WO2019069746A1 - 粘着剤組成物及び粘着シート - Google Patents
粘着剤組成物及び粘着シート Download PDFInfo
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- WO2019069746A1 WO2019069746A1 PCT/JP2018/035399 JP2018035399W WO2019069746A1 WO 2019069746 A1 WO2019069746 A1 WO 2019069746A1 JP 2018035399 W JP2018035399 W JP 2018035399W WO 2019069746 A1 WO2019069746 A1 WO 2019069746A1
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- adhesive composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
Definitions
- the present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet, and more particularly to a pressure-sensitive adhesive composition containing a compound having a (meth) acryloyl group, and a pressure-sensitive adhesive sheet having a cured product of the pressure-sensitive adhesive composition.
- Various optical films are used for optical components, such as liquid crystal displays, such as a smart phone, a personal computer, and a television, and a touch panel.
- a protective sheet pressure-sensitive adhesive sheet
- a protective sheet is generally laminated on the surface of these optical films for the purpose of preventing contamination and damage in the transportation step, the manufacturing step, and the inspection step.
- the protective sheet is peeled off in a post process such as an assembly process.
- Various urethane pressure-sensitive adhesives have been proposed as pressure-sensitive adhesives for such protective sheets.
- Patent Document 1 a polyurethane having a polyoxyalkylene polyol as a skeleton and having a (meth) acryloyl group at an end thereof, a polyurethane having a weight average molecular weight of 10,000 to 300,000, a (meth) acrylic acid ester having a hydroxy group, and the like
- a photocurable composition for a transparent pressure-sensitive adhesive sheet which comprises a photopolymerizable monomer and a photopolymerization initiator.
- Patent Document 2 a polyurethane in which a (meth) acryloyl group is bonded to an end of a polyoxyalkylene chain via a urethane bond, a (meth) acrylic acid ester having a hydroxy group, and a (meth) acrylic acid ester having an aromatic ring
- a photocurable composition for a transparent pressure-sensitive adhesive sheet which contains another polymerizable monomer and a photopolymerization initiator.
- the protective sheet In the inspection process, it may be required that, with the protective sheet laminated to the product or part, it is possible to sufficiently detect or detect fine foreign substances or scratches on the product or part. Therefore, the protective sheet is required to have low haze, that is, low haze.
- the protective sheet may be repeatedly laminated and peeled off. Therefore, the protective sheet is required to be easy to laminate on the adherend (high wettability to the adherend) and easy to peel off. Further, recently, with the increase in the screen size of displays and the reduction in thickness of panel parts and the like, optical parts themselves are easily broken. Therefore, the protective sheet is also required to be able to be peeled by a lighter force (light peelability) while having an appropriate adhesiveness (peel strength). Furthermore, it is also required that there is no so-called adhesive residue (removability) in which a part of the adhesive layer or the like remains on the product surface (adherend) after peeling off the protective sheet.
- compositions described in Patent Document 1 and Patent Document 2 are not intended for use as a protective sheet for peeling in the manufacturing process, and PSA sheets using these compositions have high peel strength. .
- an object of the present invention is to provide a pressure-sensitive adhesive composition for a pressure-sensitive adhesive sheet which has a low haze, is easy to laminate, and is easy to peel, and further can suppress adhesive residue after peeling.
- Another object of the present invention is to provide a pressure-sensitive adhesive sheet which has a low haze, is easy to laminate, and is easy to peel, and further can suppress the adhesive residue after peeling.
- the polyurethane (A) further includes a polyurethane (a2), and the polyurethane (a2) has a skeleton containing a structure derived from a polyoxyalkylene polyol and a polyisocyanate, and only at one end (
- a pressure-sensitive adhesive composition for a pressure-sensitive adhesive sheet which is low in haze, easy to laminate, easy to peel, and can suppress adhesive residue after peeling. Further, according to the present invention, it is possible to provide a pressure-sensitive adhesive sheet which has low haze, is easy to laminate, and is easy to peel, and further, can suppress adhesive residue after peeling.
- FIG. 2 is a cross-sectional view taken along line AA in FIG.
- a (meth) acryloyl group means a group represented by a chemical formula CH 2 CHCH—CO— or a functional group represented by a chemical formula CH 2 CC (CH 3 ) —CO— (meta).
- the acryloyloxy group means a group represented by the chemical formula CH 2 CHCH—CO—O— or a functional group represented by the chemical formula CH 2 CC (CH 3 ) —CO—O—.
- the pressure-sensitive adhesive composition according to the present embodiment is a compound other than polyurethane (A) having a skeleton containing a structure derived from polyoxyalkylene polyol and a structure derived from polyisocyanate, and a compound other than polyurethane (A), which is (meth) acryloylyl.
