビニルピロール、ビニルイミダゾール、ビニルオキサゾール、ビニルモルホリン、N-ビニルカルボン酸アミド類などが挙げられるが、これらに限定されない。本発明の好ましい実施形態において、窒素含有モノマー(b2)は、N-ビニルピロリドン、メチルビニルピロリドン、N,N-ジメチル(メタ)アクリルアミドであってよい。本発明のより好ましい実施形態において、窒素含有モノマー(b2)は、N-ビニルピロリドンであってよい。 (2-2) Nitrogen-containing monomer (b2)
In the present invention, the base polymer may include a nitrogen-containing monomer (b2) as a copolymerizable monomer unit. Examples of the nitrogen-containing monomer (b2) include vinyl monomers having a lactam ring (for example, vinylpyrrolidone monomers such as N-vinylpyrrolidone and methylvinylpyrrolidone, β-lactam ring, δ-lactam ring, and ε-). Vinyllactam-based monomers having a lactam ring such as lactam ring); Maleimide-based monomers such as maleimide, N-cyclohexylmaleimide, N-phenylmaleimide; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N , N-diethyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-methyl(meth)acrylamide, N-butyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N -(N-substituted)amide-based monomers such as methylolpropane (meth)acrylamide; aminoethyl (meth)acrylate, aminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, (meth) Aminoalkyl-based (meth)acrylate monomers such as t-butylaminoethyl acrylate and 3-(3-pyridinyl)propyl(meth)acrylate; N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6 -Succinimide-based monomers such as oxyhexamethylene succinimide and N-(meth)acryloyl-8-oxyoctamethylene succinimide; Cyano (meth)acrylate-based monomers such as acrylonitrile and methacrylonitrile; vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine , Vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, N-vinylcarboxylic acid amides and the like, but are not limited thereto. In a preferred embodiment of the present invention, the nitrogen-containing monomer (b2) may be N-vinylpyrrolidone, methylvinylpyrrolidone, N,N-dimethyl(meth)acrylamide. In a more preferred embodiment of the present invention, the nitrogen-containing monomer (b2) may be N-vinylpyrrolidone.
本発明において、ベースポリマーは、共重合性モノマー単位として、窒素含有モノマー(b2)を含むことができる。窒素含有モノマー(b2)としては、例えば、ラクタム環を有するビニル系モノマー(例えば、N-ビニルピロリドン、メチルビニルピロリドンなどのビニルピロリドン系モノマー、及びβ-ラクタム環、δ-ラクタム環、及びε-ラクタム環などのラクタム環を有するビニルラクタム系モノマーなど);マレイミド、N-シクロへキシルマレイミド、N-フェニルマレイミドなどのマレイミド系モノマー;(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N-ヘキシル(メタ)アクリルアミド、N-メチル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-メチロールプロパン(メタ)アクリルアミドなどの(N-置換)アミド系モノマー;(メタ)アクリル酸アミノエチル、(メタ)アクリル酸アミノプロピル、(メタ)アクリル酸N,N-ジメチルアミノエチル、(メタ)アクリル酸t-ブチルアミノエチル、3-(3-ピリニジル)プロピル(メタ)アクリレートなどの(メタ)アクリル酸アミノアルキル系モノマー;N-(メタ)アクリロイルオキシメチレンスクシンイミド、N-(メタ)アクリロイル-6-オキシヘキサメチレンスクシンイミド、N-(メタ)アクリロイル-8-オキシオクタメチレンスクシンイミドなどのスクシンイミド系モノマー;アクリロニトリル、メタクリロニトリルなどのシアノ(メタ)アクリレート系モノマー;ビニルピリジン、ビニルピペリドン、ビニルピリミジン、ビニルピペラジン、ビニルピラジン、ビニルピロール、ビニルイミダゾール、ビニルオキサゾール、ビニルモルホリン、N-ビニルカルボン酸アミド類などが挙げられるが、これらに限定されない。本発明の好ましい実施形態において、窒素含有モノマー(b2)は、N-ビニルピロリドン、メチルビニルピロリドン、N,N-ジメチル(メタ)アクリルアミドであってよい。本発明のより好ましい実施形態において、窒素含有モノマー(b2)は、N-ビニルピロリドンであってよい。 (2-2) Nitrogen-containing monomer (b2)
In the present invention, the base polymer may include a nitrogen-containing monomer (b2) as a copolymerizable monomer unit. Examples of the nitrogen-containing monomer (b2) include vinyl monomers having a lactam ring (for example, vinylpyrrolidone monomers such as N-vinylpyrrolidone and methylvinylpyrrolidone, β-lactam ring, δ-lactam ring, and ε-). Vinyllactam-based monomers having a lactam ring such as lactam ring); Maleimide-based monomers such as maleimide, N-cyclohexylmaleimide, N-phenylmaleimide; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N , N-diethyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-methyl(meth)acrylamide, N-butyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N -(N-substituted)amide-based monomers such as methylolpropane (meth)acrylamide; aminoethyl (meth)acrylate, aminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, (meth) Aminoalkyl-based (meth)acrylate monomers such as t-butylaminoethyl acrylate and 3-(3-pyridinyl)propyl(meth)acrylate; N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6 -Succinimide-based monomers such as oxyhexamethylene succinimide and N-(meth)acryloyl-8-oxyoctamethylene succinimide; Cyano (meth)acrylate-based monomers such as acrylonitrile and methacrylonitrile; vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine , Vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, N-vinylcarboxylic acid amides and the like, but are not limited thereto. In a preferred embodiment of the present invention, the nitrogen-containing monomer (b2) may be N-vinylpyrrolidone, methylvinylpyrrolidone, N,N-dimethyl(meth)acrylamide. In a more preferred embodiment of the present invention, the nitrogen-containing monomer (b2) may be N-vinylpyrrolidone.
(メタ)アクリル系ポリマーを得る方法は特に限定されず、溶液重合法、エマルション重合法、バルク重合法、懸濁重合法、光重合法等の、アクリル系ポリマーの合成手法として知られている各種の重合方法を適宜採用することができる。いくつかの態様において、溶液重合法を好ましく採用し得る。溶液重合を行う際の重合温度は、使用するモノマーおよび溶媒の種類、重合開始剤の種類等に応じて適宜選択することができ、例えば20℃~170℃程度(典型的には40℃~140℃程度)とすることができる。
The method for obtaining the (meth)acrylic polymer is not particularly limited, and various known methods for synthesizing acrylic polymers, such as solution polymerization method, emulsion polymerization method, bulk polymerization method, suspension polymerization method, and photopolymerization method. The above-mentioned polymerization method can be appropriately adopted. In some embodiments, the solution polymerization method may be preferably adopted. The polymerization temperature at the time of performing solution polymerization can be appropriately selected according to the type of monomer and solvent used, the type of polymerization initiator, etc., and is, for example, about 20°C to 170°C (typically 40°C to 140°C). C.).
重合に用いる開始剤は、重合方法に応じて、従来既知の熱重合開始剤や光重合開始剤等から適宜選択することができる。重合開始剤は、1種を単独でまたは2種以上を組み合わせて使用することができる。
The initiator used for the polymerization can be appropriately selected from conventionally known thermal polymerization initiators, photopolymerization initiators, etc. according to the polymerization method. The polymerization initiators may be used alone or in combination of two or more.
熱重合開始剤としては、例えば、アゾ系重合開始剤(例えば、2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス-2-メチルブチロニトリル、2,2’-アゾビス(2-メチルプロピオン酸)ジメチル、4,4’-アゾビス-4-シアノバレリアン酸、アゾビスイソバレロニトリル、2,2’-アゾビス(2-アミジノプロパン)ジヒドロクロライド、2,2’-アゾビス[2-(5-メチル-2-イミダゾリン-2-イル)プロパン]ジヒドロクロライド、2,2’-アゾビス(2-メチルプロピオンアミジン)二硫酸塩、2,2’-アゾビス(N,N’-ジメチレンイソブチルアミジン)ジヒドロクロライド等);過硫酸カリウム等の過硫酸塩;過酸化物系重合開始剤(例えば、ジベンゾイルペルオキシド、t-ブチルペルマレエート、過酸化ラウロイル等);レドックス系重合開始剤等が挙げられる。熱重合開始剤の使用量は、特に制限されないが、例えば、アクリル系ポリマーの調製に用いられるモノマー成分100重量部に対して0.01重量部~5重量部、好ましくは0.05重量部~3重量部の範囲内の量とすることができる。
Examples of the thermal polymerization initiator include azo polymerization initiators (eg, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis( 2-methylpropionic acid)dimethyl, 4,4′-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 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'-dimethylene Isobutylamidine) dihydrochloride, etc.); Persulfate such as potassium persulfate; Peroxide type polymerization initiator (eg, dibenzoyl peroxide, t-butyl permaleate, lauroyl peroxide, etc.); Redox type polymerization initiator, etc. Is mentioned. The amount of the thermal polymerization initiator used is not particularly limited, but is, for example, 0.01 parts by weight to 5 parts by weight, preferably 0.05 parts by weight to 100 parts by weight of the monomer component used for preparing the acrylic polymer. The amount can be within the range of 3 parts by weight.
光重合開始剤としては、特に制限されないが、例えば、ベンゾインエーテル系光重合開始剤、アセトフェノン系光重合開始剤、α-ケトール系光重合開始剤、芳香族スルホニルクロリド系光重合開始剤、光活性オキシム系光重合開始剤、ベンゾイン系光重合開始剤、ベンジル系光重合開始剤、ベンゾフェノン系光重合開始剤、ケタール系光重合開始剤、チオキサントン系光重合開始剤、アシルフォスフィンオキサイド系光重合開始剤等を用いることができる。光重合開始剤の使用量は、特に制限されないが、例えば、アクリル系ポリマーの調製に用いられるモノマー成分100重量部に対して0.01重量部~5重量部、好ましくは0.05重量部~3重量部の範囲内の量とすることができる。
The photopolymerization initiator is not particularly limited, and examples thereof include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, α-ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactivators. Oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone photopolymerization initiator, acylphosphine oxide photopolymerization initiator Agents and the like can be used. The amount of the photopolymerization initiator used is not particularly limited, but for example, 0.01 part by weight to 5 parts by weight, preferably 0.05 part by weight to 100 parts by weight of the monomer component used for the preparation of the acrylic polymer. The amount can be within the range of 3 parts by weight.
本発明の一実施形態において、(メタ)アクリル系ポリマーは、上述のようなモノマー成分に重合開始剤を配合した混合物に、重合溶媒として、例えば、酢酸エチル、トルエン等を用い、溶液重合にて(メタ)アクリル系ポリマーを得ることができる。溶液重合例としては、反応は窒素等の不活性ガス気流下で、重合開始剤を加え、通常、50~70℃程度で、5~30時間程度の反応条件で行われる。本明細書において開示される粘着剤層は、例えば、上記(メタ)アクリル系ポリマーと後述するシリコーンオリゴマーPs、その他添加剤とを含む粘着剤組成物を用いて形成され得る。
In one embodiment of the present invention, the (meth)acrylic polymer is solution-polymerized by using, for example, ethyl acetate, toluene or the like as a polymerization solvent in a mixture of the above-mentioned monomer component and a polymerization initiator. A (meth)acrylic polymer can be obtained. As an example of solution polymerization, the reaction is usually carried out under a stream of an inert gas such as nitrogen with a polymerization initiator at about 50 to 70° C. for about 5 to 30 hours. The pressure-sensitive adhesive layer disclosed in the present specification can be formed using, for example, a pressure-sensitive adhesive composition containing the (meth)acrylic polymer, the silicone oligomer Ps described below, and other additives.
本発明において、上述のベースポリマーの重量平均分子量Mwは50万~250万であってよい。本発明の一実施形態において、ベースポリマーの重量平均分子量Mwは、好ましくは、70万~270万であり、より好ましくは、80万~250万であり得る。
In the present invention, the weight average molecular weight Mw of the above-mentioned base polymer may be 500,000 to 2,500,000. In one embodiment of the present invention, the weight average molecular weight Mw of the base polymer may be preferably 700,000 to 2.7 million, more preferably 800,000 to 2.5 million.
<シリコーンオリゴマーPs>
本発明において、粘着剤層はシリコーンオリゴマーPsを含む。シリコーンオリゴマーPsは、シロキサン構造の低極性および運動性によって、初期粘着力の抑制および粘着力上昇比の向上に寄与する粘着力上昇遅延剤として機能し得る。シリコーンオリゴマーPsとしては、側鎖にシロキサン構造を有するポリマーが好ましく用いられ得る。 <Silicone Oligomer Ps>
In the present invention, the pressure-sensitive adhesive layer contains silicone oligomer Ps. Silicone oligomer Ps can function as a tackiness increase retarder that contributes to suppression of initial tackiness and improvement of tackiness increase ratio due to the low polarity and mobility of the siloxane structure. As the silicone oligomer Ps, a polymer having a siloxane structure in its side chain can be preferably used.
本発明において、粘着剤層はシリコーンオリゴマーPsを含む。シリコーンオリゴマーPsは、シロキサン構造の低極性および運動性によって、初期粘着力の抑制および粘着力上昇比の向上に寄与する粘着力上昇遅延剤として機能し得る。シリコーンオリゴマーPsとしては、側鎖にシロキサン構造を有するポリマーが好ましく用いられ得る。 <Silicone Oligomer Ps>
In the present invention, the pressure-sensitive adhesive layer contains silicone oligomer Ps. Silicone oligomer Ps can function as a tackiness increase retarder that contributes to suppression of initial tackiness and improvement of tackiness increase ratio due to the low polarity and mobility of the siloxane structure. As the silicone oligomer Ps, a polymer having a siloxane structure in its side chain can be preferably used.
本発明において用いられるシリコーンオリゴマーPsは、そのガラス転移温度(Tg)が-50℃以上100℃以下の範囲のものである。本発明の一実施形態において、シリコーンオリゴマーPsのTgは、好ましくは-30℃以上70℃以下であり、より好ましくは、-20℃以上60℃以下であってよい。シリコーンオリゴマーPsのTgが上記範囲内であると、初期の低粘着性と使用時の粘着力の上昇(強粘着性)とを高レベルで両立することができる。
The silicone oligomer Ps used in the present invention has a glass transition temperature (Tg) in the range of -50°C to 100°C. In one embodiment of the present invention, the Tg of the silicone oligomer Ps may preferably be -30°C or higher and 70°C or lower, and more preferably -20°C or higher and 60°C or lower. When the Tg of the silicone oligomer Ps is in the above range, it is possible to achieve both a low initial tackiness and an increase in tackiness during use (strong tackiness) at a high level.
本発明において用いられるシリコーンオリゴマーPsは、その重量平均分子量Mwが10000以上300000以下の範囲のものである。本発明の一実施形態において、シリコーンオリゴマーPsの重量平均分子量Mwは、好ましくは12500以上2500000以下であり、より好ましくは15000以上2000000以下であってよい。シリコーンオリゴマーPsの重量平均分子量Mwが上記範囲内であると、粘着剤層内における相溶性や移動性を適度な範囲に調節しやすく、初期の低粘着性と使用時の強粘着性とを高レベルで両立する粘着シートを実現しやすくなる。
The silicone oligomer Ps used in the present invention has a weight average molecular weight Mw of 10,000 or more and 300,000 or less. In one embodiment of the present invention, the weight average molecular weight Mw of the silicone oligomer Ps may be preferably 12,500 or more and 2500000 or less, more preferably 15000 or more and 2000000 or less. When the weight average molecular weight Mw of the silicone oligomer Ps is within the above range, it is easy to adjust the compatibility and mobility in the pressure-sensitive adhesive layer to an appropriate range, and the initial low tackiness and strong tackiness during use are high. It becomes easier to realize a pressure-sensitive adhesive sheet that is compatible at both levels.
本発明の好ましい実施形態において、シリコーンオリゴマーPsは、Tgが-50℃以上100℃以下であり、側鎖のシリコーン官能基当量が1000~20000g/molであり、重量平均分子量Mwが10000以上300000以下であってよい。
In a preferred embodiment of the present invention, the silicone oligomer Ps has a Tg of −50° C. or higher and 100° C. or lower, a side chain silicone functional group equivalent of 1000 to 20000 g/mol, and a weight average molecular weight Mw of 10,000 or more and 300,000 or less. May be
本発明の一実施形態において、シリコーンオリゴマーPsは、ポリオルガノシロキサン骨格を有するモノマーS1と、ホモポリマーのガラス転移温度が-70℃以上180℃以下のモノマーとをモノマー単位として含み得る。
In one embodiment of the present invention, the silicone oligomer Ps may include a monomer S1 having a polyorganosiloxane skeleton and a monomer having a homopolymer glass transition temperature of −70° C. or higher and 180° C. or lower as monomer units.
(1)ポリオルガノシロキサン骨格を有するモノマーS1
本発明のシリコーンオリゴマーPsに用いることができるポリオルガノシロキサン骨格を有するモノマーS1は、特に限定されず、ポリオルガノシロキサン骨格を有する任意のモノマーを用いることができる。ポリオルガノシロキサン骨格としては、例えば、トリメチルシロキサン(TM)、ジメチルシロキサン(DM)、ポリオキシエチルメチルシロキサン(EOM)などが挙げられるが、これらに限定されない。 (1) Monomer S1 having a polyorganosiloxane skeleton
The monomer S1 having a polyorganosiloxane skeleton that can be used in the silicone oligomer Ps of the present invention is not particularly limited, and any monomer having a polyorganosiloxane skeleton can be used. Examples of the polyorganosiloxane skeleton include, but are not limited to, trimethylsiloxane (TM), dimethylsiloxane (DM), polyoxyethylmethylsiloxane (EOM), and the like.
本発明のシリコーンオリゴマーPsに用いることができるポリオルガノシロキサン骨格を有するモノマーS1は、特に限定されず、ポリオルガノシロキサン骨格を有する任意のモノマーを用いることができる。ポリオルガノシロキサン骨格としては、例えば、トリメチルシロキサン(TM)、ジメチルシロキサン(DM)、ポリオキシエチルメチルシロキサン(EOM)などが挙げられるが、これらに限定されない。 (1) Monomer S1 having a polyorganosiloxane skeleton
The monomer S1 having a polyorganosiloxane skeleton that can be used in the silicone oligomer Ps of the present invention is not particularly limited, and any monomer having a polyorganosiloxane skeleton can be used. Examples of the polyorganosiloxane skeleton include, but are not limited to, trimethylsiloxane (TM), dimethylsiloxane (DM), polyoxyethylmethylsiloxane (EOM), and the like.
ポリオルガノシロキサン骨格を有するモノマーS1としては、例えば、下記一般式(1)または(2)で表される化合物を用いることができる。より具体的には、信越化学工業株式会社製の片末端反応性シリコーンオイルとして、X-22-174ASX、X-22-2426、X-22-2475、KF-2012、X-22-174BX、X-22-2404などが挙げられる。ポリオルガノシロキサン骨格を有するモノマーS1は、1種を単独でまたは2種以上を組み合わせて使用することができる。
ここで、上記一般式(1),(2)中のR3は水素またはメチルであり、R4はメチル基または1価の有機基であり、mおよびnは0以上の整数である。 As the monomer S1 having a polyorganosiloxane skeleton, for example, a compound represented by the following general formula (1) or (2) can be used. More specifically, as one-end reactive silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., X-22-174ASX, X-22-2426, X-22-2475, KF-2012, X-22-174BX, X -22-2404 and the like. The monomer S1 having a polyorganosiloxane skeleton may be used alone or in combination of two or more.
Here, R 3 in the general formulas (1) and (2) is hydrogen or methyl, R 4 is a methyl group or a monovalent organic group, and m and n are integers of 0 or more.
ここで、上記一般式(1),(2)中のR3は水素またはメチルであり、R4はメチル基または1価の有機基であり、mおよびnは0以上の整数である。 As the monomer S1 having a polyorganosiloxane skeleton, for example, a compound represented by the following general formula (1) or (2) can be used. More specifically, as one-end reactive silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., X-22-174ASX, X-22-2426, X-22-2475, KF-2012, X-22-174BX, X -22-2404 and the like. The monomer S1 having a polyorganosiloxane skeleton may be used alone or in combination of two or more.
Here, R 3 in the general formulas (1) and (2) is hydrogen or methyl, R 4 is a methyl group or a monovalent organic group, and m and n are integers of 0 or more.
本発明において用いられるシリコーンオリゴマーPsは、その側鎖のシリコーン官能基当量が1000~20000g/molである。本発明の一実施形態において、シリコーンオリゴマーPsの側鎖のシリコーン官能基当量は、好ましくは1200~18000g/molであり、より好ましくは1500~15000g/molであってよい。シリコーンオリゴマーPsの側鎖のシリコーン官能基当量が上記範囲内であると、粘着剤層内における相溶性(例えば、ベースポリマーとの相溶性)や移動性を適度な範囲に調節しやすく、初期の低粘着性と使用時の強粘着性とを高レベルで両立する粘着シートを実現しやすくなる。
The silicone oligomer Ps used in the present invention has a silicone functional group equivalent of its side chain of 1000 to 20000 g/mol. In one embodiment of the present invention, the silicone functional group equivalent of the side chain of the silicone oligomer Ps may be preferably 1200 to 18000 g/mol, more preferably 1500 to 15000 g/mol. When the silicone functional group equivalent of the side chain of the silicone oligomer Ps is within the above range, it is easy to adjust the compatibility (for example, the compatibility with the base polymer) and the mobility in the pressure-sensitive adhesive layer to an appropriate range and It becomes easy to realize a pressure-sensitive adhesive sheet that achieves both low tackiness and strong tackiness during use at a high level.
ここで、「官能基当量」とは、官能基1個当たりに結合している主骨格(例えばポリジメチルシロキサン)の重量を意味する。標記単位g/molに関しては、官能基1molと換算している。ポリオルガノシロキサン骨格を有するモノマーS1の官能基当量は、例えば、核磁気共鳴(NMR)に基づく1H-NMR(プロトンNMR)のスペクトル強度から算出することができる。1H-NMRのスペクトル強度に基づく、ポリオルガノシロキサン骨格を有するモノマーS1の官能基当量(g/mol)の算出は、1H-NMRスペクトル解析に係る一般的な構造解析手法に基づいて、必要であれば日本国特許第5951153号公報の記載を参照して行うことができる。
Here, the “functional group equivalent” means the weight of the main skeleton (for example, polydimethylsiloxane) bonded to each functional group. The unit of g/mol is converted to 1 mol of the functional group. The functional group equivalent of the monomer S1 having a polyorganosiloxane skeleton can be calculated from the spectrum intensity of 1 H-NMR (proton NMR) based on nuclear magnetic resonance (NMR), for example. Calculation of the functional group equivalent (g/mol) of the monomer S1 having a polyorganosiloxane skeleton based on the 1 H-NMR spectrum intensity is required based on a general structural analysis method related to 1 H-NMR spectrum analysis. In that case, it can be performed by referring to the description of Japanese Patent No. 5915153.
なお、ポリオルガノシロキサン骨格を有するモノマーS1として官能基当量が異なる2種類以上のモノマーを用いる場合、モノマーS1の官能基当量としては、算術平均値を用いることができる。すなわち、官能基当量が異なるn種類のモノマー(モノマーS11,モノマーS12・・・モノマーS1n)からなるモノマーS1の官能基当量は、下記式により計算することができる。
モノマーS1の官能基当量(g/mol)=(モノマーS11の官能基当量×モノマーS11の配合量+モノマーS12の官能基当量×モノマーS12の配合量+・・・+モノマーS1nの官能基当量×モノマーS1nの配合量)/(モノマーS11の配合量+モノマーS12の配合量+・・・+モノマーS1nの配合量) When two or more kinds of monomers having different functional group equivalents are used as the monomer S1 having a polyorganosiloxane skeleton, an arithmetic average value can be used as the functional group equivalent of the monomer S1. That is, the functional group equivalent of the monomer S1 composed of n kinds of monomers (monomer S1 1 , monomer S1 2 ... Monomer S1 n ) having different functional group equivalents can be calculated by the following formula.
Functional group equivalent of the monomer S1 (g / mol) = (monomer S1 1 functional group equivalent × monomer S1 1 of the amount + monomer S1 2 functional group equivalent × monomer S1 2 of the amount + ... + monomer S1 n Functional group equivalent×monomer S1 n blending amount)/(monomer S1 1 blending amount+monomer S1 2 blending amount+...+monomer S1 n blending amount)
モノマーS1の官能基当量(g/mol)=(モノマーS11の官能基当量×モノマーS11の配合量+モノマーS12の官能基当量×モノマーS12の配合量+・・・+モノマーS1nの官能基当量×モノマーS1nの配合量)/(モノマーS11の配合量+モノマーS12の配合量+・・・+モノマーS1nの配合量) When two or more kinds of monomers having different functional group equivalents are used as the monomer S1 having a polyorganosiloxane skeleton, an arithmetic average value can be used as the functional group equivalent of the monomer S1. That is, the functional group equivalent of the monomer S1 composed of n kinds of monomers (monomer S1 1 , monomer S1 2 ... Monomer S1 n ) having different functional group equivalents can be calculated by the following formula.
Functional group equivalent of the monomer S1 (g / mol) = (monomer S1 1 functional group equivalent × monomer S1 1 of the amount + monomer S1 2 functional group equivalent × monomer S1 2 of the amount + ... + monomer S1 n Functional group equivalent×monomer S1 n blending amount)/(monomer S1 1 blending amount+monomer S1 2 blending amount+...+monomer S1 n blending amount)
ポリオルガノシロキサン骨格を有するモノマーS1の含有量は、シリコーンオリゴマーPsを調製するための全モノマー成分に対して、例えば5重量%以上であってよく、粘着力上昇遅延剤としての効果をよりよく発揮する観点から10重量%以上とすることが好ましく、15重量%以上としてもよい。いくつかの態様において、上記モノマーS1の含有量は、例えば20重量%以上であってもよい。また、ポリオルガノシロキサン骨格を有するモノマーS1の含有量は、重合反応性や相溶性の観点から、シリコーンオリゴマーPsを調製するための全モノマー成分に対して、60重量%以下とすることが適当であり、50重量%以下としてもよく、40重量%以下としてもよく、30重量%以下としてもよい。ポリオルガノシロキサン骨格を有するモノマーS1の含有量が上記範囲内にあると、初期の低粘着性と使用時の粘着力の上昇(強粘着性)とを高レベルで両立する粘着シートを実現しやすくなる。
The content of the monomer S1 having a polyorganosiloxane skeleton may be, for example, 5% by weight or more based on the total monomer components for preparing the silicone oligomer Ps, and the effect as a tackiness increase retarder can be better exhibited. From the viewpoint of the above, the amount is preferably 10% by weight or more, and may be 15% by weight or more. In some embodiments, the content of the monomer S1 may be, for example, 20% by weight or more. From the viewpoint of polymerization reactivity and compatibility, the content of the monomer S1 having a polyorganosiloxane skeleton is appropriately 60% by weight or less based on the total monomer components for preparing the silicone oligomer Ps. Yes, it may be 50% by weight or less, 40% by weight or less, or 30% by weight or less. When the content of the monomer S1 having a polyorganosiloxane skeleton is within the above range, it is easy to realize a pressure-sensitive adhesive sheet that achieves a high level of both low initial tackiness and increase in tackiness (strong tackiness) during use. Become.
(2)ホモポリマーのガラス転移温度が-70℃以上180℃以下のモノマー
本発明のシリコーンオリゴマーPsは、上記ポリオルガノシロキサン骨格を有するモノマーS1と共重合可能な(メタ)アクリル系モノマーまたは他の共重合性モノマーを含む。本発明のシリコーンオリゴマーPsに用いることができる共重合可能な(メタ)アクリル系モノマーまたは他の共重合性モノマーとしては、ホモポリマーのガラス転移温度が-70℃以上180℃以下のモノマーを用いることができ、例えば、(メタ)アクリル酸アルキルエステル、脂環式炭化水素基を有する(メタ)アクリル酸エステルが挙げられるが、これらに限定されない。(メタ)アクリル酸アルキルエステルとしては、メチルメタクリレート(MMA)、ブチルメタクリレート(BMA)、2-エチルヘキシルメタクリレート(2-EHMA)、ブチルアクリレート(BA)、2-エチルヘキシルアクリレート(2-EHA)が挙げられ、脂環式炭化水素基を有する(メタ)アクリル酸エステルとしては、2-((3-ヒドロキシメチル)-アダマンタン-1-イル)メトキシ-2-オキソエチル メタクリレート(2EHAMA)、シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、1-アダマンチル(メタ)アクリレートなどが挙げられるが、これらに限定されない。本発明の一実施形態において、2-((3-ヒドロキシメチル)-アダマンタン-1-イル)メトキシ-2-オキソエチル メタクリレート(2EHAMA)、およびイソボルニル メタクリレート(IBXMA)から選択される少なくとも1種をモノマー単位として含有し得る。本発明の別の実施形態において、ジシクロペンタニルメタクリレート、イソボルニルメタクリレートおよびシクロヘキシルメタクリレートから選択される少なくとも1種をモノマー単位として含有し得る。これらのモノマーは、1種を単独でまたは2種以上を組み合わせて使用することができる。 (2) Monomer whose homopolymer has a glass transition temperature of −70° C. or higher and 180° C. or lower The silicone oligomer Ps of the present invention is a (meth)acryl-based monomer or another monomer copolymerizable with the monomer S1 having the polyorganosiloxane skeleton. It contains a copolymerizable monomer. As the copolymerizable (meth)acrylic monomer or other copolymerizable monomer that can be used in the silicone oligomer Ps of the present invention, a homopolymer having a glass transition temperature of −70° C. to 180° C. is used. Examples thereof include, but are not limited to, (meth)acrylic acid alkyl ester and (meth)acrylic acid ester having an alicyclic hydrocarbon group. Examples of the (meth)acrylic acid alkyl ester include methyl methacrylate (MMA), butyl methacrylate (BMA), 2-ethylhexyl methacrylate (2-EHMA), butyl acrylate (BA), and 2-ethylhexyl acrylate (2-EHA). Examples of the (meth)acrylic acid ester having an alicyclic hydrocarbon group include 2-((3-hydroxymethyl)-adamantan-1-yl)methoxy-2-oxoethyl methacrylate (2EHAMA), cyclopentyl (meth)acrylate, Examples thereof include, but are not limited to, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, and the like. In one embodiment of the present invention, at least one selected from 2-((3-hydroxymethyl)-adamantan-1-yl)methoxy-2-oxoethyl methacrylate (2EHAMA) and isobornyl methacrylate (IBXMA) is a monomer unit. Can be included as In another embodiment of the present invention, it may contain at least one selected from dicyclopentanyl methacrylate, isobornyl methacrylate and cyclohexyl methacrylate as a monomer unit. These monomers may be used alone or in combination of two or more.
本発明のシリコーンオリゴマーPsは、上記ポリオルガノシロキサン骨格を有するモノマーS1と共重合可能な(メタ)アクリル系モノマーまたは他の共重合性モノマーを含む。本発明のシリコーンオリゴマーPsに用いることができる共重合可能な(メタ)アクリル系モノマーまたは他の共重合性モノマーとしては、ホモポリマーのガラス転移温度が-70℃以上180℃以下のモノマーを用いることができ、例えば、(メタ)アクリル酸アルキルエステル、脂環式炭化水素基を有する(メタ)アクリル酸エステルが挙げられるが、これらに限定されない。(メタ)アクリル酸アルキルエステルとしては、メチルメタクリレート(MMA)、ブチルメタクリレート(BMA)、2-エチルヘキシルメタクリレート(2-EHMA)、ブチルアクリレート(BA)、2-エチルヘキシルアクリレート(2-EHA)が挙げられ、脂環式炭化水素基を有する(メタ)アクリル酸エステルとしては、2-((3-ヒドロキシメチル)-アダマンタン-1-イル)メトキシ-2-オキソエチル メタクリレート(2EHAMA)、シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、1-アダマンチル(メタ)アクリレートなどが挙げられるが、これらに限定されない。本発明の一実施形態において、2-((3-ヒドロキシメチル)-アダマンタン-1-イル)メトキシ-2-オキソエチル メタクリレート(2EHAMA)、およびイソボルニル メタクリレート(IBXMA)から選択される少なくとも1種をモノマー単位として含有し得る。本発明の別の実施形態において、ジシクロペンタニルメタクリレート、イソボルニルメタクリレートおよびシクロヘキシルメタクリレートから選択される少なくとも1種をモノマー単位として含有し得る。これらのモノマーは、1種を単独でまたは2種以上を組み合わせて使用することができる。 (2) Monomer whose homopolymer has a glass transition temperature of −70° C. or higher and 180° C. or lower The silicone oligomer Ps of the present invention is a (meth)acryl-based monomer or another monomer copolymerizable with the monomer S1 having the polyorganosiloxane skeleton. It contains a copolymerizable monomer. As the copolymerizable (meth)acrylic monomer or other copolymerizable monomer that can be used in the silicone oligomer Ps of the present invention, a homopolymer having a glass transition temperature of −70° C. to 180° C. is used. Examples thereof include, but are not limited to, (meth)acrylic acid alkyl ester and (meth)acrylic acid ester having an alicyclic hydrocarbon group. Examples of the (meth)acrylic acid alkyl ester include methyl methacrylate (MMA), butyl methacrylate (BMA), 2-ethylhexyl methacrylate (2-EHMA), butyl acrylate (BA), and 2-ethylhexyl acrylate (2-EHA). Examples of the (meth)acrylic acid ester having an alicyclic hydrocarbon group include 2-((3-hydroxymethyl)-adamantan-1-yl)methoxy-2-oxoethyl methacrylate (2EHAMA), cyclopentyl (meth)acrylate, Examples thereof include, but are not limited to, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, and the like. In one embodiment of the present invention, at least one selected from 2-((3-hydroxymethyl)-adamantan-1-yl)methoxy-2-oxoethyl methacrylate (2EHAMA) and isobornyl methacrylate (IBXMA) is a monomer unit. Can be included as In another embodiment of the present invention, it may contain at least one selected from dicyclopentanyl methacrylate, isobornyl methacrylate and cyclohexyl methacrylate as a monomer unit. These monomers may be used alone or in combination of two or more.
上記(メタ)アクリル酸アルキルエステルおよび上記脂環式炭化水素基を有する(メタ)アクリル酸エステルの使用量は、シリコーンオリゴマーPsを調製するための全モノマー成分に対して、例えば10重量%以上95重量%以下であってよく、20重量%以上95重量%以下であってもよく、30重量%以上90重量%以下であってもよく、40重量%以上90重量%以下であってもよく、50重量%以上85重量%以下であってもよい。
The amount of the above-mentioned (meth)acrylic acid alkyl ester and the above-mentioned (meth)acrylic acid ester having an alicyclic hydrocarbon group used is, for example, 10% by weight or more and 95% by weight or more based on all the monomer components for preparing the silicone oligomer Ps. May be 20% by weight or more, 95% by weight or less, 30% by weight or more and 90% by weight or less, or 40% by weight or more and 90% by weight or less, It may be 50% by weight or more and 85% by weight or less.