- the polyurethane (A) includes a polyurethane (a1), and the polyurethane (a1) has a skeleton including a structure derived from a polyoxyalkylene polyol and a structure derived from a polyisocyanate, and a plurality of polyurethanes (a1) There is a (meth) acryloyl group at the end of
- the weight average molecular weight of the polyurethane (A) is 30,000 to 200,000.
- the adhesive composition concerning this embodiment may also contain additives, such as a fatty acid ester, as needed.
- the pressure-sensitive adhesive composition according to the present embodiment may contain a solvent, if necessary.
- each component contained in an adhesive composition is demonstrated.
- the component which consists of polyurethane (A), a polyfunctional monomer (B), and the other monomer (C) may be called "component (A)-(C)." .
- the polyurethane (A) further includes a polyurethane (a2) having a skeleton containing a structure derived from a polyoxyalkylene polyol and a structure derived from a polyisocyanate, and having a (meth) acryloyl group at only one end. It is also good.
- the components other than polyurethane (a1) and polyurethane (a2) are not contained in polyurethane (A).
- the adjustment method of the number of the (meth) acryloyl group of the terminal of polyurethane mentions the example in the section of the manufacturing method of polyurethane (A) later.
- the polyoxyalkylene polyol is preferably one having an alkylene chain of 2 to 4 carbon atoms, and specific examples thereof include, for example, polyoxyethylene polyol, polyoxypropylene polyol, polyoxybutylene polyol and the like.
- polyoxyalkylene polyols polyoxyalkylene diols are preferably used, and polypropylene glycol is particularly preferably used.
- the polyoxyalkylene polyol may be a copolymer of two or more oxyalkylene polyols.
- a polyurethane (A) the structure from which the structure derived from 2 or more types of different polyoxyalkylene polyols may be superposed
- the number average molecular weight of the polyoxyalkylene polyol is preferably 500 to 5,000, more preferably 800 to 4,000, and still more preferably 1,000 to 3,000. .
- the polyisocyanate is not particularly limited, but is preferably diisocyanate.
- diisocyanates include tolylene diisocyanate and its hydrogenated product, xylylene diisocyanate and its hydrogenated product, diphenylmethane diisocyanate and its hydrogenated product, 1,5-naphthyl diisocyanate and its hydrogenated product, hexamethylene diisocyanate, trimethyl Hexamethylene diisocyanate, tetramethyl xylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexyl diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, norbornane diisocyanate and the like can be mentioned.
- a hydrogenated product of isophorone diisocyanate or diphenylmethane diisocyanate is preferable from the viewpoint of control of light resistance and reactivity, and a hydrogenated product of diphenylmethane diisocyanate is more preferable from the viewpoint of reactivity.
- the structure derived from polyisocyanate contained in polyurethane (A) may consist of one type, or may be a structure including two or more types.
- the weight average molecular weight of the polyurethane (A) is 30,000 to 200,000, preferably 50,000 to 150,000, and more preferably 70,000 to 100,000. If the weight average molecular weight of the polyurethane (A) is 30,000 or more, the pressure-sensitive adhesive layer obtained by curing the pressure-sensitive adhesive composition has sufficient flexibility, so the pressure-sensitive adhesive sheet having this pressure-sensitive adhesive layer can be easily laminated . Moreover, if the weight average molecular weight of polyurethane (A) is 200,000 or less, the handling as an adhesive composition is easy and it can improve workability.
- the content of the polyurethane (A) is preferably 30 to 60% by mass, more preferably 34 to 56% by mass, based on the total amount of the components (A) to (C). And 37 to 53% by mass.
- the content of the polyurethane (A) is 30 to 60% by mass, the cohesion and the peel strength at the time of using as a pressure-sensitive adhesive sheet become suitable.
- the polyfunctional monomer (B) is other than the polyurethane (A) and has a plurality of (meth) acryloyl groups, but is particularly limited as long as the number of (meth) acryloyl groups is 2 or more. Absent. However, from the viewpoint of curability, the polyfunctional monomer (B) preferably has 3 or more (meth) acryloyl groups.
- the polyfunctional monomer (B) is preferably a polyol poly (meth) acrylate, for example, polyethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, 1,3-bis (hydroxyethyl) -5,5-dimethylhydantoin (meth) ) Acrylate, ⁇ , ⁇ -di (meth) acrylic bisdiethylene glycol phthalate, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate Ta) Acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanedio
- 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol triol from the viewpoint of easily adjusting the peel strength of the pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition to a low level. More preferred are hydroxy (meth) acrylate and pentaerythritol tetra (meth) acrylate, and more preferred is trimethylolpropane tri (meth) acrylate.