シリコーンオリゴマーPsを構成するモノマー単位としてモノマーS1とともに含まれ得るモノマーの他の例として、アルキル(メタ)アクリレート(A)に用いられ得るモノマーとして上記で例示したカルボキシル基含有モノマー、酸無水物基含有モノマー、水酸基含有モノマー、エポキシ基含有モノマー、シアノ基含有モノマー、イソシアネート基含有モノマー、アミド基含有モノマー、窒素原子含有環を有するモノマー、スクシンイミド骨格を有するモノマー、マレイミド類、イタコンイミド類、(メタ)アクリル酸アミノアルキル類、ビニルエステル類、ビニルエーテル類、オレフィン類、芳香族炭化水素基を有する(メタ)アクリル酸エステル、複素環含有(メタ)アクリレート、ハロゲン原子含有(メタ)アクリレート、テルペン化合物誘導体アルコールから得られる(メタ)アクリル酸エステル等が挙げられる。
As another example of the monomer that can be included together with the monomer S1 as a monomer unit constituting the silicone oligomer Ps, a carboxyl group-containing monomer and an acid anhydride group-containing monomer exemplified above as the monomer that can be used in the alkyl (meth)acrylate (A) are included. Monomer, hydroxyl group-containing monomer, epoxy group-containing monomer, cyano group-containing monomer, isocyanate group-containing monomer, amide group-containing monomer, nitrogen atom-containing ring-containing monomer, succinimide skeleton-containing monomer, maleimides, itaconimides, (meth)acrylic Acid aminoalkyls, vinyl esters, vinyl ethers, olefins, aromatic hydrocarbon group-containing (meth)acrylic acid esters, heterocycle-containing (meth)acrylates, halogen atom-containing (meth)acrylates, terpene compound derivative alcohols The (meth)acrylic acid ester etc. which are obtained are mentioned.
シリコーンオリゴマーPsを構成するモノマー単位としてモノマーS1とともに含まれ得るモノマーのさらに他の例として、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート等のオキシアルキレンジ(メタ)アクリレート;ポリオキシアルキレン骨格を有するモノマー、例えばポリエチレングリコールやポリプロピレングリコール等のポリオキシアルキレン鎖の一方の末端に(メタ)アクリロイル基、ビニル基、アリル基等の重合性官能基を有し、他方の末端にエーテル構造(アルキルエーテル、アリールエーテル、アリールアルキルエーテル等)を有する重合性ポリオキシアルキレンエーテル;(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸エトキシエチル、(メタ)アクリル酸プロポキシエチル、(メタ)アクリル酸ブトキシエチル、(メタ)アクリル酸エトキシプロピル等の(メタ)アクリル酸アルコキシアルキル;(メタ)アクリル酸アルカリ金属塩等の塩;トリメチロールプロパントリ(メタ)アクリル酸エステル等の多価(メタ)アクリレート:塩化ビニリデン、(メタ)アクリル酸-2-クロロエチル等のハロゲン化ビニル化合物;2-ビニル-2-オキサゾリン、2-ビニル-5-メチル-2-オキサゾリン、2-イソプロペニル-2-オキサゾリン等のオキサゾリン基含有モノマー;(メタ)アクリロイルアジリジン、(メタ)アクリル酸-2-アジリジニルエチル等のアジリジン基含有モノマー;(メタ)アクリル酸-2-ヒドロキシエチル、(メタ)アクリル酸-2-ヒドロキシプロピル、ラクトン類と(メタ)アクリル酸-2-ヒドロキシエチルとの付加物等の水酸基含有ビニルモノマー;フッ素置換(メタ)アクリル酸アルキルエステル等の含フッ素ビニルモノマー;2-クロルエチルビニルエーテル、モノクロロ酢酸ビニル等の反応性ハロゲン含有ビニルモノマー;ビニルトリメトキシシラン、γ-(メタ)アクリロキシプロピルトリメトキシシラン、アリルトリメトキシシラン、トリメトキシシリルプロピルアリルアミン、2-メトキシエトキシトリメトキシシランのような有機ケイ素含有ビニルモノマー;その他、ビニル基を重合したモノマー末端にラジカル重合性ビニル基を有するマクロモノマー類;等を挙げることができる。これらは、1種を単独であるいは組み合わせてモノマーS1と共重合させることができる。
As still another example of the monomer that can be included together with the monomer S1 as a monomer unit constituting the silicone oligomer Ps, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di Oxyalkylene di(meth)acrylates such as (meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate; monomers having a polyoxyalkylene skeleton, for example polyethylene Polyoxyalkylene chain such as glycol or polypropylene glycol has a polymerizable functional group such as (meth)acryloyl group, vinyl group or allyl group at one end and an ether structure (alkyl ether, aryl ether, aryl) at the other end. Polymerizable polyoxyalkylene ether having alkyl ether, etc.; methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, (meth)acrylic acid Alkoxyalkyl (meth)acrylates such as ethoxypropyl; salts such as alkali metal salts of (meth)acrylic acid; polyvalent (meth)acrylates such as trimethylolpropane tri(meth)acrylic acid ester: vinylidene chloride, (meth)acrylic Halogenated vinyl compounds such as acid-2-chloroethyl; 2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline and other oxazoline group-containing monomers; (meth) Aziridine group-containing monomers such as acryloyl aziridine and 2-aziridinylethyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, lactones and (meth) Hydroxyl group-containing vinyl monomer such as adduct with 2-hydroxyethyl acrylate; Fluorine-containing vinyl monomer such as fluorine-substituted (meth)acrylic acid alkyl ester; Reactive halogen-containing vinyl such as 2-chloroethyl vinyl ether and monochlorovinyl acetate Monomers: vinyltrimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, allyltrimethoxysilane, trimethoxysilylpropylallylamine, 2-methoxyethoxytrimethoxysilane Silicon-containing vinyl monomers; other macromonomers having a radically polymerizable vinyl group at the terminal of a vinyl group-polymerized monomer; and the like. These can be copolymerized alone or in combination with the monomer S1.
シリコーンオリゴマーPsの調製に用いられるモノマー成分がモノマーS1および(メタ)アクリル系モノマーを含む態様において、上記モノマー成分全体に占めるモノマーS1と(メタ)アクリル系モノマーとの合計量は、例えば50重量%以上であってよく、70重量%以上でもよく、85重量%以上でもよく、90重量%以上でもよく、95重量%以上でもよく、実質的に100重量%でもよい。
In an embodiment in which the monomer component used for the preparation of the silicone oligomer Ps includes the monomer S1 and the (meth)acrylic monomer, the total amount of the monomer S1 and the (meth)acrylic monomer in the entire monomer component is, for example, 50% by weight. The amount may be 70% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, or substantially 100% by weight.
上記モノマー成分に含まれる(メタ)アクリル系モノマーの組成は、例えば、当該(メタ)アクリル系モノマーの組成に基づくガラス転移温度Tm1が0℃より高くなるように設定することができる。ここで、(メタ)アクリル系モノマーの組成に基づくガラス転移温度Tm1とは、シリコーンオリゴマーPsの調製に用いられるモノマー成分のうち(メタ)アクリル系モノマーのみの組成に基づいて、Foxの式により求められるTgをいう。Tm1は、シリコーンオリゴマーPsの調製に用いられるモノマー成分のうち(メタ)アクリル系モノマーのみを対象として、上述したFoxの式を適用し、各(メタ)アクリル系モノマーのホモポリマーのガラス転移温度と、当該(メタ)アクリル系モノマーの合計量に占める各(メタ)アクリル系モノマー重量分率とから算出することができる。ガラス転移温度Tm1が0℃より高いシリコーンオリゴマーPsによると、初期粘着力が抑制されやすい。また、ガラス転移温度Tm1が0℃より高いシリコーンオリゴマーPsを用いることにより、粘着力上昇比の大きい粘着シートが得られやすい。
The composition of the (meth)acrylic monomer contained in the monomer component can be set such that the glass transition temperature T m1 based on the composition of the (meth)acrylic monomer is higher than 0° C., for example. Here, the glass transition temperature T m1 based on the composition of the (meth)acrylic monomer is based on the composition of only the (meth)acrylic monomer among the monomer components used for the preparation of the silicone oligomer Ps, and according to the Fox equation. Refers to the required Tg. T m1 is the glass transition temperature of the homopolymer of each (meth)acrylic monomer, which is obtained by applying the above-described Fox equation to only the (meth)acrylic monomer among the monomer components used for the preparation of the silicone oligomer Ps. And the weight fraction of each (meth)acrylic monomer in the total amount of the (meth)acrylic monomer. According to the silicone oligomer Ps having a glass transition temperature T m1 higher than 0° C., the initial adhesive force is easily suppressed. Further, by using the silicone oligomer Ps having a glass transition temperature T m1 higher than 0° C., it is easy to obtain a pressure-sensitive adhesive sheet having a large adhesive force increase ratio.
いくつかの態様において、Tm1は、-20℃以上でもよく、-10℃以上でもよく、0℃以上でもよく、10℃以上でもよい。Tm1が高くなると、貼付け初期の粘着力は、概して、よりよく抑制される傾向にある。また、Tm1は、例えば90℃以下でもよく、80℃以下でもよく、70℃以下または70℃未満でもよい。Tm1が低くなると、加熱による粘着力上昇が容易化する傾向にある。ここに開示される技術は、Tm1が、例えば-20℃~90℃、または-10℃~80℃、また0℃~70℃の範囲にあるシリコーンオリゴマーPsを用いて好ましく実施され得る。
In some embodiments, T m1 may be −20° C. or higher, −10° C. or higher, 0° C. or higher, or 10° C. or higher. At higher T m1, the adhesive strength in the early stage of application generally tends to be better suppressed. Further, T m1 may be, for example, 90° C. or lower, 80° C. or lower, 70° C. or lower, or lower than 70° C. When T m1 is low, increase in adhesive strength due to heating tends to be facilitated. The technique disclosed herein can be preferably carried out using a silicone oligomer Ps having T m1 in the range of, for example, −20° C. to 90° C., or −10° C. to 80° C., and 0° C. to 70° C.
シリコーンオリゴマーPsは、例えば、上述したモノマーを、溶液重合法、エマルション重合法、バルク重合法、懸濁重合法、光重合法等の既知の手法により重合させることで作製することができる。
The silicone oligomer Ps can be produced, for example, by polymerizing the above-mentioned monomer by a known method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or a photopolymerization method.
シリコーンオリゴマーPsの分子量を調整するために連鎖移動剤を用いることができる。使用する連鎖移動剤の例としては、オクチルメルカプタン、ラウリルメルカプタン、t-ノニルメルカプタン、t-ドデシルメルカプタン、メルカプトエタノール、α-チオグリセロール等のメルカプト基を有する化合物;チオグリコール酸、チオグリコール酸メチル、チオグリコール酸エチル、チオグリコール酸プロピル、チオグリコール酸ブチル、チオグリコール酸t-ブチル、チオグリコール酸2-エチルヘキシル、チオグリコール酸オクチル、チオグリコール酸イソオクチル、チオグリコール酸デシル、チオグリコール酸ドデシル、エチレングリコールのチオグリコール酸エステル、ネオペンチルグリコールのチオグリコール酸エステル、ペンタエリスリトールのチオグリコール酸エステル等のチオグリコール酸エステル類;α-メチルスチレンダイマー;等が挙げられる。
A chain transfer agent can be used to adjust the molecular weight of the silicone oligomer Ps. Examples of the chain transfer agent to be used include compounds having a mercapto group such as octyl mercaptan, lauryl mercaptan, t-nonyl mercaptan, t-dodecyl mercaptan, mercaptoethanol and α-thioglycerol; thioglycolic acid, methyl thioglycolate, Ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, ethylene Examples thereof include thioglycolic acid esters such as thioglycolic acid ester of glycol, thioglycolic acid ester of neopentyl glycol, and thioglycolic acid ester of pentaerythritol; α-methylstyrene dimer; and the like.
連鎖移動剤の使用量としては、特に制限されないが、通常、モノマー100重量部に対して、連鎖移動剤を0.05重量部~20重量部、好ましくは、0.1重量部~15重量部、さらに好ましくは0.2重量部~10重量部含有する。このように連鎖移動剤の添加量を調整することで、好適な分子量のシリコーンオリゴマーPsを得ることができる。なお、連鎖移動剤は、1種を単独でまたは2種以上を組み合わせて使用することができる。
The amount of the chain transfer agent used is not particularly limited, but is usually 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the monomer. And more preferably 0.2 to 10 parts by weight. By adjusting the addition amount of the chain transfer agent in this way, a silicone oligomer Ps having a suitable molecular weight can be obtained. The chain transfer agents may be used alone or in combination of two or more.
本発明の一実施形態において、シリコーンオリゴマーPsは、ベースポリマーである上述の(メタ)アクリル系ポリマー100重量部に対し、0.1~20重量部で含まれ得る。本発明の実施形態において、シリコーンオリゴマーPsは、上述の(メタ)アクリル系ポリマー100重量部に対し、好ましくは、0.25~10重量部で含まれ、より好ましくは、0.5~5重量部で含まれ得る。粘着剤層に含まれるシリコーンオリゴマーPsの含量が上記の範囲内であると、初期粘着力を抑制することができ、より高い加熱後粘着力を得ることができる。
In an embodiment of the present invention, the silicone oligomer Ps may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the above-mentioned (meth)acrylic polymer that is the base polymer. In the embodiment of the present invention, the silicone oligomer Ps is preferably contained in an amount of 0.25 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the above-mentioned (meth)acrylic polymer. May be included in the section. When the content of the silicone oligomer Ps contained in the adhesive layer is within the above range, the initial adhesive force can be suppressed and a higher adhesive force after heating can be obtained.
なお、上述のようなシリコーンオリゴマーPsは、粘着剤層に配合されることで、粘着力上昇遅延剤として好ましく機能し得る。ここに開示される粘着シートは、粘着剤層を構成する粘着剤がベースポリマーおよび粘着力上昇遅延剤を含み、該粘着力上昇遅延剤がシリコーンオリゴマーPsを含む態様で好ましく実施され得る。ここで、シリコーンオリゴマーPsが粘着力上昇遅延剤として機能するのは、被着体への貼付け前から貼付け初期の粘着シートにおいては粘着剤層の表面に存在するシリコーンオリゴマーPsによって初期粘着力が抑制され、貼付け後の経時や加熱等により粘着剤が流動することで粘着剤層表面におけるシリコーンオリゴマーPsの存在量が減少してシリコーンオリゴマーPsが粘着剤と相溶し、粘着力が上昇するためと考えられる。したがって、ここに開示される技術における上記粘着力上昇遅延剤としては、シリコーンオリゴマーPsに代えて、あるいはシリコーンオリゴマーPsと組み合わせて、同種の機能を発揮し得る他の材料が用いられ得る。そのような材料の非限定的な例として、分子内にポリオキシアルキレン構造を有するポリマー(以下「ポリマーPo」ともいう。)が挙げられる。ポリマーPoは、例えば、ポリオキシアルキレン骨格を有するモノマーに由来するモノマー単位を含む重合体であり得る。具体例としては、上述のようなポリオキシアルキレン骨格を有するモノマーのいずれか1種の単独重合体や2種以上の共重合体、ポリオキシアルキレン骨格を有するモノマーの1種または2種以上と他のモノマー(例えば、(メタ)アクリル系モノマー)との共重合体等をポリマーPoとして使用し得る。ポリオキシアルキレン骨格を有するモノマーの使用量は、特に限定されないが、例えば、上述したシリコーンオリゴマーPsにおけるモノマーS1の使用量を、ポリマーPoにおけるポリオキシアルキレン骨格を有するモノマーの使用量にも適用することができる。また、粘着剤層におけるポリマーPoの使用量は、特に限定されないが、例えば、上述したベースポリマーに対するシリコーンオリゴマーPsの使用量を、ベースポリマーに対するポリマーPoの使用量にも適用することができる。あるいは、上述したベースポリマーに対するシリコーンオリゴマーPsの使用量のうち一部(例えば、シリコーンオリゴマーPsの全使用量のうち5重量%~95重量%程度、または15重量%~85重量%程度、または30重量%~70重量%程度)をポリマーPoに置き換えてもよい。
Incidentally, the silicone oligomer Ps as described above can function favorably as an agent for increasing the adhesive strength by being mixed in the adhesive layer. The pressure-sensitive adhesive sheet disclosed herein can be preferably implemented in a mode in which the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer contains a base polymer and a pressure-sensitive adhesive force increase retarder, and the pressure-sensitive adhesive force increase retarder contains a silicone oligomer Ps. Here, the silicone oligomer Ps functions as an adhesive force increase retarder because the initial adhesive force is suppressed by the silicone oligomer Ps existing on the surface of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet from before attachment to the adherend and in the initial stage of attachment. As a result, the amount of the silicone oligomer Ps present on the surface of the pressure-sensitive adhesive layer decreases due to the pressure-sensitive adhesive flowing due to the passage of time after application, heating, etc., and the silicone oligomer Ps is compatible with the pressure-sensitive adhesive, increasing the adhesive strength. Conceivable. Therefore, as the above-mentioned adhesive force increase retarder in the technology disclosed herein, other materials capable of exhibiting the same kind of function may be used instead of the silicone oligomer Ps or in combination with the silicone oligomer Ps. A non-limiting example of such a material is a polymer having a polyoxyalkylene structure in the molecule (hereinafter, also referred to as “polymer Po”). The polymer Po can be, for example, a polymer including a monomer unit derived from a monomer having a polyoxyalkylene skeleton. Specific examples thereof include homopolymers or copolymers of any one of the above-mentioned monomers having a polyoxyalkylene skeleton, and one or more of monomers having a polyoxyalkylene skeleton and others. A copolymer with the monomer (eg, a (meth)acrylic monomer) or the like can be used as the polymer Po. The amount of the monomer having a polyoxyalkylene skeleton is not particularly limited, but for example, the amount of the monomer S1 used in the silicone oligomer Ps described above may be applied to the amount of the monomer having a polyoxyalkylene skeleton in the polymer Po. You can The amount of the polymer Po used in the pressure-sensitive adhesive layer is not particularly limited. For example, the amount of the silicone oligomer Ps used for the base polymer described above can be applied to the amount of the polymer Po used for the base polymer. Alternatively, a part of the amount of the silicone oligomer Ps used with respect to the above-mentioned base polymer (for example, about 5% by weight to 95% by weight, or about 15% by weight to 85% by weight of the total amount of the silicone oligomer Ps used, or 30 % To about 70% by weight) may be replaced with the polymer Po.