- a polyfunctional monomer (B) may consist of one type of compound, and may consist of two or more types of compounds.
- the content of the polyfunctional monomer (B) is preferably 10 to 20% by mass and 11 to 19% by mass with respect to the total amount of the components (A) to (C). And more preferably 12 to 18% by mass.
- the content of the polyfunctional monomer (B) is 10 to 20 parts by mass, a pressure-sensitive adhesive sheet excellent in light releasability can be obtained.
- the other monomer (C) is a compound other than polyurethane (A) and is a compound other than polyfunctional monomer (B), and is a compound of polyurethane (A) and polyfunctional monomer (B) It is not particularly limited as long as it can be polymerized.
- the other monomer (C) preferably has a radically polymerizable ethylenic unsaturated bond as a functional group for polymerizing with the polyurethane (A) and the polyfunctional monomer (B), Among them, a vinyl group or a (meth) acryloyl group is more preferable, and a (meth) acryloyl group is more preferable.
- the other monomer (C) is not particularly limited, but alkyl (meth) acrylate, cyclic alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, alkoxy (poly) alkylene glycol (meth) acrylate, hydroxy group-containing Examples include (meth) acrylates, carboxy group-containing (meth) acrylates, fluorinated alkyl (meth) acrylates, dialkylaminoalkyl (meth) acrylates, (meth) acrylamides, epoxy group-containing (meth) acrylates, and the like.
- alkyl (meth) acrylate for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-hexyl (meth) acrylate, isooctyl (meth) acrylate, isostearyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, etc. It can be mentioned.
- cyclic alkyl (meth) acrylates examples include cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, norbornanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) ) Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate and the like.
- alkoxyalkyl (meth) acrylate for example, ethoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl (meth) An acrylate etc. are mentioned.
- alkoxy (poly) alkylene glycol (meth) acrylate examples include methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate and the like.
- hydroxy group-containing (meth) acrylate for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,3-butanediol (meth) acrylate, Examples include 1,4-butanediol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 3-methylpentanediol (meth) acrylate and the like.
- carboxy group-containing (meth) acrylates examples include (meth) acrylic acid, ⁇ -carboxyethyl (meth) acrylate and the like.
- fluorinated alkyl (meth) acrylates examples include octafluoropentyl (meth) acrylate and the like.
- dialkylaminoalkyl (meth) acrylates examples include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate and the like.
- Examples of (meth) acrylamides include (meth) acrylamides, N-methyl (meth) acrylamides, N-ethyl (meth) acrylamides, N-propyl (meth) acrylamides, N-isopropylacrylamides, and N-hexyl (meth) acrylamides. And N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, (meth) acryloyl morpholine, diacetone acrylamide and the like.
- epoxy group-containing (meth) acrylates examples include glycidyl (meth) acrylate and the like.
- the other monomer (C) in addition to the above compounds, for example, acrylonitrile, methacrylonitrile, styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, Alkyl vinyl ethers, vinyl toluene, N-vinyl pyridine, N-vinyl pyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, 4-hydroxymethyl cyclohexyl methyl vinyl ether, triethylene glycol monovinyl ether Or diethylene glycol monovinyl ether, methyl vinyl ketone, N-acrylamidomethyl trimethyl ammonium chloride, allyltrime Le ammonium chloride, dimethyl allyl vinyl ketone.
- alkyl (meth) acrylates are preferable from the viewpoint of the compatibility with the polyurethane (A), the viscosity of the pressure-sensitive adhesive composition, and the peel strength, 2-ethylhexyl (meth) acrylate and isooctyl (Meth) acrylate, isostearyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acryloyl morpholine are more preferred, and 2-ethylhexyl (meth) acrylate is even more preferred.
- another monomer (C) may consist of one type of compound, and may consist of two or more types of compounds.
- the content of the other monomer (C) is preferably 20 to 50% by mass, preferably 23 to 47% by mass, with respect to the total amount of the components (A) to (C). And more preferably 25 to 45% by mass. If the content of the other monomer (C) is 20 to 50% by mass, the cohesion of the pressure-sensitive adhesive layer obtained by curing the pressure-sensitive adhesive composition is sufficiently obtained, which is preferable.
- Photopolymerization initiator (D) is not particularly limited. However, carbonyl photopolymerization initiator, sulfide photopolymerization initiator, acyl phosphine oxides, quinone photopolymerization initiator, sulfochloride photopolymerization initiator, thioxanthone And photopolymerization initiators and the like.