本発明の一実施形態において、シリコーンオリゴマーPsの溶融温度は、-20~120℃であってよい。本発明の別の実施形態において、シリコーンオリゴマーPsの溶融温度は、-10~90℃、0~80℃であってよい。
In one embodiment of the present invention, the melting temperature of the silicone oligomer Ps may be -20 to 120°C. In another embodiment of the present invention, the melting temperature of the silicone oligomer Ps may be −10 to 90° C., 0 to 80° C.
<その他の成分>
(架橋剤)
本明細書に開示される粘着剤層には、凝集力の調整等の目的で、架橋剤が用いられ得る。架橋剤は、通常用いる架橋剤を使用することができ、例えば、エポキシ系架橋剤、イソシアネート系架橋剤、シリコーン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、シラン系架橋剤、アルキルエーテル化メラミン系架橋剤、金属キレート系架橋剤等を挙げることができる。特に、イソシアネート系架橋剤、エポキシ系架橋剤、金属キレート系架橋剤を好適に使用することができる。架橋剤は、1種を単独でまたは2種以上を組み合わせて用いることができる。 <Other ingredients>
(Crosslinking agent)
A crosslinking agent may be used in the pressure-sensitive adhesive layer disclosed in the present specification for the purpose of adjusting cohesive force and the like. As the cross-linking agent, a commonly used cross-linking agent can be used, and examples thereof include epoxy cross-linking agents, isocyanate cross-linking agents, silicone cross-linking agents, oxazoline cross-linking agents, aziridine cross-linking agents, silane cross-linking agents, alkyl etherifications. Examples thereof include a melamine-based crosslinking agent and a metal chelate-based crosslinking agent. In particular, an isocyanate cross-linking agent, an epoxy cross-linking agent, and a metal chelate cross-linking agent can be preferably used. The cross-linking agents can be used alone or in combination of two or more.
(架橋剤)
本明細書に開示される粘着剤層には、凝集力の調整等の目的で、架橋剤が用いられ得る。架橋剤は、通常用いる架橋剤を使用することができ、例えば、エポキシ系架橋剤、イソシアネート系架橋剤、シリコーン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、シラン系架橋剤、アルキルエーテル化メラミン系架橋剤、金属キレート系架橋剤等を挙げることができる。特に、イソシアネート系架橋剤、エポキシ系架橋剤、金属キレート系架橋剤を好適に使用することができる。架橋剤は、1種を単独でまたは2種以上を組み合わせて用いることができる。 <Other ingredients>
(Crosslinking agent)
A crosslinking agent may be used in the pressure-sensitive adhesive layer disclosed in the present specification for the purpose of adjusting cohesive force and the like. As the cross-linking agent, a commonly used cross-linking agent can be used, and examples thereof include epoxy cross-linking agents, isocyanate cross-linking agents, silicone cross-linking agents, oxazoline cross-linking agents, aziridine cross-linking agents, silane cross-linking agents, alkyl etherifications. Examples thereof include a melamine-based crosslinking agent and a metal chelate-based crosslinking agent. In particular, an isocyanate cross-linking agent, an epoxy cross-linking agent, and a metal chelate cross-linking agent can be preferably used. The cross-linking agents can be used alone or in combination of two or more.
具体的には、イソシアネート系架橋剤の例としては、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添ジフェニルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート、ナフタリンジイソシアネート、トリフェニルメタントリイソシアネート、ポリメチレンポリフェニルイソシアネート、および、これらとトリメチロールプロパン等のポリオールとのアダクト体を挙げることができる。あるいは、1分子中に少なくとも1つ以上のイソシアネート基と、1つ以上の不飽和結合を有する化合物、具体的には、2-イソシアナートエチル(メタ)アクリレートなどもイソシアネート系架橋剤として使用することができる。これらは1種を単独でまたは2種以上を組み合わせて用いることができる。
Specifically, examples of the isocyanate cross-linking agent include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene. Examples thereof include diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, and adducts of these with polyols such as trimethylolpropane. Alternatively, a compound having at least one or more isocyanate group and one or more unsaturated bond in one molecule, specifically 2-isocyanatoethyl (meth)acrylate, etc., should also be used as an isocyanate cross-linking agent. You can These may be used alone or in combination of two or more.
エポキシ系架橋剤としては、ビスフェノールA、エピクロルヒドリン型のエポキシ系樹脂、エチレングリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、1,6-ヘキサンジオールグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、ジアミングリシジルアミン、N,N,N’,N’-テトラグリシジル-m-キシリレンジアミンおよび1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン等を挙げることができる。これらは1種を単独でまたは2種以上を組み合わせて用いることができる。
Epoxy crosslinking agents include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane tri Glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N,N,N',N'-tetraglycidyl-m-xylylenediamine and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane You can These may be used alone or in combination of two or more.
金属キレート化合物としては、金属成分としてアルミニウム、鉄、スズ、チタン、ニッケルなど、キレート成分としてアセチレン、アセト酢酸メチル、乳酸エチルなどが挙げられる。これらは1種を単独でまたは2種以上を組み合わせて用いることができる。
Examples of the metal chelate compound include aluminum, iron, tin, titanium and nickel as metal components, and acetylene, methyl acetoacetate and ethyl lactate as chelate components. These may be used alone or in combination of two or more.
架橋剤の使用量は、ベースポリマー100重量部に対して、例えば0.01重量部以上とすることができ、0.05重量部以上とすることが好ましい。架橋剤の使用量の増大により、より高い凝集力が得られる傾向にある。いくつかの態様において、ベースポリマー100重量部に対する架橋剤の使用量は、0.1重量部以上であってもよく、0.5重量部以上であってもよく、1重量部以上であってもよい。一方、過度な凝集力向上によるタックの低下を避ける観点から、ベースポリマー100重量部に対する架橋剤の使用量は、通常、15重量部以下とすることが適当であり、10重量部以下としてもよく、5重量部以下としてもよい。シリコーンオリゴマーPsまたは他の粘着力上昇遅延剤を含む組成の粘着剤では、架橋剤の使用量が多過ぎないことは、粘着剤の流動性を利用して粘着力上昇遅延剤の使用効果をよりよく発現させる観点からも有利となり得る。
The amount of the crosslinking agent used can be, for example, 0.01 part by weight or more, and preferably 0.05 part by weight or more, based on 100 parts by weight of the base polymer. A higher cohesive force tends to be obtained by increasing the amount of the crosslinking agent used. In some embodiments, the amount of the cross-linking agent used may be 0.1 part by weight or more, 100 parts by weight or more, 0.5 parts by weight or more, and 1 part by weight or more. Good. On the other hand, from the viewpoint of avoiding a decrease in tack due to excessive improvement in cohesive force, the amount of the cross-linking agent to be used is usually 15 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the base polymer. It may be 5 parts by weight or less. In the PSA having a composition containing the silicone oligomer Ps or the other PSA retarder, the use amount of the crosslinking agent is not too large. It may be advantageous from the viewpoint of good expression.
本明細書に開示される技術は、架橋剤として少なくともイソシアネート系架橋剤を用いる態様で好ましく実施され得る。加熱後凝集力が高く、かつ粘着力上昇比が大きい粘着シートを実現しやすくする観点から、いくつかの態様において、ベースポリマー100重量部に対するイソシアネート系架橋剤の使用量は、例えば5重量部以下とすることができ、3重量部以下としてもよく、1重量部以下としてもよく、0.7重量部以下としてもよく、0.5重量部以下としてもよい。
The technique disclosed in the present specification can be preferably carried out in a mode in which at least an isocyanate cross-linking agent is used as the cross-linking agent. From the viewpoint of facilitating the realization of a pressure-sensitive adhesive sheet having a high cohesive force after heating and a high adhesive force increase ratio, in some embodiments, the amount of the isocyanate-based cross-linking agent based on 100 parts by weight of the base polymer is, for example, 5 parts by weight or less. It may be 3 parts by weight or less, 1 part by weight or less, 0.7 parts by weight or less, and 0.5 parts by weight or less.
上述したいずれかの架橋反応をより効果的に進行させるために、架橋触媒を用いてもよい。架橋触媒としては、例えばスズ系触媒(特にジラウリン酸ジオクチルスズ)を好ましく用いることができる。架橋触媒の使用量は特に制限されないが、例えば、ベースポリマー100重量部に対して凡そ0.0001重量部~1重量部とすることができる。
A cross-linking catalyst may be used in order to more effectively promote any of the above-mentioned cross-linking reactions. As the crosslinking catalyst, for example, a tin-based catalyst (particularly dioctyltin dilaurate) can be preferably used. The amount of the crosslinking catalyst used is not particularly limited, but can be, for example, approximately 0.0001 parts by weight to 1 part by weight with respect to 100 parts by weight of the base polymer.
(シランカップリング剤)
本明細書に開示される粘着剤層には、さらに、シランカップリング剤を含有することできる。シランカップリング剤を用いることにより、耐久性を向上させることができる。シランカップリング剤としては、任意の適切な官能基を有するものを用いることができる。具体的には、官能基としては、例えば、ビニル基、エポキシ基、アミノ基、メルカプト基、(メタ)アクリロキシ基、アセトアセチル基、イソシアネート基、スチリル基、ポリスルフィド基等が挙げられる。具体的には、例えば、ビニルトリエトキシシラン、ビニルトリプロポキシシラン、ビニルトリイソプロポキシシラン、ビニルトリブトキシシラン等のビニル基含有シランカップリング剤;γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランなどのエポキシ基含有シランカップリング剤;γ-アミノプロピルトリメトキシシラン、N-β-(アミノエチル)-γ-アミノプロピルメチルジメトキシシラン、N-(2-アミノエチル)3-アミノプロピルメチルジメトキシシラン、γ-トリエトキシシリル-N-(1,3-ジメチルブチリデン)プロピルアミン、N-フェニル-γ-アミノプロピルトリメトキシシラン等のアミノ基含有シランカップリング剤;γ-メルカプトプロピルメチルジメトキシシランなどのメルカプト基含有シランカップリング剤;p-スチリルトリメトキシシラン等のスチリル基含有シランカップリング剤;γ-アクリロキシプロピルトリメトキシシラン、γ-メタクリロキシプロピルトリエトキシランなどの(メタ)アクリル基含有シランカップリング剤;3-イソシアネートプロピルトリエトキシシランなどのイソシアネート基含有シランカップリング剤;ビス(トリエトキシシリルプロピル)テトラスルフィド等のポリスルフィド基含有シランカップリング剤などが挙げられる。シランカップリング剤は、例えば、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-メルカプトプロピルメチルジメトキシシランを好適に用いることができる。 (Silane coupling agent)
The pressure-sensitive adhesive layer disclosed in the present specification may further contain a silane coupling agent. The durability can be improved by using the silane coupling agent. As the silane coupling agent, one having any appropriate functional group can be used. Specific examples of the functional group include a vinyl group, an epoxy group, an amino group, a mercapto group, a (meth)acryloxy group, an acetoacetyl group, an isocyanate group, a styryl group, and a polysulfide group. Specifically, for example, vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, and vinyltributoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycine Epoxy group-containing silane coupling agents such as cidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, γ-triethoxysilyl-N-(1,3-dimethylbutylidene) Amino group-containing silane coupling agents such as propylamine and N-phenyl-γ-aminopropyltrimethoxysilane; mercapto group-containing silane coupling agents such as γ-mercaptopropylmethyldimethoxysilane; p-styryltrimethoxysilane and other styryls Group-containing silane coupling agent; (meth)acryl group-containing silane coupling agent such as γ-acryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane; isocyanate group-containing silane such as 3-isocyanatepropyltriethoxysilane Coupling agents; polysulfide group-containing silane coupling agents such as bis(triethoxysilylpropyl) tetrasulfide and the like. As the silane coupling agent, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and γ-mercaptopropylmethyldimethoxysilane are preferably used. You can
本明細書に開示される粘着剤層には、さらに、シランカップリング剤を含有することできる。シランカップリング剤を用いることにより、耐久性を向上させることができる。シランカップリング剤としては、任意の適切な官能基を有するものを用いることができる。具体的には、官能基としては、例えば、ビニル基、エポキシ基、アミノ基、メルカプト基、(メタ)アクリロキシ基、アセトアセチル基、イソシアネート基、スチリル基、ポリスルフィド基等が挙げられる。具体的には、例えば、ビニルトリエトキシシラン、ビニルトリプロポキシシラン、ビニルトリイソプロポキシシラン、ビニルトリブトキシシラン等のビニル基含有シランカップリング剤;γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランなどのエポキシ基含有シランカップリング剤;γ-アミノプロピルトリメトキシシラン、N-β-(アミノエチル)-γ-アミノプロピルメチルジメトキシシラン、N-(2-アミノエチル)3-アミノプロピルメチルジメトキシシラン、γ-トリエトキシシリル-N-(1,3-ジメチルブチリデン)プロピルアミン、N-フェニル-γ-アミノプロピルトリメトキシシラン等のアミノ基含有シランカップリング剤;γ-メルカプトプロピルメチルジメトキシシランなどのメルカプト基含有シランカップリング剤;p-スチリルトリメトキシシラン等のスチリル基含有シランカップリング剤;γ-アクリロキシプロピルトリメトキシシラン、γ-メタクリロキシプロピルトリエトキシランなどの(メタ)アクリル基含有シランカップリング剤;3-イソシアネートプロピルトリエトキシシランなどのイソシアネート基含有シランカップリング剤;ビス(トリエトキシシリルプロピル)テトラスルフィド等のポリスルフィド基含有シランカップリング剤などが挙げられる。シランカップリング剤は、例えば、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-メルカプトプロピルメチルジメトキシシランを好適に用いることができる。 (Silane coupling agent)
The pressure-sensitive adhesive layer disclosed in the present specification may further contain a silane coupling agent. The durability can be improved by using the silane coupling agent. As the silane coupling agent, one having any appropriate functional group can be used. Specific examples of the functional group include a vinyl group, an epoxy group, an amino group, a mercapto group, a (meth)acryloxy group, an acetoacetyl group, an isocyanate group, a styryl group, and a polysulfide group. Specifically, for example, vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, and vinyltributoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycine Epoxy group-containing silane coupling agents such as cidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, γ-triethoxysilyl-N-(1,3-dimethylbutylidene) Amino group-containing silane coupling agents such as propylamine and N-phenyl-γ-aminopropyltrimethoxysilane; mercapto group-containing silane coupling agents such as γ-mercaptopropylmethyldimethoxysilane; p-styryltrimethoxysilane and other styryls Group-containing silane coupling agent; (meth)acryl group-containing silane coupling agent such as γ-acryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane; isocyanate group-containing silane such as 3-isocyanatepropyltriethoxysilane Coupling agents; polysulfide group-containing silane coupling agents such as bis(triethoxysilylpropyl) tetrasulfide and the like. As the silane coupling agent, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and γ-mercaptopropylmethyldimethoxysilane are preferably used. You can
前記シランカップリング剤は、単独で使用してもよく、また2種以上を混合して使用してもよいが、全体としての含有量は、ベースポリマー100重量部に対し、前記シランカップリング剤0.001~5重量部が好ましく、さらには0.01~1重量部が好ましく、さらには0.02~1重量部がより好ましく、さらには0.05~0.6重量部が好ましい。
The silane coupling agent may be used alone or in combination of two or more kinds, but the total content is 100 parts by weight of the base polymer and the silane coupling agent. The amount is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, further preferably 0.02 to 1 part by weight, further preferably 0.05 to 0.6 part by weight.
その他、ここに開示される技術における粘着剤層は、本発明の効果が著しく妨げられない範囲で、粘着付与剤、レベリング剤、可塑剤、軟化剤、着色剤(染料、顔料等)、充填剤、帯電防止剤、老化防止剤、紫外線吸収剤、酸化防止剤、光安定剤、防腐剤等の、粘着剤に使用され得る公知の添加剤を必要に応じて含んでいてもよい。
In addition, the pressure-sensitive adhesive layer in the technique disclosed herein is a tackifier, a leveling agent, a plasticizer, a softening agent, a colorant (a dye, a pigment, etc.), a filler, etc. within a range that does not significantly impair the effects of the present invention. If necessary, known additives such as antistatic agents, antiaging agents, ultraviolet absorbers, antioxidants, light stabilizers and preservatives that can be used for pressure-sensitive adhesives may be included.
(粘着剤層の形成)
粘着剤層を形成する方法としては、例えば、前記粘着剤組成物を剥離処理したセパレータ等に塗布し、重合溶剤等を乾燥除去して粘着剤層を形成した後に偏光フィルムに転写する方法、または偏光フィルムに前記粘着剤組成物を塗布し、重合溶剤等を乾燥除去して粘着剤層を偏光フィルムに形成する方法等により作製される。なお、粘着剤の塗布にあたっては、適宜に、重合溶剤以外の一種以上の溶剤を新たに加えてもよい。 (Formation of adhesive layer)
As a method for forming a pressure-sensitive adhesive layer, for example, a method in which the pressure-sensitive adhesive composition is applied to a release-treated separator or the like, and a polymerization solvent or the like is dried and removed to form a pressure-sensitive adhesive layer, and then transferred to a polarizing film, or It is prepared by a method of applying the above-mentioned pressure-sensitive adhesive composition to a polarizing film, drying and removing a polymerization solvent and the like to form an adhesive layer on the polarizing film. When applying the pressure-sensitive adhesive, one or more solvents other than the polymerization solvent may be newly added as appropriate.