- carbonyl-based photopolymerization initiators include benzophenone, benzyl, benzoin, ⁇ -bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone and p-dimethylamino Acetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzyl methyl Ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl) -2 Hydroxy-2-methylpropan-1-one, methyl benzoyl
- sulfide photopolymerization initiators include diphenyl disulfide, dibenzyl disulfide, tetraethylthiuram disulfide, tetramethylammonium monosulfide and the like.
- acyl phosphine oxides examples include 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,4,6- trimethyl benzoyl phenyl ethoxy phosphine oxide and the like.
- quinone system photoinitiators such as benzoquinone and anthraquinone, are mentioned, for example.
- sulfochloride-based photopolymerization initiators examples include 2-naphthalenesulfonyl chloride and the like.
- thioxanthone photopolymerization initiators examples include thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone and the like.
- a photoinitiator (D) may consist of one type of compound, and may consist of two or more types of compounds.
- the content of the photopolymerization initiator (D) is preferably 0.2 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the total amount of the components (A) to (C). Is more preferably 0.5 to 2 parts by mass. If the content of the photopolymerization initiator (D) is 0.2 parts by mass or more, it is an amount sufficient for photocuring, and if 5 parts by mass or less, the releasability of the obtained adhesive sheet is also good. It is.
- a fatty acid ester is added to the pressure-sensitive adhesive composition as necessary in order to improve the laminating property (wettability) and the defoaming property (easiness of air bubbles inserted at the time of bonding) of the obtained pressure-sensitive adhesive sheet. It is also good.
- fatty acid esters include monobasic acids having 8 to 18 carbon atoms, esters of polybasic acids and branched alcohols having 18 or less carbon atoms, unsaturated fatty acids having 14 to 18 carbon atoms, or branched chains. The ester etc. with the acid and tetravalent alcohol which it has, etc. are mentioned.
- Specific examples preferred as fatty acid esters include isopropyl myristate.
- the amount of fatty acid ester added is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and further 5 to 15 parts by mass with respect to 100 parts by mass of the total amount of components (A) to (C). preferable.
- additives may be added to the pressure-sensitive adhesive composition as needed, as long as the transparency is not impaired.
- Additives include, for example, plasticizers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, UV absorbers, polymerization inhibitors, light stabilizers such as benzotriazole, phosphorus Examples thereof include acid ester-based and other flame retardants, antistatic agents such as surfactants, and dyes.
- the pressure-sensitive adhesive composition contains the polyfunctional monomer (B) and the other monomer (C) as the low molecular weight component, and therefore, the viscosity can be adjusted to a coatable viscosity without the addition of a solvent.
- a solvent may be added for the purpose of viscosity adjustment at the time of coating.
- a solvent can be suitably selected by the other component etc. which are contained in an adhesive composition, an organic solvent is preferable.
- the organic solvent to be used is not particularly limited, and methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, n-propanol, isopropanol and the like can be mentioned. These organic solvents may be used alone or in combination of two or more. The solvent is preferably removed by drying after applying the pressure-sensitive adhesive composition to a substrate or the like, and then photocuring.
- polyoxyalkylene polyol and polyisocyanate are charged at a ratio such that the amount of isocyanato groups (number basis, the same applies hereinafter) is larger than the amount of hydroxy groups (number basis, the same applies hereafter), and these are reacted to react isocyanate groups at the terminal.
- Synthesize polyurethane which it has.
- Specific examples of polyoxyalkylene polyols and polyisocyanates are as exemplified in the section of polyurethane (A).
- the molecular weight degree of polymerization
- the amount of isocyanato groups relative to the amount of hydroxy groups. Specifically, the smaller the excess of the amount of isocyanato groups to the amount of hydroxy groups, the higher the molecular weight of the polyurethane having isocyanato groups, and the larger the excess of the amount of isocyanato groups to the amount of hydroxy groups, the polyurethanes having isocyanato groups Molecular weight decreases.
- a polyurethane having an isocyanato group at the terminal and a compound having a hydroxy group and a (meth) acryloyl group are reacted to synthesize a polyurethane (A) having a (meth) acryloyl group at the molecular chain terminal.
- the (meth) acryloyl group contained in this compound is a part of (meth) acryloyloxy group.
- the compound having a hydroxy group and a (meth) acryloyl group is not particularly limited, and hydroxyalkyl (such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate ( Meta) acrylate; 1,3-butanediol mono (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, 3-methylpentanediol mono (meth) acrylate And monools having (meth) acryloyl groups derived from various polyols. These may be used alone or in combination of two or more. Among them, 2-hydroxyethyl (meth) acrylate is preferable in terms of reactivity with an isocyanato group and light curing.
- an alkyl alcohol having one (one) hydroxy group without a (meth) acryloyl group is used in combination to react with a polyurethane having an isocyanato group at the end.
- the introduction amount of (meth) acryloyl group can be adjusted.
- the alkyl alcohol is not particularly limited, and includes, for example, linear, branched and alicyclic alkyl alcohols, which may be used alone or in combination of two or more. . This produces a polyurethane having a structure derived from the alkyl alcohol at at least one of the ends.
- the polyurethane (A) includes a polyurethane having no (meth) acryloyl group at at least one of the ends. Therefore, polyurethane having a (meth) acryloyl group at only one end may also be included.
- a (meth) acryloyl group is introduced to 90 to 100% of the terminal of the polyurethane contained in the polyurethane (A) on a numerical basis, more preferably 95 to 100%, and still more preferably 100%.
- the amount of (meth) acryloyl group introduced is 90% or more based on the number of isocyanato groups, the cohesion of the pressure-sensitive adhesive layer obtained by curing the pressure-sensitive adhesive composition is sufficiently obtained.
- the ratio of the number of ends into which (meth) acryloyl groups are introduced to the number of ends of all polyurethane molecular chains can be measured by IR, NMR or the like.
- the amount of the urethanization catalyst used is preferably 50 to 500 mass ppm based on the total mass of the reactants.
- a polyoxyalkylene polyol and a polyisocyanate are reacted at a rate at which the amount of hydroxy groups is larger than the amount of isocyanato groups to synthesize a polyurethane having a hydroxy group at an end.
- the molecular weight by adjusting the ratio of the amount of hydroxy groups to the amount of isocyanato groups as in the above example. Specifically, the smaller the excess of the amount of hydroxy groups to the amount of isocyanato groups, the higher the molecular weight of the polyurethane having hydroxy groups, and the greater the excess of the amount of hydroxy groups to the amount of isocyanato groups, the more polyurethane of hydroxy group containing Molecular weight decreases.
- a polyurethane having a hydroxy group at the end and a compound having an isocyanato group and a (meth) acryloyl group are reacted to synthesize a polyurethane (A) having a (meth) acryloyl group at the molecular chain end.
- the (meth) acryloyl group contained in this compound is a part of (meth) acryloyloxy group.
- the compound having an isocyanato group and a (meth) acryloyl group is not particularly limited, but 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl An isocyanate etc. are mentioned.
- a commercial item of the compound which has an isocyanato group and a (meth) acryloyl group Karen MOI (trademark) by Kayo Denko KK, Karen AOI (trademark), etc. can be illustrated, for example. These may be used alone or in combination of two or more.
- 2- (meth) acryloyloxyethyl isocyanate is preferable from the viewpoint of the reactivity with a hydroxy group and the photo-curing property.
- an alkyl isocyanate having one (1) isocyanate group which does not have a (meth) acryloyl group, is used in combination to react with a polyurethane having a hydroxy group at an end.
- the introduction amount of (meth) acryloyl group can be adjusted.
- the alkyl isocyanate is not particularly limited, and examples thereof include linear, branched and alicyclic alkyl isocyanates, etc., and these may be used alone or in combination of two or more. . This produces a polyurethane having a structure derived from the above alkyl isocyanate at at least one end.
- the polyurethane (A) includes a polyurethane having no (meth) acryloyl group at at least one of the ends. Therefore, in this case, the polyurethane (A) can also include a polyurethane having a (meth) acryloyl group at only one end.
- a (meth) acryloyl group is introduced to 90 to 100% of the terminal of the polyurethane contained in the polyurethane (A) on a numerical basis, more preferably 95 to 100%, and still more preferably 100%.
- the amount of (meth) acryloyl group introduced is 90% or more based on the number of isocyanato groups, the cohesion of the pressure-sensitive adhesive layer obtained by curing the pressure-sensitive adhesive composition is sufficiently obtained.
- the pressure-sensitive adhesive composition is manufactured by mixing the organic solvent and the organic solvent.
- the mixing method is not particularly limited, for example, it can be carried out using a stirring device attached with stirring blades such as homodisper and paddle blades.
- all the components may be added and mixed at one time, or addition and mixing may be repeated for each component in multiple times.
- this component is added as one dissolved in a solvent, or one dispersed in a dispersion medium, or by adding as one melted by heating, etc. It becomes easy to be mixed in the adhesive composition with high uniformity.
- Composition of adhesive sheet> In the pressure-sensitive adhesive sheet according to the present embodiment, a pressure-sensitive adhesive layer containing a cured product of the pressure-sensitive adhesive composition is formed on one side of a substrate.