粘着剤層を形成する方法としては、例えば、前記粘着剤組成物を剥離処理したセパレータ等に塗布し、重合溶剤等を乾燥除去して粘着剤層を形成した後に偏光フィルムに転写する方法、または偏光フィルムに前記粘着剤組成物を塗布し、重合溶剤等を乾燥除去して粘着剤層を偏光フィルムに形成する方法等により作製される。なお、粘着剤の塗布にあたっては、適宜に、重合溶剤以外の一種以上の溶剤を新たに加えてもよい。 (Formation of adhesive layer)
As a method for forming a pressure-sensitive adhesive layer, for example, a method in which the pressure-sensitive adhesive composition is applied to a release-treated separator or the like, and a polymerization solvent or the like is dried and removed to form a pressure-sensitive adhesive layer, and then transferred to a polarizing film, or It is prepared by a method of applying the above-mentioned pressure-sensitive adhesive composition to a polarizing film, drying and removing a polymerization solvent and the like to form an adhesive layer on the polarizing film. When applying the pressure-sensitive adhesive, one or more solvents other than the polymerization solvent may be newly added as appropriate.
剥離処理したセパレータとしては、シリコーン剥離ライナーが好ましく用いられる。このようなライナー上に本発明の接着剤組成物を塗布、乾燥させて粘着剤層を形成する工程において、粘着剤を乾燥させる方法としては、目的に応じて、適宜、適切な方法が採用され得る。好ましくは、上記塗布膜を加熱乾燥する方法が用いられる。加熱乾燥温度は、好ましくは40℃~200℃であり、さらに好ましくは、50℃~180℃であり、特に好ましくは70℃~170℃である。加熱温度を上記の範囲とすることによって、優れた粘着特性を有する粘着剤を得ることができる。
A silicone release liner is preferably used as the release-treated separator. In the step of forming the pressure-sensitive adhesive layer by applying the adhesive composition of the present invention on such a liner, and drying the pressure-sensitive adhesive layer, as a method for drying the pressure-sensitive adhesive, an appropriate method is appropriately adopted depending on the purpose. obtain. Preferably, a method of heating and drying the above coating film is used. The heat drying temperature is preferably 40°C to 200°C, more preferably 50°C to 180°C, and particularly preferably 70°C to 170°C. By setting the heating temperature in the above range, a pressure-sensitive adhesive having excellent pressure-sensitive adhesive properties can be obtained.
乾燥時間は、適宜、適切な時間が採用され得る。上記乾燥時間は、好ましくは5秒間~20分間、さらに好ましくは5秒間~10分間、特に好ましくは、10秒間~5分間である。
As for the drying time, an appropriate time can be adopted as appropriate. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.
また、偏光フィルムの表面に、アンカー層を形成したり、コロナ処理、プラズマ処理等の各種易接着処理を施した後に粘着剤層を形成したりすることができる。また、粘着剤層の表面には易接着処理をおこなってもよい。
Also, an anchor layer can be formed on the surface of the polarizing film, or an adhesive layer can be formed after various types of easy adhesion treatment such as corona treatment and plasma treatment. Further, the surface of the pressure-sensitive adhesive layer may be subjected to easy adhesion treatment.
粘着剤層の形成方法としては、各種方法が用いられる。具体的には、例えば、ロールコート、キスロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、ディップロールコート、バーコート、ナイフコート、エアーナイフコート、カーテンコート、リップコート、ダイコーター等による押出しコート法等の方法が挙げられる。
Various methods are used to form the 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 of the method include an extrusion coating method.
粘着剤層の厚さは、特に制限されず、例えば、1~100μm程度である。好ましくは、2~50μm、より好ましくは2~40μmであり、さらに好ましくは、5~35μmである。
The thickness of the adhesive layer is not particularly limited and is, for example, about 1 to 100 μm. The thickness is preferably 2 to 50 μm, more preferably 2 to 40 μm, and further preferably 5 to 35 μm.
前記粘着剤層が露出する場合には、実用に供されるまで剥離処理したシート(セパレータ)で粘着剤層を保護してもよい。
When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a release-treated sheet (separator) until practical use.
セパレータの構成材料としては、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリエステルフィルム等のプラスチックフィルム、紙、布、不織布等の多孔質材料、ネット、発泡シート、金属箔、およびこれらのラミネート体等の適宜な薄葉体等を挙げることができるが、表面平滑性に優れる点からプラスチックフィルムが好適に用いられる。
As a constituent material of the separator, for example, polyethylene, polypropylene, polyethylene terephthalate, a plastic film such as a polyester film, a porous material such as paper, cloth, non-woven fabric, a net, a foamed sheet, a metal foil, and a laminated body thereof are appropriately used. Examples thereof include plastic thin films, and plastic films are preferably used because they have excellent surface smoothness.
そのプラスチックフィルムとしては、前記粘着剤層を保護し得るフィルムであれば特に限定されず、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフイルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン-酢酸ビニル共重合体フィルム等が挙げられる。
The plastic film is not particularly limited as long as it is a film capable of protecting the pressure-sensitive adhesive layer, and examples thereof include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film and vinyl chloride. Examples thereof include polymer films, polyethylene terephthalate films, polybutylene terephthalate films, polyurethane films, ethylene-vinyl acetate copolymer films and the like.
前記セパレータの厚みは、通常5~200μm、好ましくは5~100μm程度である。前記セパレータには、必要に応じて、シリコーン系、フッ素系、長鎖アルキル系もしくは脂肪酸アミド系の離型剤、シリカ粉等による離型および防汚処理や、塗布型、練り込み型、蒸着型等の帯電防止処理もすることもできる。特に、前記セパレータの表面にシリコーン処理、長鎖アルキル処理、フッ素処理等の剥離処理を適宜おこなうことにより、前記粘着剤層からの剥離性をより高めることができる。
The thickness of the separator is usually 5 to 200 μm, preferably about 5 to 100 μm. In the separator, if necessary, a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, release and antifouling treatment with silica powder or the like, coating type, kneading type, vapor deposition type It is also possible to perform antistatic treatment such as. Particularly, by appropriately performing a peeling treatment such as a silicone treatment, a long-chain alkyl treatment, or a fluorine treatment on the surface of the separator, the peelability from the pressure-sensitive adhesive layer can be further enhanced.
なお、上記の粘着剤層付き偏光フィルムの作製にあたって用いた、剥離処理したシートは、そのまま粘着剤層付き偏光フィルムのセパレータとして用いることができ、工程面における簡略化ができる。
The release-treated sheet used in the production of the pressure-sensitive adhesive layer-attached polarizing film can be used as it is as a separator for the pressure-sensitive adhesive layer-attached polarizing film, which simplifies the process.
以下に、本発明について実施例を挙げて説明するが、本発明は以下に示した実施例に制限されるものではない。なお、各例中の部および%はいずれも重量基準である。以下に特に規定のない室温放置条件は全て23℃65%RHである。
The present invention will be described below with reference to examples, but the present invention is not limited to the examples shown below. In addition, all parts and% in each example are based on weight. Unless otherwise specified below, the room temperature standing condition is 23° C. and 65% RH.
なお、下記の各ポリマーの重量平均分子量Mwは、GPC装置(東ソー社製、HLC-8220GPC)を用いて下記の条件で測定を行い、ポリスチレン換算により求めた。
・サンプル濃度:0.2wt%(テトラヒドロフラン(THF)溶液)
・サンプル注入量:10μl
・溶離液:THF・流速:0.6ml/min
・測定温度:40℃ The weight average molecular weight Mw of each of the following polymers was determined by using a GPC device (manufactured by Tosoh Corporation, HLC-8220GPC) under the following conditions, and calculated in terms of polystyrene.
-Sample concentration: 0.2 wt% (tetrahydrofuran (THF) solution)
・Sample injection volume: 10 μl
・Eluent: THF ・Flow rate: 0.6 ml/min
・Measuring temperature: 40℃
・サンプル濃度:0.2wt%(テトラヒドロフラン(THF)溶液)
・サンプル注入量:10μl
・溶離液:THF・流速:0.6ml/min
・測定温度:40℃ The weight average molecular weight Mw of each of the following polymers was determined by using a GPC device (manufactured by Tosoh Corporation, HLC-8220GPC) under the following conditions, and calculated in terms of polystyrene.
-Sample concentration: 0.2 wt% (tetrahydrofuran (THF) solution)
・Sample injection volume: 10 μl
・Eluent: THF ・Flow rate: 0.6 ml/min
・Measuring temperature: 40℃
<偏光子の作製>
平均重合度2400、ケン化度99.9モル%の厚み75μmのポリビニルアルコールフィルムを、30℃の温水中に60秒間浸漬し膨潤させた。次いで、ヨウ素/ヨウ化カリウム(重量比=0.5/8)の濃度0.3%の水溶液に浸漬し、3.5倍まで延伸させながらフィルムを染色した。その後、65℃のホウ酸エステル水溶液中で、トータルの延伸倍率が6倍となるように延伸を行った。延伸後に、40℃のオーブンにて3分間乾燥を行い、PVA系偏光子(SP値32.8、厚み23μm)を得た。水分率は14重量%であった。 <Production of polarizer>
A polyvinyl alcohol film having an average polymerization degree of 2400 and a saponification degree of 99.9 mol% and a thickness of 75 μm was dipped in warm water at 30° C. for 60 seconds to be swollen. Next, the film was immersed in an aqueous solution of iodine/potassium iodide (weight ratio=0.5/8) having a concentration of 0.3%, and the film was dyed while stretching up to 3.5 times. Then, stretching was performed in a boric acid ester aqueous solution at 65° C. so that the total stretching ratio was 6 times. After stretching, it was dried in an oven at 40° C. for 3 minutes to obtain a PVA-based polarizer (SP value 32.8, thickness 23 μm). The water content was 14% by weight.
平均重合度2400、ケン化度99.9モル%の厚み75μmのポリビニルアルコールフィルムを、30℃の温水中に60秒間浸漬し膨潤させた。次いで、ヨウ素/ヨウ化カリウム(重量比=0.5/8)の濃度0.3%の水溶液に浸漬し、3.5倍まで延伸させながらフィルムを染色した。その後、65℃のホウ酸エステル水溶液中で、トータルの延伸倍率が6倍となるように延伸を行った。延伸後に、40℃のオーブンにて3分間乾燥を行い、PVA系偏光子(SP値32.8、厚み23μm)を得た。水分率は14重量%であった。 <Production of polarizer>
A polyvinyl alcohol film having an average polymerization degree of 2400 and a saponification degree of 99.9 mol% and a thickness of 75 μm was dipped in warm water at 30° C. for 60 seconds to be swollen. Next, the film was immersed in an aqueous solution of iodine/potassium iodide (weight ratio=0.5/8) having a concentration of 0.3%, and the film was dyed while stretching up to 3.5 times. Then, stretching was performed in a boric acid ester aqueous solution at 65° C. so that the total stretching ratio was 6 times. After stretching, it was dried in an oven at 40° C. for 3 minutes to obtain a PVA-based polarizer (SP value 32.8, thickness 23 μm). The water content was 14% by weight.
<透明保護フィルムの作製>
厚み40μm、透湿度60g/m2/24hのアクリル系樹脂フィルム(SP値22.2)の易接着処理面にコロナ処理を施して用いた。 <Preparation of transparent protective film>
The acrylic resin film (SP value 22.2) having a thickness of 40 μm and a water vapor permeability of 60 g/m 2 /24 h was subjected to corona treatment before use.
厚み40μm、透湿度60g/m2/24hのアクリル系樹脂フィルム(SP値22.2)の易接着処理面にコロナ処理を施して用いた。 <Preparation of transparent protective film>
The acrylic resin film (SP value 22.2) having a thickness of 40 μm and a water vapor permeability of 60 g/m 2 /24 h was subjected to corona treatment before use.
<活性エネルギー線>
活性エネルギー線として、
・紫外線照射装置(ガリウム封入メタルハライドランプ):Fusion UV Systems,Inc社製Light HAMMER10
・バルブ:Vバルブ
・ピーク照度:1600mW/cm2、
・積算照射量1000/mJ/cm2(波長380~440nm)を使用した。なお、紫外線の照度は、Solatell社製Sola-Checkシステムを使用して測定した。 <Active energy ray>
As active energy rays,
・Ultraviolet irradiation device (gallium-encapsulated metal halide lamp): Fusion UV Systems, Inc. Light HAMMER10
・Valve: V valve ・Peak illuminance: 1600 mW/cm 2 ,
An integrated dose of 1000/mJ/cm 2 (wavelength 380 to 440 nm) was used. The illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell.
活性エネルギー線として、
・紫外線照射装置(ガリウム封入メタルハライドランプ):Fusion UV Systems,Inc社製Light HAMMER10
・バルブ:Vバルブ
・ピーク照度:1600mW/cm2、
・積算照射量1000/mJ/cm2(波長380~440nm)を使用した。なお、紫外線の照度は、Solatell社製Sola-Checkシステムを使用して測定した。 <Active energy ray>
As active energy rays,
・Ultraviolet irradiation device (gallium-encapsulated metal halide lamp): Fusion UV Systems, Inc. Light HAMMER10
・Valve: V valve ・Peak illuminance: 1600 mW/cm 2 ,
An integrated dose of 1000/mJ/cm 2 (wavelength 380 to 440 nm) was used. The illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell.
<活性エネルギー線硬化型接着剤の調製>
ラジカル重合性化合物(A)として、N-ヒドロキシエチルアクリルアミド(SP値2
9.6,ホモポリマーのTg123℃,興人社製)を38.3部、 ラジカル重合性化合物(B)として、トリプロピレングリコールジアクリレート(商品名:アロニックスM-220,SP値19.0,ホモポリマーのTg69℃,東亞合成社製)を19.1部、 ラジカル重合性化合物(C)として、アクリロイルモルホリン(SP値22.9,ホモポリマーのTg150℃,興人社製)を38.3部、および 光重合開始剤(商品名:KAYACURE DETX-S,ジエチルチオキサントン,日本化薬社製)1.4部を混合して50℃で1時間撹拌して活性エネルギー線硬化型接着剤を得た。 <Preparation of active energy ray-curable adhesive>
As the radically polymerizable compound (A), N-hydroxyethyl acrylamide (SP value 2
9.6, homopolymer Tg123° C., manufactured by Kojin Co., Ltd., 38.3 parts, and as a radically polymerizable compound (B), tripropylene glycol diacrylate (trade name: Aronix M-220, SP value 19.0, Homopolymer Tg 69° C., manufactured by Toagosei Co., Ltd. 19.1 parts, and acryloylmorpholine (SP value 22.9, homopolymer Tg 150° C., manufactured by Kojin Co., Ltd.) 38.3 as the radically polymerizable compound (C). And 1.4 parts of a photopolymerization initiator (trade name: KAYACURE DETX-S, diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) are mixed and stirred at 50° C. for 1 hour to obtain an active energy ray-curable adhesive. It was
ラジカル重合性化合物(A)として、N-ヒドロキシエチルアクリルアミド(SP値2
9.6,ホモポリマーのTg123℃,興人社製)を38.3部、 ラジカル重合性化合物(B)として、トリプロピレングリコールジアクリレート(商品名:アロニックスM-220,SP値19.0,ホモポリマーのTg69℃,東亞合成社製)を19.1部、 ラジカル重合性化合物(C)として、アクリロイルモルホリン(SP値22.9,ホモポリマーのTg150℃,興人社製)を38.3部、および 光重合開始剤(商品名:KAYACURE DETX-S,ジエチルチオキサントン,日本化薬社製)1.4部を混合して50℃で1時間撹拌して活性エネルギー線硬化型接着剤を得た。 <Preparation of active energy ray-curable adhesive>
As the radically polymerizable compound (A), N-hydroxyethyl acrylamide (
9.6, homopolymer Tg123° C., manufactured by Kojin Co., Ltd., 38.3 parts, and as a radically polymerizable compound (B), tripropylene glycol diacrylate (trade name: Aronix M-220, SP value 19.0, Homopolymer Tg 69° C., manufactured by Toagosei Co., Ltd. 19.1 parts, and acryloylmorpholine (SP value 22.9, homopolymer Tg 150° C., manufactured by Kojin Co., Ltd.) 38.3 as the radically polymerizable compound (C). And 1.4 parts of a photopolymerization initiator (trade name: KAYACURE DETX-S, diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) are mixed and stirred at 50° C. for 1 hour to obtain an active energy ray-curable adhesive. It was
<偏光フィルムAの作製>
上記アクリル系樹脂フィルム上に、厚さ0.5μmのウレタン系易接着剤層を形成した後に、当該易接着剤層に、上記活性エネルギー線硬化型接着剤を、MCDコーター(富士機械社製)(セル形状:ハニカム、グラビアロール線数:1000本/inch、回転速度140%/対ライン速)を用いて、接着剤層の厚みが0.5μmになるように塗工した。次いで、前記接着剤を介して、前記アクリル系樹脂フィルムを、視認側およびパネル側の透明保護フィルムとして、上記偏光子の両面にロール機で貼り合わせた。その後、貼り合わせたアクリル系樹脂フィルムの両側から、IRヒーターを用いて50℃に加温し、上記紫外線を両面に照射して、活性エネルギー線硬化型接着剤を硬化させた。さらに、70℃で3分間熱風乾燥して、偏光子の両面に透明保護フィルムを有する偏光フィルムAを得た(表1)。貼り合わせのライン速度は25m/minで行った。 <Production of Polarizing Film A>
After forming a urethane-based easy-adhesive layer having a thickness of 0.5 μm on the acrylic resin film, the active energy ray-curable adhesive was applied to the easy-adhesive layer by an MCD coater (manufactured by Fuji Machine Co., Ltd.). (Cell shape: honeycomb, gravure roll number of lines: 1000/inch, rotation speed 140%/vs line speed) was used to coat the adhesive layer to a thickness of 0.5 μm. Next, the acrylic resin film was bonded to both sides of the above-mentioned polarizer by a roll machine as a transparent protective film on the viewing side and the panel side via the adhesive. Then, the both sides of the bonded acrylic resin film were heated to 50° C. using an IR heater, and both sides were irradiated with the above-mentioned ultraviolet rays to cure the active energy ray-curable adhesive. Further, it was dried with hot air at 70° C. for 3 minutes to obtain a polarizing film A having transparent protective films on both sides of the polarizer (Table 1). The bonding line speed was 25 m/min.
上記アクリル系樹脂フィルム上に、厚さ0.5μmのウレタン系易接着剤層を形成した後に、当該易接着剤層に、上記活性エネルギー線硬化型接着剤を、MCDコーター(富士機械社製)(セル形状:ハニカム、グラビアロール線数:1000本/inch、回転速度140%/対ライン速)を用いて、接着剤層の厚みが0.5μmになるように塗工した。次いで、前記接着剤を介して、前記アクリル系樹脂フィルムを、視認側およびパネル側の透明保護フィルムとして、上記偏光子の両面にロール機で貼り合わせた。その後、貼り合わせたアクリル系樹脂フィルムの両側から、IRヒーターを用いて50℃に加温し、上記紫外線を両面に照射して、活性エネルギー線硬化型接着剤を硬化させた。さらに、70℃で3分間熱風乾燥して、偏光子の両面に透明保護フィルムを有する偏光フィルムAを得た(表1)。貼り合わせのライン速度は25m/minで行った。 <Production of Polarizing Film A>
After forming a urethane-based easy-adhesive layer having a thickness of 0.5 μm on the acrylic resin film, the active energy ray-curable adhesive was applied to the easy-adhesive layer by an MCD coater (manufactured by Fuji Machine Co., Ltd.). (Cell shape: honeycomb, gravure roll number of lines: 1000/inch, rotation speed 140%/vs line speed) was used to coat the adhesive layer to a thickness of 0.5 μm. Next, the acrylic resin film was bonded to both sides of the above-mentioned polarizer by a roll machine as a transparent protective film on the viewing side and the panel side via the adhesive. Then, the both sides of the bonded acrylic resin film were heated to 50° C. using an IR heater, and both sides were irradiated with the above-mentioned ultraviolet rays to cure the active energy ray-curable adhesive. Further, it was dried with hot air at 70° C. for 3 minutes to obtain a polarizing film A having transparent protective films on both sides of the polarizer (Table 1). The bonding line speed was 25 m/min.
<アンカーコート層の作製>
(アンカー層塗布液Aの調製およびアンカーコート層Aの形成)
固形分でウレタン系ポリマーを30~90重量%、およびポリチオフェン系ポリマーを10~50重量%含む溶液[ナガセケムテックス社製商品名「デナトロンP-580W」と固形分でオキサゾリン基含有アクリル系ポリマーを10~70重量%、およびポリオキシエチレン基含有メタクリレートを10~70重量%含む溶液[日本触媒社製商品名「エポクロスWS-700」を、水100重量%の(混合)溶液中に添加し、固形分濃度(ベース濃度)が0.4重量%となるように調製した。調製後の溶液をマイヤーバー#5を用いて、前記偏光フィルムの視認側とは反対面のアクリルフィルム側に塗布し、乾燥オーブンに入れるまでの時間(乾燥を開始するまでの時間)を5秒設けた後、50℃で25秒間乾燥させ、厚み48nmのアンカーコート層Aを形成した。乾燥厚みから計算される乾燥前の塗布厚は約12μmであった。作業は、23℃55%RH雰囲気化で行った。また塗れ性を向上させるドライ処理として、プラズマ処理またはコロナ処理を施してもよい。 <Preparation of anchor coat layer>
(Preparation of anchor layer coating liquid A and formation of anchor coat layer A)
A solution containing 30 to 90% by weight of a urethane-based polymer and 10 to 50% by weight of a polythiophene-based polymer in terms of solid content [Nagase Chemtex's trade name "Denatron P-580W" and oxazoline group-containing acrylic polymer in terms of solid content A solution containing 10 to 70% by weight and a polyoxyethylene group-containing methacrylate of 10 to 70% by weight [Nippon Shokubai Co., Ltd. trade name "Epocros WS-700" was added to a 100% by weight water (mixed) solution, The solid content concentration (base concentration) was adjusted to 0.4% by weight. The prepared solution was applied to the acrylic film side opposite to the visible side of the polarizing film by usingMeyer bar # 5, and the time until the oven was placed in a drying oven (the time until the drying was started) was 5 seconds. After providing, it was dried at 50° C. for 25 seconds to form an anchor coat layer A having a thickness of 48 nm. The coating thickness before drying calculated from the dry thickness was about 12 μm. The work was performed in a 23° C. 55% RH atmosphere. Plasma treatment or corona treatment may be performed as dry treatment for improving wettability.
(アンカー層塗布液Aの調製およびアンカーコート層Aの形成)
固形分でウレタン系ポリマーを30~90重量%、およびポリチオフェン系ポリマーを10~50重量%含む溶液[ナガセケムテックス社製商品名「デナトロンP-580W」と固形分でオキサゾリン基含有アクリル系ポリマーを10~70重量%、およびポリオキシエチレン基含有メタクリレートを10~70重量%含む溶液[日本触媒社製商品名「エポクロスWS-700」を、水100重量%の(混合)溶液中に添加し、固形分濃度(ベース濃度)が0.4重量%となるように調製した。調製後の溶液をマイヤーバー#5を用いて、前記偏光フィルムの視認側とは反対面のアクリルフィルム側に塗布し、乾燥オーブンに入れるまでの時間(乾燥を開始するまでの時間)を5秒設けた後、50℃で25秒間乾燥させ、厚み48nmのアンカーコート層Aを形成した。乾燥厚みから計算される乾燥前の塗布厚は約12μmであった。作業は、23℃55%RH雰囲気化で行った。また塗れ性を向上させるドライ処理として、プラズマ処理またはコロナ処理を施してもよい。 <Preparation of anchor coat layer>
(Preparation of anchor layer coating liquid A and formation of anchor coat layer A)
A solution containing 30 to 90% by weight of a urethane-based polymer and 10 to 50% by weight of a polythiophene-based polymer in terms of solid content [Nagase Chemtex's trade name "Denatron P-580W" and oxazoline group-containing acrylic polymer in terms of solid content A solution containing 10 to 70% by weight and a polyoxyethylene group-containing methacrylate of 10 to 70% by weight [Nippon Shokubai Co., Ltd. trade name "Epocros WS-700" was added to a 100% by weight water (mixed) solution, The solid content concentration (base concentration) was adjusted to 0.4% by weight. The prepared solution was applied to the acrylic film side opposite to the visible side of the polarizing film by using
(アンカー層塗布液Bの調製およびアンカーコート層Bの形成)
固形分でウレタン系ポリマーを50重量%以上含む溶液[ナガセケムテックス社製 商品名「デナトロンB-510C」]と固形分でオキサゾリン基含有アクリル系ポリマーを10~70重量%、およびポリオキシエチレン基含有メタクリレートを10~70重量%含む溶液[日本触媒社製商品名「エポクロスWS-700」を、水100重量%の(混合)溶液中に添加し、固形分濃度(ベース濃度)が0.2重量%となるように調製した。調製後の溶液をマイヤーバー#5を用いて、前記偏光フィルムの視認側とは反対面のアクリルフィルム側に塗布し、乾燥オーブンに入れるまでの時間(乾燥を開始するまでの時間)を5秒設けた後、50℃で25秒間乾燥させ、厚み48nmのアンカーコート層Bを形成した。乾燥厚みから計算される乾燥前の塗布厚は約12μmであった。作業は、23℃55%RH雰囲気化で行った。また塗れ性を向上させるドライ処理として、プラズマ処理またはコロナ処理を施してもよい。 (Preparation of anchor layer coating liquid B and formation of anchor coat layer B)
A solution containing 50% by weight or more of urethane polymer in solid content [Nagase Chemtex's trade name "Denatron B-510C"] and 10 to 70% by weight of oxazoline group-containing acrylic polymer in solid content, and polyoxyethylene group A solution containing 10 to 70% by weight of the contained methacrylate [Nippon Shokubai Co., Ltd., trade name "Epocros WS-700" was added to a 100% by weight water (mixed) solution to give a solid content concentration (base concentration) of 0.2. It was prepared so as to be wt%. The prepared solution was applied to the acrylic film side opposite to the visible side of the polarizing film by usingMeyer bar # 5, and the time until the oven was placed in a drying oven (the time until the drying was started) was 5 seconds. After being provided, it was dried at 50° C. for 25 seconds to form an anchor coat layer B having a thickness of 48 nm. The coating thickness before drying calculated from the dry thickness was about 12 μm. The work was performed in a 23° C. 55% RH atmosphere. Plasma treatment or corona treatment may be performed as dry treatment for improving wettability.
固形分でウレタン系ポリマーを50重量%以上含む溶液[ナガセケムテックス社製 商品名「デナトロンB-510C」]と固形分でオキサゾリン基含有アクリル系ポリマーを10~70重量%、およびポリオキシエチレン基含有メタクリレートを10~70重量%含む溶液[日本触媒社製商品名「エポクロスWS-700」を、水100重量%の(混合)溶液中に添加し、固形分濃度(ベース濃度)が0.2重量%となるように調製した。調製後の溶液をマイヤーバー#5を用いて、前記偏光フィルムの視認側とは反対面のアクリルフィルム側に塗布し、乾燥オーブンに入れるまでの時間(乾燥を開始するまでの時間)を5秒設けた後、50℃で25秒間乾燥させ、厚み48nmのアンカーコート層Bを形成した。乾燥厚みから計算される乾燥前の塗布厚は約12μmであった。作業は、23℃55%RH雰囲気化で行った。また塗れ性を向上させるドライ処理として、プラズマ処理またはコロナ処理を施してもよい。 (Preparation of anchor layer coating liquid B and formation of anchor coat layer B)
A solution containing 50% by weight or more of urethane polymer in solid content [Nagase Chemtex's trade name "Denatron B-510C"] and 10 to 70% by weight of oxazoline group-containing acrylic polymer in solid content, and polyoxyethylene group A solution containing 10 to 70% by weight of the contained methacrylate [Nippon Shokubai Co., Ltd., trade name "Epocros WS-700" was added to a 100% by weight water (mixed) solution to give a solid content concentration (base concentration) of 0.2. It was prepared so as to be wt%. The prepared solution was applied to the acrylic film side opposite to the visible side of the polarizing film by using
アンカーコート層の組成について、下記表2に示す。
The composition of the anchor coat layer is shown in Table 2 below.
<粘着剤の調製>
(ポリマー溶液Aの調製)
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、アクリル酸ブチル100部、アクリル酸5部、アクリル酸2-ヒドロキシエチル0.075部および2,2’-アゾビスイソブチロニトリル0.3部を酢酸エチルと共に加えて溶液を調製した。次いで、この溶液に窒素ガスを吹き込みながら撹拌して、60℃で4時間反応させて、重量平均Mwが220万のアクリル系ポリマーを含有する溶液を得た。さらに、このアクリル系ポリマーを含有する溶液に、酢酸エチルを加えて固形分濃度を30%に調整したアクリル系ポリマー溶液Aを得た。 <Preparation of adhesive>
(Preparation of polymer solution A)
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 100 parts of butyl acrylate, 5 parts of acrylic acid, 0.075 parts of 2-hydroxyethyl acrylate and 2,2'-azobisisobutyrate. A solution was prepared by adding 0.3 part of ronitrile together with ethyl acetate. Next, this solution was stirred while blowing nitrogen gas and reacted at 60° C. for 4 hours to obtain a solution containing an acrylic polymer having a weight average Mw of 2,200,000. Further, ethyl acetate was added to the solution containing the acrylic polymer to obtain an acrylic polymer solution A in which the solid content concentration was adjusted to 30%.
(ポリマー溶液Aの調製)
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、アクリル酸ブチル100部、アクリル酸5部、アクリル酸2-ヒドロキシエチル0.075部および2,2’-アゾビスイソブチロニトリル0.3部を酢酸エチルと共に加えて溶液を調製した。次いで、この溶液に窒素ガスを吹き込みながら撹拌して、60℃で4時間反応させて、重量平均Mwが220万のアクリル系ポリマーを含有する溶液を得た。さらに、このアクリル系ポリマーを含有する溶液に、酢酸エチルを加えて固形分濃度を30%に調整したアクリル系ポリマー溶液Aを得た。 <Preparation of adhesive>
(Preparation of polymer solution A)
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 100 parts of butyl acrylate, 5 parts of acrylic acid, 0.075 parts of 2-hydroxyethyl acrylate and 2,2'-azobisisobutyrate. A solution was prepared by adding 0.3 part of ronitrile together with ethyl acetate. Next, this solution was stirred while blowing nitrogen gas and reacted at 60° C. for 4 hours to obtain a solution containing an acrylic polymer having a weight average Mw of 2,200,000. Further, ethyl acetate was added to the solution containing the acrylic polymer to obtain an acrylic polymer solution A in which the solid content concentration was adjusted to 30%.
前記アクリル系ポリマー溶液Aの固形分100部に対して、架橋剤として、0.6部のイソシアネート基を有する化合物を主成分とする架橋剤(日本ポリウレタン(株)製,商品名「コロネートL」)と、シランカップリング剤として、0.075部のγ-グリシドキシプロピルトリメトキシシラン(信越化学工業(株)製,商品名「KBM-403」)とをこの順に配合して、粘着剤ポリマー溶液Aを調製した。
As a cross-linking agent, based on 100 parts of the solid content of the acrylic polymer solution A, a cross-linking agent containing 0.6 part of a compound having an isocyanate group as a main component (manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate L") ) And 0.075 part of γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”) as a silane coupling agent in this order, and the adhesive agent Polymer solution A was prepared.
(ポリマー溶液Bの調製)
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、2-エチルヘキシルアクリレート(2EHA)94部、アクリル酸6部および2,2’-アゾビスイソブチロニトリル0.3部を酢酸エチルと共に加えて溶液を調製した。次いで、この溶液に窒素ガスを吹き込みながら撹拌して、60℃で4時間反応させて、重量平均分子量Mwが220万のアクリル系ポリマーを含有する溶液を得た。さらに、このアクリル系ポリマーを含有する溶液に、酢酸エチルを加えて固形分濃度を30%に調整したアクリル系ポリマー溶液(B)を得た。 (Preparation of polymer solution B)
In a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer and a stirrer, 94 parts of 2-ethylhexyl acrylate (2EHA), 6 parts of acrylic acid and 0.3 parts of 2,2′-azobisisobutyronitrile are added. A solution was prepared by adding together with ethyl acetate. Then, the solution was stirred while blowing nitrogen gas and reacted at 60° C. for 4 hours to obtain a solution containing an acrylic polymer having a weight average molecular weight Mw of 2.2 million. Further, ethyl acetate was added to the solution containing the acrylic polymer to obtain an acrylic polymer solution (B) in which the solid content concentration was adjusted to 30%.
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、2-エチルヘキシルアクリレート(2EHA)94部、アクリル酸6部および2,2’-アゾビスイソブチロニトリル0.3部を酢酸エチルと共に加えて溶液を調製した。次いで、この溶液に窒素ガスを吹き込みながら撹拌して、60℃で4時間反応させて、重量平均分子量Mwが220万のアクリル系ポリマーを含有する溶液を得た。さらに、このアクリル系ポリマーを含有する溶液に、酢酸エチルを加えて固形分濃度を30%に調整したアクリル系ポリマー溶液(B)を得た。 (Preparation of polymer solution B)
In a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer and a stirrer, 94 parts of 2-ethylhexyl acrylate (2EHA), 6 parts of acrylic acid and 0.3 parts of 2,2′-azobisisobutyronitrile are added. A solution was prepared by adding together with ethyl acetate. Then, the solution was stirred while blowing nitrogen gas and reacted at 60° C. for 4 hours to obtain a solution containing an acrylic polymer having a weight average molecular weight Mw of 2.2 million. Further, ethyl acetate was added to the solution containing the acrylic polymer to obtain an acrylic polymer solution (B) in which the solid content concentration was adjusted to 30%.
前記アクリル系ポリマー溶液(B)の固形分100部に対して、架橋剤として、0.6部のイソシアネート基を有する化合物を主成分とする架橋剤(日本ポリウレタン(株)製,商品名「コロネートL」)と、シランカップリング剤として、0.075部のγ-グリシドキシプロピルトリメトキシシラン(信越化学工業(株)製,商品名「KBM-403」)とをこの順に配合して、粘着剤ポリマー溶液Bを調製した。
As a cross-linking agent, a cross-linking agent containing 0.6 part of a compound having an isocyanate group as a main component based on 100 parts of the solid content of the acrylic polymer solution (B) (manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate") L”) and 0.075 part of γ-glycidoxypropyltrimethoxysilane (trade name “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent in this order, An adhesive polymer solution B was prepared.