- the thickness of the adhesive layer is preferably 3 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, and still more preferably 10 to 30 ⁇ m. When the film thickness of the adhesive layer is 3 ⁇ m or more, the strength of the adhesive layer is sufficient, and when the film thickness is 100 ⁇ m or less, control of the film thickness of the adhesive layer is easy.
- the gel fraction of the cured product of the pressure-sensitive adhesive composition contained in the adhesive layer is preferably 85 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass. preferable.
- the gel fraction is the mass fraction of the extractable insoluble matter with respect to the solvent, and here, the solvent is selected from among the cured products of the pressure-sensitive adhesive composition that can dissolve uncrosslinked components.
- the example of the specific measuring method of a gel fraction is mentioned later in an Example.
- a resin film is mentioned, for example.
- the adhesive sheet is used, for example, as a protective sheet in a manufacturing process, and the substrate is transparent when it is carried out in a state where the protective sheet is laminated when inspecting the adherend, that is, the presence or absence of scratches or foreign matter on a product.
- transparent substrates include polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, cellulose and the like.
- the thickness of the substrate can be appropriately selected according to the application of the pressure-sensitive adhesive sheet, and is not particularly limited, but in the case of a resin film, the thickness of the substrate is preferably 5 ⁇ m or more in terms of handleability and strength. More preferably, it is 10 micrometers or more, More preferably, it is 20 micrometers or more. Further, considering the flexibility of the resin film, the thickness of the substrate is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and still more preferably 100 ⁇ m or less.
- the antistatic treatment to be applied to the substrate is not particularly limited, but a method of providing an antistatic layer on at least one surface of the substrate, a method of kneading an antistatic agent into the substrate, and the like can be used.
- the surface of the substrate on which the adhesive layer is to be formed may be subjected to an adhesion treatment such as an acid treatment, an alkali treatment, a primer treatment, a corona treatment, a plasma treatment, an ultraviolet treatment, an ozone treatment, etc. .
- a separator can be laminated on the surface of the pressure-sensitive adhesive layer for the purpose of protecting the pressure-sensitive adhesive layer.
- paper, a plastic film etc. can be used as a material of a separator, for example, a plastic film is suitable from the point which is excellent in surface smoothness.
- the plastic film used as the separator is not particularly limited as long as it can protect the above-mentioned adhesive layer, and examples thereof include polyethylene, polypropylene, polyethylene terephthalate, and polybutene.
- the manufacturing method of the adhesive sheet concerning this embodiment can be obtained by, for example, apply
- the method for applying the pressure-sensitive adhesive composition to the substrate is not particularly limited, and can be appropriately selected.
- various coaters such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater, comma coater, direct coater, etc.
- the method used, the screen printing method etc. are mentioned.
- a black light, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a xenon lamp and the like can be mentioned.
- the irradiation intensity of light it is preferable that the pressure-sensitive adhesive composition can be sufficiently cured, and it is, for example, 50 to 3000 mW / cm 2 .
- productivity is reduced.
- the protective sheet is a surface of a plastic film used as an optical component such as a polarizing plate, a wave plate, a retardation plate, an optical compensation film, a reflective sheet, a brightness improving film, etc. used in liquid crystal displays such as smartphones, personal computers and televisions. It may be suitably used for the purpose of protecting the optical component
- the pressure-sensitive adhesive sheet according to the present embodiment is used as such a protective sheet
- the pressure-sensitive adhesive sheet is required to have low haze, that is, low haze.
- the haze value of the pressure-sensitive adhesive sheet is preferably 2.0% or less, more preferably 1.5% or less, and still more preferably 1.0% or less.
- the specific measuring method of the haze value of an adhesive sheet is mentioned later in an Example.
- the pressure-sensitive adhesive sheet according to the present embodiment when used as a protective sheet as described above, the pressure-sensitive adhesive sheet needs to have a minimum peel strength so as not to be peeled off from products or parts during handling such as transportation. become.
- the peel strength of the pressure-sensitive adhesive sheet is preferably 1 to 25 gf / 25 mm, more preferably 4 to 20 gf / 25 mm, and still more preferably 7 to 15 gf / 25 mm.
- the specific measuring method of the peeling strength of an adhesive sheet is mentioned later in an Example.
- the present invention will be described in detail by way of examples.
- the present invention is not limited at all by the examples shown below.
- the weight average molecular weight of the obtained polyurethane (A) was measured by gel permeation chromatography (Shodex GPC-101 manufactured by Showa Denko KK, hereinafter referred to as GPC). It is a value in terms of polystyrene.
- the measurement conditions of GPC are as follows.