(ポリマー溶液Cの調製)
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、アクリル酸ブチル99部、アクリル酸4-ヒドロキシブチル1.0部、及び2、2-アゾビスイソブチロニトリルをモノマー(固形分)100部に対して0.3部を酢酸エチルと共に加えて窒素ガス気流下、60℃で4時間反応させた後、その反応液に酢酸エチルを加えて、重量平均分子量165万のアクリル系ポリマーを含有するポリマー溶液Cを得た(固形分濃度30重量%)。 (Preparation of polymer solution C)
In a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer and a stirring device, 99 parts of butyl acrylate, 1.0 part of 4-hydroxybutyl acrylate, and 2,2-azobisisobutyronitrile were used as monomers ( (Solid content) 0.3 part with respect to 100 parts was added together with ethyl acetate and reacted at 60° C. for 4 hours under a nitrogen gas stream, and then ethyl acetate was added to the reaction solution to give an acryl having a weight average molecular weight of 1,650,000. A polymer solution C containing a base polymer was obtained (solid content concentration 30% by weight).
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、アクリル酸ブチル99部、アクリル酸4-ヒドロキシブチル1.0部、及び2、2-アゾビスイソブチロニトリルをモノマー(固形分)100部に対して0.3部を酢酸エチルと共に加えて窒素ガス気流下、60℃で4時間反応させた後、その反応液に酢酸エチルを加えて、重量平均分子量165万のアクリル系ポリマーを含有するポリマー溶液Cを得た(固形分濃度30重量%)。 (Preparation of polymer solution C)
In a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer and a stirring device, 99 parts of butyl acrylate, 1.0 part of 4-hydroxybutyl acrylate, and 2,2-azobisisobutyronitrile were used as monomers ( (Solid content) 0.3 part with respect to 100 parts was added together with ethyl acetate and reacted at 60° C. for 4 hours under a nitrogen gas stream, and then ethyl acetate was added to the reaction solution to give an acryl having a weight average molecular weight of 1,650,000. A polymer solution C containing a base polymer was obtained (solid content concentration 30% by weight).
前記アクリル系ポリマー溶液Cの固形分100部あたり0.3部のジベンゾイルパーオキシド(日本油脂製(株):ナイパーBMT)と、0.1部のトリメチロールプロパンキシリレンジイソシアネート(三井武田ケミカル(株):タケネートD110N)と、0.2部のシランカップリング剤(綜研化学株式会社製:A-100、アセトアセチル基含有シランカップリング剤)を配合して、粘着剤ポリマー溶液Cを調製した。
0.3 part of dibenzoyl peroxide (Nippon Yushi Co., Ltd.: Niper BMT) and 0.1 part of trimethylolpropane xylylene diisocyanate (Mitsui Takeda Chemical ( Co., Ltd.: Takenate D110N) and 0.2 part of a silane coupling agent (manufactured by Soken Chemical Industry Co., Ltd.: A-100, acetoacetyl group-containing silane coupling agent) were mixed to prepare an adhesive polymer solution C. ..
アクリル系ポリマー溶液(A)(ポリマーA)、アクリル系ポリマー溶液(B)(ポリマーB)、およびアクリル系ポリマー溶液(C)(ポリマーC)の組成を下記表3に示す。
The compositions of the acrylic polymer solution (A) (polymer A), the acrylic polymer solution (B) (polymer B), and the acrylic polymer solution (C) (polymer C) are shown in Table 3 below.
(シリコーンオリゴマーAの調製)
撹拌羽根、温度計、窒素ガス導入管、冷却器、滴下ロートを備えた4つ口フラスコに、酢酸エチル100部、MMA40部、n-ブチルメタクリレート(BMA)20部、2-エチルヘキシルメタクリレート(2EHMA)20部、官能基当量が900g/molのポリオルガノシロキサン骨格含有メタクリレートモノマー(商品名:X-22-174ASX、信越化学工業株式会社製)8.7部、官能基当量が4600g/molのポリオルガノシロキサン骨格含有メタクリレートモノマー(商品名:KF-2012、信越化学工業株式会社製)11.3部および連鎖移動剤としてチオグリコール酸メチル0.2部を投入した。そして、70℃にて窒素雰囲気下で1時間撹拌した後、熱重合開始剤として2,2’-アゾビスイソブチロニトリル0.2部を投入し、70℃で2時間反応させた後に、熱重合開始剤として2,2’-アゾビスイソブチロニトリル0.1部を投入し、続いて80℃で3時間反応させた。このようにしてシリコーンオリゴマーAの溶液を得た。このシリコーンオリゴマーAの重量平均分子量Mwは18000であった。 (Preparation of Silicone Oligomer A)
A 4-neck flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a condenser, and a dropping funnel, 100 parts of ethyl acetate, 40 parts of MMA, 20 parts of n-butyl methacrylate (BMA), and 2-ethylhexyl methacrylate (2EHMA). 20 parts, polyorganosiloxane skeleton-containing methacrylate monomer having a functional group equivalent of 900 g/mol (trade name: X-22-174ASX, manufactured by Shin-Etsu Chemical Co., Ltd.) 8.7 parts, polyorgano having a functional group equivalent of 4600 g/mol. 11.3 parts of a siloxane skeleton-containing methacrylate monomer (trade name: KF-2012, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.2 part of methyl thioglycolate as a chain transfer agent were added. Then, after stirring at 70° C. under a nitrogen atmosphere for 1 hour, 0.2 part of 2,2′-azobisisobutyronitrile was added as a thermal polymerization initiator, and after reacting at 70° C. for 2 hours, As a thermal polymerization initiator, 0.1 part of 2,2′-azobisisobutyronitrile was added, and the reaction was continued at 80° C. for 3 hours. Thus, a solution of silicone oligomer A was obtained. The weight average molecular weight Mw of this silicone oligomer A was 18,000.
撹拌羽根、温度計、窒素ガス導入管、冷却器、滴下ロートを備えた4つ口フラスコに、酢酸エチル100部、MMA40部、n-ブチルメタクリレート(BMA)20部、2-エチルヘキシルメタクリレート(2EHMA)20部、官能基当量が900g/molのポリオルガノシロキサン骨格含有メタクリレートモノマー(商品名:X-22-174ASX、信越化学工業株式会社製)8.7部、官能基当量が4600g/molのポリオルガノシロキサン骨格含有メタクリレートモノマー(商品名:KF-2012、信越化学工業株式会社製)11.3部および連鎖移動剤としてチオグリコール酸メチル0.2部を投入した。そして、70℃にて窒素雰囲気下で1時間撹拌した後、熱重合開始剤として2,2’-アゾビスイソブチロニトリル0.2部を投入し、70℃で2時間反応させた後に、熱重合開始剤として2,2’-アゾビスイソブチロニトリル0.1部を投入し、続いて80℃で3時間反応させた。このようにしてシリコーンオリゴマーAの溶液を得た。このシリコーンオリゴマーAの重量平均分子量Mwは18000であった。 (Preparation of Silicone Oligomer A)
A 4-neck flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a condenser, and a dropping funnel, 100 parts of ethyl acetate, 40 parts of MMA, 20 parts of n-butyl methacrylate (BMA), and 2-ethylhexyl methacrylate (2EHMA). 20 parts, polyorganosiloxane skeleton-containing methacrylate monomer having a functional group equivalent of 900 g/mol (trade name: X-22-174ASX, manufactured by Shin-Etsu Chemical Co., Ltd.) 8.7 parts, polyorgano having a functional group equivalent of 4600 g/mol. 11.3 parts of a siloxane skeleton-containing methacrylate monomer (trade name: KF-2012, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.2 part of methyl thioglycolate as a chain transfer agent were added. Then, after stirring at 70° C. under a nitrogen atmosphere for 1 hour, 0.2 part of 2,2′-azobisisobutyronitrile was added as a thermal polymerization initiator, and after reacting at 70° C. for 2 hours, As a thermal polymerization initiator, 0.1 part of 2,2′-azobisisobutyronitrile was added, and the reaction was continued at 80° C. for 3 hours. Thus, a solution of silicone oligomer A was obtained. The weight average molecular weight Mw of this silicone oligomer A was 18,000.
(その他のシリコーンオリゴマーB~Fの調製)
シリコーンオリゴマーB~Fについては、モノマー組成および質量部を表4に記載の構成成分に変更したこと以外は、シリコーンオリゴマーAと同様にして作製した。 (Preparation of other silicone oligomers B to F)
Silicone oligomers B to F were prepared in the same manner as silicone oligomer A, except that the monomer composition and parts by weight were changed to the constituent components shown in Table 4.
シリコーンオリゴマーB~Fについては、モノマー組成および質量部を表4に記載の構成成分に変更したこと以外は、シリコーンオリゴマーAと同様にして作製した。 (Preparation of other silicone oligomers B to F)
Silicone oligomers B to F were prepared in the same manner as silicone oligomer A, except that the monomer composition and parts by weight were changed to the constituent components shown in Table 4.
(粘着剤溶液の調製)
上記調製した粘着剤ポリマー溶液Aに、1部のシリコーンオリゴマーAを配合して、実施例1で用いるアクリル系粘着剤溶液を調製した。同様にして、下記表5に記載された粘着剤ポリマー溶液とシリコーンオリゴマーとを用いて、実施例2~24で用いるアクリル系粘着剤溶液を調製した。 (Preparation of adhesive solution)
The acrylic polymer solution A prepared above was mixed with 1 part of the silicone oligomer A to prepare an acrylic adhesive solution used in Example 1. Similarly, the acrylic adhesive solutions used in Examples 2 to 24 were prepared using the adhesive polymer solutions and silicone oligomers shown in Table 5 below.
上記調製した粘着剤ポリマー溶液Aに、1部のシリコーンオリゴマーAを配合して、実施例1で用いるアクリル系粘着剤溶液を調製した。同様にして、下記表5に記載された粘着剤ポリマー溶液とシリコーンオリゴマーとを用いて、実施例2~24で用いるアクリル系粘着剤溶液を調製した。 (Preparation of adhesive solution)
The acrylic polymer solution A prepared above was mixed with 1 part of the silicone oligomer A to prepare an acrylic adhesive solution used in Example 1. Similarly, the acrylic adhesive solutions used in Examples 2 to 24 were prepared using the adhesive polymer solutions and silicone oligomers shown in Table 5 below.
(粘着剤層付き偏光フィルムの作製)
[実施例1]~[実施例24]
次いで、上記アクリル系粘着剤溶液を、シリコーン系剥離剤で処理されたポリエチレンテレフタレートフィルム(セパレータフィルム)の表面に均一に塗工し、155℃の空気循環式恒温オーブンで2分間乾燥し、セパレータフィルムの表面に厚さ20μmの粘着剤層を形成した。上記偏光フィルムAまたはBの片面に、粘着剤層を形成したセパレータを移着させ、粘着剤層付き偏光フィルムを作製した。 (Production of polarizing film with adhesive layer)
[Example 1] to [Example 24]
Then, the acrylic pressure-sensitive adhesive solution is uniformly applied to the surface of a polyethylene terephthalate film (separator film) treated with a silicone-based release agent, and dried for 2 minutes in an air circulation type constant temperature oven at 155° C. to form a separator film. An adhesive layer having a thickness of 20 μm was formed on the surface of. The separator having the pressure-sensitive adhesive layer formed thereon was transferred to one surface of the polarizing film A or B to prepare a pressure-sensitive adhesive layer-attached polarizing film.
[実施例1]~[実施例24]
次いで、上記アクリル系粘着剤溶液を、シリコーン系剥離剤で処理されたポリエチレンテレフタレートフィルム(セパレータフィルム)の表面に均一に塗工し、155℃の空気循環式恒温オーブンで2分間乾燥し、セパレータフィルムの表面に厚さ20μmの粘着剤層を形成した。上記偏光フィルムAまたはBの片面に、粘着剤層を形成したセパレータを移着させ、粘着剤層付き偏光フィルムを作製した。 (Production of polarizing film with adhesive layer)
[Example 1] to [Example 24]
Then, the acrylic pressure-sensitive adhesive solution is uniformly applied to the surface of a polyethylene terephthalate film (separator film) treated with a silicone-based release agent, and dried for 2 minutes in an air circulation type constant temperature oven at 155° C. to form a separator film. An adhesive layer having a thickness of 20 μm was formed on the surface of. The separator having the pressure-sensitive adhesive layer formed thereon was transferred to one surface of the polarizing film A or B to prepare a pressure-sensitive adhesive layer-attached polarizing film.
[比較例1]
比較例1において、シリコーンオリゴマーAを除いたこと以外は実施例1と同じようにして、粘着剤層付き偏光フィルムを作製した。 [Comparative Example 1]
A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the silicone oligomer A was removed in Comparative Example 1.
比較例1において、シリコーンオリゴマーAを除いたこと以外は実施例1と同じようにして、粘着剤層付き偏光フィルムを作製した。 [Comparative Example 1]
A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the silicone oligomer A was removed in Comparative Example 1.
[比較例2]~[比較例5]
比較例2~5において、シリコーンオリゴマーAの代わりにエーテル基含有ポリシロキサン(信越化学工業株式会社製、商品名「変性シリコーンオイル KF-353」)を用い、配合量を表5に示すように変えたこと以外は実施例1と同じようにして、粘着剤層付き偏光フィルムを作製した。 [Comparative Example 2] to [Comparative Example 5]
In Comparative Examples 2 to 5, an ether group-containing polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “modified silicone oil KF-353”) was used in place of the silicone oligomer A, and the compounding amount was changed as shown in Table 5. A polarizing film with an adhesive layer was produced in the same manner as in Example 1 except for the above.
比較例2~5において、シリコーンオリゴマーAの代わりにエーテル基含有ポリシロキサン(信越化学工業株式会社製、商品名「変性シリコーンオイル KF-353」)を用い、配合量を表5に示すように変えたこと以外は実施例1と同じようにして、粘着剤層付き偏光フィルムを作製した。 [Comparative Example 2] to [Comparative Example 5]
In Comparative Examples 2 to 5, an ether group-containing polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “modified silicone oil KF-353”) was used in place of the silicone oligomer A, and the compounding amount was changed as shown in Table 5. A polarizing film with an adhesive layer was produced in the same manner as in Example 1 except for the above.
[参考例1]
参考例1において、シリコーンオリゴマーAの代わりに別のリワーク向上剤(カネカ社製、商品名「SAT10」)を用い、配合量を表5に示すように変えたこと以外は実施例1と同じようにして、粘着剤層付き偏光フィルムを作製した。 [Reference Example 1]
Same as Example 1 except that another rework improver (manufactured by Kaneka, trade name "SAT10") was used in place of the silicone oligomer A in Reference Example 1 and the compounding amount was changed as shown in Table 5. Then, a polarizing film with an adhesive layer was produced.
参考例1において、シリコーンオリゴマーAの代わりに別のリワーク向上剤(カネカ社製、商品名「SAT10」)を用い、配合量を表5に示すように変えたこと以外は実施例1と同じようにして、粘着剤層付き偏光フィルムを作製した。 [Reference Example 1]
Same as Example 1 except that another rework improver (manufactured by Kaneka, trade name "SAT10") was used in place of the silicone oligomer A in Reference Example 1 and the compounding amount was changed as shown in Table 5. Then, a polarizing film with an adhesive layer was produced.
上記実施例1~24、比較例1~5、および参考例1で得られた粘着剤層付き偏光フィルムについて、下記評価を行った。結果を表5に示す。
The following evaluation was performed on the polarizing film with the adhesive layer obtained in Examples 1 to 24, Comparative Examples 1 to 5 and Reference Example 1. The results are shown in Table 5.
<耐久性の評価>
粘着剤層付偏光フィルム(15インチ)のセパレータフィルムを剥がし、厚さ0.7mmの無アルカリガラス(コーニング社製,EG-XG)にラミネーターを用いて貼着した。次いで、50℃、0.5MPaで、15分間のオートクレーブ処理を行って、前記偏光フィルムを完全に無アルカリガラスに密着させた。次いで、これを、80℃の加熱オーブン(加熱)条件下にそれぞれ投入して、500時間後の偏光板の剥がれの有無を、下記基準で評価した。
A:全く剥がれが認められなかった。
B:目視で確認できない程度の発泡が認められた。
C:目視では確認できない程度の剥がれが認められた。
D:目視で確認できる小さな発泡または剥がれが認められた。
E:明らかな発泡または剥がれが認められた。 <Evaluation of durability>
The separator film of the pressure-sensitive adhesive layer-attached polarizing film (15 inches) was peeled off and adhered to a 0.7 mm-thick non-alkali glass (EG-XG, manufactured by Corning Incorporated) using a laminator. Then, autoclave treatment was carried out at 50° C. and 0.5 MPa for 15 minutes to completely adhere the polarizing film to the alkali-free glass. Next, this was put into a heating oven (heating) condition of 80° C., and the presence or absence of peeling of the polarizing plate after 500 hours was evaluated based on the following criteria.
A: No peeling was observed at all.
B: Foaming was recognized to the extent that it could not be visually confirmed.
C: Peeling that could not be visually confirmed was observed.
D: Small bubbles or peeling that can be visually confirmed were observed.
E: Clear foaming or peeling was recognized.
粘着剤層付偏光フィルム(15インチ)のセパレータフィルムを剥がし、厚さ0.7mmの無アルカリガラス(コーニング社製,EG-XG)にラミネーターを用いて貼着した。次いで、50℃、0.5MPaで、15分間のオートクレーブ処理を行って、前記偏光フィルムを完全に無アルカリガラスに密着させた。次いで、これを、80℃の加熱オーブン(加熱)条件下にそれぞれ投入して、500時間後の偏光板の剥がれの有無を、下記基準で評価した。
A:全く剥がれが認められなかった。
B:目視で確認できない程度の発泡が認められた。
C:目視では確認できない程度の剥がれが認められた。
D:目視で確認できる小さな発泡または剥がれが認められた。
E:明らかな発泡または剥がれが認められた。 <Evaluation of durability>
The separator film of the pressure-sensitive adhesive layer-attached polarizing film (15 inches) was peeled off and adhered to a 0.7 mm-thick non-alkali glass (EG-XG, manufactured by Corning Incorporated) using a laminator. Then, autoclave treatment was carried out at 50° C. and 0.5 MPa for 15 minutes to completely adhere the polarizing film to the alkali-free glass. Next, this was put into a heating oven (heating) condition of 80° C., and the presence or absence of peeling of the polarizing plate after 500 hours was evaluated based on the following criteria.
A: No peeling was observed at all.
B: Foaming was recognized to the extent that it could not be visually confirmed.
C: Peeling that could not be visually confirmed was observed.
D: Small bubbles or peeling that can be visually confirmed were observed.
E: Clear foaming or peeling was recognized.
<粘着力の評価>
(1)初期粘着力の測定
23℃、50%RHの標準環境下にて、作製した粘着剤層付偏光フィルムを、縦120mm×横25mmに裁断したものをサンプルとした。当該サンプルを、厚さ0.7mmの無アルカリガラス板(コーニング社製、EG-XG)に、2kgのローラーを1往復させて圧着した後、当該サンプルの粘着力を測定した。粘着力は、当該サンプルを引張り試験機(オートグラフSHIMAZU AG-1 1OKN)にて、剥離角度90°、剥離速度300mm/minで引き剥がす際の粘着力(N/25mm、測定長80mm)を測定することにより求めた。測定は、1回/0.5sの間隔で200回サンプリングし、その平均値を測定値とした。検体数は3検体で行った。それらの平均値を初期粘着力として表5の「2kgローラー」の欄に示した。そして粘着力の水準からリワーク性を下記基準で判断した。
A:4N/25mm以下、リワークは90%成功する。
B:4N/25mm超5N/25mm以下、リワークは80%以上成功する。
C:5N/25mm超6N/25mm以下、リワークは70%以上成功する。
D:6N/25mm超7N/25mm以下、リワークは60%以上成功する。
E:7N/25mm超、リワークは40%より多く失敗する。 <Evaluation of adhesive strength>
(1) Measurement of initial adhesive strength A polarizing film with an adhesive layer produced was cut into a sample having a length of 120 mm and a width of 25 mm under a standard environment of 23° C. and 50% RH as a sample. The sample was pressure-bonded to a 0.7 mm-thick non-alkali glass plate (EG-XG, manufactured by Corning Inc.) by reciprocating a 2 kg roller once, and then the adhesive force of the sample was measured. The adhesive force is measured by a tensile tester (Autograph SHIMAZU AG-1 1OKN) at a peeling angle of 90° and a peeling speed of 300 mm/min. (N/25 mm, measuring length 80 mm) Was obtained by doing. The measurement was performed 200 times at intervals of 1 time/0.5 s, and the average value was used as the measured value. The number of samples was three. The average value thereof is shown in the column of "2 kg roller" in Table 5 as the initial adhesive strength. Then, the reworkability was judged based on the level of adhesive strength according to the following criteria.
A: 4 N/25 mm or less, rework is 90% successful.
B: More than 4 N/25 mm and 5 N/25 mm or less, and rework succeeds 80% or more.
C: More than 5N/25mm and 6N/25mm or less, and rework succeeds 70% or more.
D: More than 6 N/25 mm and 7 N/25 mm or less, and rework succeeds 60% or more.
E: Over 7 N/25 mm, rework fails more than 40%.
(1)初期粘着力の測定
23℃、50%RHの標準環境下にて、作製した粘着剤層付偏光フィルムを、縦120mm×横25mmに裁断したものをサンプルとした。当該サンプルを、厚さ0.7mmの無アルカリガラス板(コーニング社製、EG-XG)に、2kgのローラーを1往復させて圧着した後、当該サンプルの粘着力を測定した。粘着力は、当該サンプルを引張り試験機(オートグラフSHIMAZU AG-1 1OKN)にて、剥離角度90°、剥離速度300mm/minで引き剥がす際の粘着力(N/25mm、測定長80mm)を測定することにより求めた。測定は、1回/0.5sの間隔で200回サンプリングし、その平均値を測定値とした。検体数は3検体で行った。それらの平均値を初期粘着力として表5の「2kgローラー」の欄に示した。そして粘着力の水準からリワーク性を下記基準で判断した。
A:4N/25mm以下、リワークは90%成功する。
B:4N/25mm超5N/25mm以下、リワークは80%以上成功する。
C:5N/25mm超6N/25mm以下、リワークは70%以上成功する。
D:6N/25mm超7N/25mm以下、リワークは60%以上成功する。
E:7N/25mm超、リワークは40%より多く失敗する。 <Evaluation of adhesive strength>
(1) Measurement of initial adhesive strength A polarizing film with an adhesive layer produced was cut into a sample having a length of 120 mm and a width of 25 mm under a standard environment of 23° C. and 50% RH as a sample. The sample was pressure-bonded to a 0.7 mm-thick non-alkali glass plate (EG-XG, manufactured by Corning Inc.) by reciprocating a 2 kg roller once, and then the adhesive force of the sample was measured. The adhesive force is measured by a tensile tester (Autograph SHIMAZU AG-1 1OKN) at a peeling angle of 90° and a peeling speed of 300 mm/min. (N/25 mm, measuring length 80 mm) Was obtained by doing. The measurement was performed 200 times at intervals of 1 time/0.5 s, and the average value was used as the measured value. The number of samples was three. The average value thereof is shown in the column of "2 kg roller" in Table 5 as the initial adhesive strength. Then, the reworkability was judged based on the level of adhesive strength according to the following criteria.
A: 4 N/25 mm or less, rework is 90% successful.
B: More than 4 N/25 mm and 5 N/25 mm or less, and rework succeeds 80% or more.
C: More than 5N/25mm and 6N/25mm or less, and rework succeeds 70% or more.
D: More than 6 N/25 mm and 7 N/25 mm or less, and rework succeeds 60% or more.
E: Over 7 N/25 mm, rework fails more than 40%.
(2)加熱後粘着力の測定
作製した粘着剤層付偏光フィルムを、縦120mm×横25mmに裁断したものをサンプルとした。当該サンプルを、厚さ0.7mmの無アルカリガラス板(コーニング社製、EG-XG)に、ラミネーターを用いて貼り付け、次いで50℃、5atmで15分間オートクレーブ処理して完全に密着させた後、当該サンプルの粘着力を測定した。粘着力は、当該サンプルを引張り試験機(オートグラフSHIMAZU AG-1 1OKN)にて、剥離角度90°、剥離速度300mm/minで引き剥がす際の粘着力(N/25mm、測定長80mm)を測定することにより求めた。測定は、1回/0.5sの間隔で200回サンプリングし、その平均値を測定値とした。検体数は3検体で行った。表5中、「60℃×2h」および「60℃×24h」は、60℃でそれぞれ2時間および24時間放置した後の粘着力を示す。 (2) Measurement of adhesive strength after heating The produced polarizing film with an adhesive layer was cut into a length of 120 mm and a width of 25 mm to obtain a sample. The sample was attached to a 0.7 mm-thick non-alkali glass plate (EG-XG, manufactured by Corning Incorporated) using a laminator, and then autoclaved at 50° C. and 5 atm for 15 minutes for complete adhesion. The adhesive strength of the sample was measured. The adhesive force is measured by a tensile tester (Autograph SHIMAZU AG-1 1OKN) at a peeling angle of 90° and a peeling speed of 300 mm/min. (N/25 mm, measuring length 80 mm) Was obtained by doing. The measurement was performed 200 times at intervals of 1 time/0.5 s, and the average value was used as the measured value. The number of samples was three. In Table 5, “60° C.×2 h” and “60° C.×24 h” indicate the adhesive force after standing at 60° C. for 2 hours and 24 hours, respectively.
作製した粘着剤層付偏光フィルムを、縦120mm×横25mmに裁断したものをサンプルとした。当該サンプルを、厚さ0.7mmの無アルカリガラス板(コーニング社製、EG-XG)に、ラミネーターを用いて貼り付け、次いで50℃、5atmで15分間オートクレーブ処理して完全に密着させた後、当該サンプルの粘着力を測定した。粘着力は、当該サンプルを引張り試験機(オートグラフSHIMAZU AG-1 1OKN)にて、剥離角度90°、剥離速度300mm/minで引き剥がす際の粘着力(N/25mm、測定長80mm)を測定することにより求めた。測定は、1回/0.5sの間隔で200回サンプリングし、その平均値を測定値とした。検体数は3検体で行った。表5中、「60℃×2h」および「60℃×24h」は、60℃でそれぞれ2時間および24時間放置した後の粘着力を示す。 (2) Measurement of adhesive strength after heating The produced polarizing film with an adhesive layer was cut into a length of 120 mm and a width of 25 mm to obtain a sample. The sample was attached to a 0.7 mm-thick non-alkali glass plate (EG-XG, manufactured by Corning Incorporated) using a laminator, and then autoclaved at 50° C. and 5 atm for 15 minutes for complete adhesion. The adhesive strength of the sample was measured. The adhesive force is measured by a tensile tester (Autograph SHIMAZU AG-1 1OKN) at a peeling angle of 90° and a peeling speed of 300 mm/min. (N/25 mm, measuring length 80 mm) Was obtained by doing. The measurement was performed 200 times at intervals of 1 time/0.5 s, and the average value was used as the measured value. The number of samples was three. In Table 5, “60° C.×2 h” and “60° C.×24 h” indicate the adhesive force after standing at 60° C. for 2 hours and 24 hours, respectively.
<粘着剤層の投錨力の測定方法>インジウムスズ酸化物を蒸着処理したポリエチレンテレフタレートフィルム[尾池工業(株)製商品名「125テトライトOES」(厚み125μm)]の処理面に、25mm幅の粘着剤層付き偏光フィルムを、2kgローラーで1往復圧着し、23℃で1分間養成後、かかるポリエチレンテレフタレートフィルムを粘着剤層ごと180度方向に300mm/分で引き剥がす際の接着強度を測定した。そして投錨力は下記基準で判定した。
A:15N/25mm以上
B:10N/25mm以上15N/25mm未満
C:7.5N/25mm以上10N/25mm未満
D:7.5N/25mm未満
E:2kgローラー圧着後の粘着力より低い <Measuring method of anchoring force of pressure-sensitive adhesive layer> A polyethylene terephthalate film [Oike Industry Co., Ltd., trade name "125 Tetraite OES" (thickness 125 μm)] having a 25 mm width, which was vapor-deposited with indium tin oxide, was used. The polarizing film with the pressure-sensitive adhesive layer was pressure-bonded back and forth once with a 2 kg roller and cured at 23° C. for 1 minute, and the adhesive strength was measured when the polyethylene terephthalate film was peeled together with the pressure-sensitive adhesive layer in the 180° direction at 300 mm/min. .. Then, the anchoring power was judged according to the following criteria.
A: 15 N/25 mm or more B: 10 N/25 mm or more and 15 N/25 mm or less C: 7.5 N/25 mm or more and 10 N/25 mm or less D: 7.5 N/25 mm or less E: 2 kg Lower than the adhesive strength after roller pressure bonding
A:15N/25mm以上
B:10N/25mm以上15N/25mm未満
C:7.5N/25mm以上10N/25mm未満
D:7.5N/25mm未満
E:2kgローラー圧着後の粘着力より低い <Measuring method of anchoring force of pressure-sensitive adhesive layer> A polyethylene terephthalate film [Oike Industry Co., Ltd., trade name "125 Tetraite OES" (thickness 125 μm)] having a 25 mm width, which was vapor-deposited with indium tin oxide, was used. The polarizing film with the pressure-sensitive adhesive layer was pressure-bonded back and forth once with a 2 kg roller and cured at 23° C. for 1 minute, and the adhesive strength was measured when the polyethylene terephthalate film was peeled together with the pressure-sensitive adhesive layer in the 180° direction at 300 mm/min. .. Then, the anchoring power was judged according to the following criteria.
A: 15 N/25 mm or more B: 10 N/25 mm or more and 15 N/25 mm or less C: 7.5 N/25 mm or more and 10 N/25 mm or less D: 7.5 N/25 mm or less E: 2 kg Lower than the adhesive strength after roller pressure bonding
以上の通り、本発明によれば、高耐久性とリワーク性とを兼ね備え、かつ偏光フィルムと粘着剤との密着性(投錨力)に優れた粘着剤層付き偏光フィルムを提供することができる。
As described above, according to the present invention, it is possible to provide a polarizing film with an adhesive layer, which has both high durability and reworkability and is excellent in the adhesiveness (anchoring force) between the polarizing film and the adhesive.
1 偏光子
2 第1の保護フィルム
2’ 第2の保護フィルム
3 偏光フィルム
4 粘着剤層
5 セパレータ
10 粘着剤層付き偏光フィルム 1Polarizer 2 1st protective film 2'2nd protective film 3 Polarizing film 4 Adhesive layer 5 Separator 10 Polarizing film with an adhesive layer
2 第1の保護フィルム
2’ 第2の保護フィルム
3 偏光フィルム
4 粘着剤層
5 セパレータ
10 粘着剤層付き偏光フィルム 1
Claims (9)
- 偏光子と、前記偏光子の視認側に設けられた第1の保護フィルムと、前記偏光子の視認側とは反対側に設けられた第2の保護フィルムと、を備える偏光フィルムと、
前記第2の保護フィルム上に設けられる粘着剤層と、を備える粘着剤層付き偏光フィルムであって、
前記粘着剤層は、ベースポリマーと、シリコーンオリゴマーPsとを含み、
前記シリコーンオリゴマーPsは、前記ベースポリマー100重量部に対し、0.1~20重量部で含まれ、
前記シリコーンオリゴマーPsは、Tgが-50℃以上100℃以下、側鎖のシリコーン官能基当量が1000~20000g/molであり、重量平均分子量が10000以上300000以下である、粘着剤層付き偏光フィルム。 A polarizing film comprising a polarizer, a first protective film provided on the viewing side of the polarizer, and a second protective film provided on the opposite side of the viewing side of the polarizer,
A pressure-sensitive adhesive layer-provided polarizing film comprising: a pressure-sensitive adhesive layer provided on the second protective film,
The pressure-sensitive adhesive layer includes a base polymer and a silicone oligomer Ps,
The silicone oligomer Ps is included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the base polymer,
The silicone oligomer Ps has a Tg of −50° C. or higher and 100° C. or lower, a side chain silicone functional group equivalent of 1000 to 20000 g/mol, and a weight average molecular weight of 10,000 or more and 300,000 or less. - 前記シリコーンオリゴマーPsが、モノマー単位として、ポリオルガノシロキサン骨格を有するモノマーS1と、ホモポリマーのガラス転移温度が-70℃以上180℃以下のモノマーとを含む、請求項1に記載の粘着剤層付き偏光フィルム。 The pressure-sensitive adhesive layer according to claim 1, wherein the silicone oligomer Ps contains, as monomer units, a monomer S1 having a polyorganosiloxane skeleton and a monomer having a homopolymer glass transition temperature of −70° C. or higher and 180° C. or lower. Polarizing film.
- 前記ベースポリマーが、モノマー単位として、ホモポリマーのガラス転移温度が-80℃以上0℃以下であるアルキル(メタ)アクリレート(A)を80重量%以上で含有する、請求項1または2に記載の粘着剤層付き偏光フィルム。 3. The base polymer according to claim 1, wherein the base polymer contains 80% by weight or more of an alkyl (meth)acrylate (A) having a glass transition temperature of a homopolymer of −80° C. or higher and 0° C. or lower as a monomer unit. Polarizing film with adhesive layer.
- 前記ベースポリマーが、モノマー単位として、カルボキシル基含有モノマー(b1)および窒素含有モノマー(b2)からなる群より選択される少なくとも1種の極性モノマー(B)を0~20重量%で更に含有する、請求項3に記載の粘着剤層付き偏光フィルム。 The base polymer further contains, as a monomer unit, at least one polar monomer (B) selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2) in an amount of 0 to 20% by weight. The polarizing film with an adhesive layer according to claim 3.
- 前記ベースポリマーが、モノマー単位として、水酸基含有モノマーを0.01~5重量%で含有する、請求項4に記載の粘着剤層付き偏光フィルム。 The polarizing film with an adhesive layer according to claim 4, wherein the base polymer contains 0.01 to 5% by weight of a hydroxyl group-containing monomer as a monomer unit.
- 前記ベースポリマーの重量平均分子量が50万~250万である、請求項1~5のいずれか1項に記載の粘着剤層付き偏光フィルム。 The polarizing film with an adhesive layer according to any one of claims 1 to 5, wherein the base polymer has a weight average molecular weight of 500,000 to 2,500,000.
- 前記第2の保護フィルムと前記粘着剤層との間に機能性コーティング層を更に備える、請求項1~6のいずれか1項に記載の粘着剤層付き偏光フィルム。 The polarizing film with an adhesive layer according to any one of claims 1 to 6, further comprising a functional coating layer between the second protective film and the adhesive layer.
- 前記機能性コーティング層が、オキサゾリン基含有ポリマーを含有する、請求項7に記載の粘着剤層付き偏光フィルム。 The polarizing film with an adhesive layer according to claim 7, wherein the functional coating layer contains an oxazoline group-containing polymer.
- 前記シリコーンオリゴマーPsの溶融温度が、-20℃~120℃である、請求項1~8のいずれか1項に記載の粘着剤層付き偏光フィルム。 The polarizing film with a pressure-sensitive adhesive layer according to any one of claims 1 to 8, wherein a melting temperature of the silicone oligomer Ps is -20°C to 120°C.
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