- Desmodur W manufactured by Sumika Kobastro Urethane
- A-2) An acryloyl group is prepared in the same manner as in the synthesis of polyurethane (A-1) except that 21 mol (4.67 kg) of isophorone diisocyanate (Desmodur I, manufactured by Sumika Kobastro Urethane) is used in place of the hydrogenated substance of diphenylmethane diisocyanate. A polyurethane (A-2) having at each end was obtained. The weight average molecular weight of the resulting polyurethane (A-2) was 67,000.
- A-4 Except that 4 mol (1.05 kg) of a hydrogenated substance of diphenylmethane diisocyanate and hydroxy group-terminated polypropylene glycol D-2000 (Mitsui Chemical Co., Ltd.) having a hydroxyl value of 56 mg KOH / g are changed to 3 mol (6.0 kg)
- a polyurethane (A-3) having an acryloyl group at all the ends was obtained in the same manner as in the synthesis of the polyurethane (A-1).
- the weight average molecular weight of the resulting polyurethane (A-3) was 12,000.
- a pressure-sensitive adhesive sheet having a substrate for an optical PET film on one side was produced.
- the prepared pressure-sensitive adhesive composition is applied onto a 50- ⁇ m-thick optical PET film (A4300 manufactured by Toyobo Co., Ltd.) using an applicator, and 75 ⁇ m-thick from the top of the applied pressure-sensitive adhesive composition. It covered with the peeling PET film (Toyobo Co., Ltd. E7006).
- the sheet covered with the peeling PET film is irradiated with ultraviolet light from the surface on the peeling PET film side
- the composition was light cured.
- the irradiation distance of ultraviolet light is 25 cm
- the moving speed of the lamp is 1.0 m / min
- the irradiation amount is 1000 mJ / cm 2 .
- the thickness of the adhesive sheet was measured using a dial gauge
- the thickness of the adhesive layer after curing was calculated by subtracting the thickness of the substrate of 50 ⁇ m from the measured value.
- the measuring surface of the dial gauge was a circular plane with a diameter of 5 mm, and the measuring force was 0.8N.
- the thickness was 20 ⁇ m in any of Examples 1 to 14 and Comparative Examples 1 and 2.
- the pressure-sensitive adhesive composition according to each of Examples 1 to 14 and Comparative Examples 1 to 2 was peeled off to a thickness of 50 ⁇ m so that the thickness of the adhesive layer after curing was 50 ⁇ m. It apply
- the confirmation method of the thickness of the adhesion layer is the same as the measuring method mentioned above by the term of preparation of an adhesive sheet.
- the pressure-sensitive adhesive composition on the release PET film was covered with a 75 ⁇ m-thick release PET film (E7006 manufactured by Toyobo Co., Ltd.).
- a UV irradiation device I-Graphics Co., Ltd., UV irradiation device 3 kW, high-pressure mercury lamp
- the adhesive composition covered on both sides with a peeling PET film is a 75 ⁇ m thick surface on the peeling PET film side
- the adhesive composition was photocured by irradiation with ultraviolet light.
- the irradiation distance of ultraviolet light is 25 cm
- the moving speed of the lamp is 1.0 m / min
- the irradiation amount is 1000 mJ / cm 2 .
- the prepared sheet was cut into a size of 100 mm ⁇ 100 mm, and the release PET film on both sides was peeled off from the cured product of the pressure-sensitive adhesive composition to obtain a measurement sample.
- the sample for measurement was immersed in 50 ml of toluene at 25 ° C. for 24 hours, dried at 80 ° C. for 5 hours, and the gel fraction was calculated by the following equation (1) from the mass of the sample for measurement before and after immersion in toluene. .
- Tables 1 and 2 The results are shown in Tables 1 and 2.
- the pressure-sensitive adhesive sheets produced in each of Examples 1 to 14 and Comparative Examples 1 and 2 were cut into a size of 25 mm ⁇ 150 mm, and the peeling PET film was peeled off. Thereafter, the entire surface of the exposed pressure-sensitive adhesive layer was laminated on a glass plate, and a 2 kg rubber (load: 19.6 N) rubber roller (diameter: 85 mm, width: 50 mm) was reciprocated once to prepare a measurement sample . The obtained measurement sample was left for 1 hour in an environment of a temperature of 23 ° C. and a relative humidity of 50%.
- FIG. 1 is a plan view showing a method for evaluating the laminateability of the pressure-sensitive adhesive sheet 10
- FIG. 2 is a cross-sectional view taken along the line AA in FIG.
- the adhesive sheet 10 is cut into a size of 20 mm ⁇ 100 mm, and the release PET film is peeled off.
- the adhesive layer 12 is attached to the glass substrate 30 in the range of 15 mm from one end of the adhesive sheet 10 in the longitudinal direction, the adhesive part is fixed to the glass substrate 30, and as shown in FIG. Lift the end.
- FIG. 1 As a fixing method of the adhesive part, as shown in FIG. 1, the upper surface of the adhesive sheet 10 in the range from the one end of the adhesive sheet 10 to 15 mm and the glass substrate 30 outside both sides in the width direction of the adhesive sheet 10 Cellophane tape 20 is attached so as to cover it.
- the laminateability was evaluated according to the following criteria. (Evaluation criteria for laminateability) :: Less than 5 seconds until adhesion ⁇ : More than 5 seconds, less than 10 seconds until adhesion ⁇ : More than 10 seconds, less than 15 seconds until adhesion ⁇ : Not more than 15 seconds until adhesion
- the pressure-sensitive adhesive sheet was cut into a size of 50 mm ⁇ 50 mm, and the release PET film was peeled off. Next, the exposed adhesive surface was laminated to a glass plate and used as a sample. After leaving this sample to stand at 85 ° C. and relative humidity 85% for 3 days, the adhesive sheet was peeled off from the glass plate, and the adhesive residue on the surface of the glass plate was visually confirmed and evaluated according to the following criteria.
- evaluation standard of adhesive residue ⁇ : There is no change in the surface of the glass plate compared to before bonding. ⁇ : Slight adhesion is slightly confirmed on the surface of the glass plate. X: Adhesive residue is clearly confirmed on the surface of the glass plate.
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Abstract
Description
本願は、2017年10月5日に、日本に出願された特願2017-195411号に基づき優先権を主張し、その内容をここに援用する。
〔1〕ポリオキシアルキレンポリオール由来の構造及びポリイソシアネート由来の構造を含む骨格を有するポリウレタン(A)と、ポリウレタン(A)以外の化合物であって、(メタ)アクリロイル基を複数有する多官能性単量体(B)と、ポリウレタン(A)以外であり、かつ多官能性単量体(B)以外の化合物であって、ポリウレタン(A)及び多官能性単量体(B)と重合可能な、その他の単量体(C)と、光重合開始剤(D)と、を含み、前記ポリウレタン(A)が、ポリウレタン(a1)を含み、前記ポリウレタン(a1)は、ポリオキシアルキレンポリオール由来の構造及びポリイソシアネート由来の構造を含む骨格を有し、かつ、前記ポリウレタン(a1)の複数の末端に(メタ)アクリロイル基を有し、
ポリウレタン(A)の重量平均分子量が30,000~200,000であることを特徴とする粘着剤組成物。
〔2〕ポリウレタン(A)、多官能性単量体(B)、及びその他の単量体(C)の合計量に対して、ポリウレタン(A)を30~60質量%、多官能性単量体(B)を10~20質量%、その他の単量体(C)を20~50質量%含む〔1〕に記載の粘着剤組成物。
〔3〕ポリウレタン(A)に含まれるポリオキシアルキレンポリオール由来の構造は、数平均分子量500~5,000のポリオキシアルキレンポリオール由来の構造である〔1〕または〔2〕に記載の粘着剤組成物。
〔4〕ポリウレタン(A)の骨格は、ポリオキシアルキレングリコール及びジイソシアネートとの共重合体である〔1〕~〔3〕のいずれかに記載の粘着剤組成物。
〔5〕ポリウレタン(A)の骨格は、ポリプロピレングリコール及びジフェニルメタンジイソシアネートの水素添加物との共重合体である〔4〕に記載の粘着剤組成物。
〔6〕ポリウレタン(A)における、(メタ)アクリロイル基は、(メタ)アクリロイルオキシ基の一部である〔1〕~〔5〕のいずれかに記載の粘着剤組成物。
〔7〕多官能性単量体(B)は、(メタ)アクリロイル基を3個以上有する〔1〕~〔6〕のいずれかに記載の粘着剤組成物。
〔8〕多官能性単量体(B)は、トリメチロールプロパントリアクリレートである〔7〕に記載の粘着剤組成物。
〔9〕その他の単量体(C)は、(メタ)アクリロイル基を有する〔8〕に記載の粘着剤組成物。
〔10〕その他の単量体(C)は、(メタ)アルキルアクリレートを含む〔9〕に記載の粘着剤組成物。
〔11〕ポリウレタン(A)は、ポリウレタン(a2)をさらに含み、前記ポリウレタン(a2)は、ポリオキシアルキレンポリオール及びポリイソシアネート由来の構造を含む骨格を有し、かついずれか1つ末端のみに(メタ)アクリロイル基を有する〔1〕~〔10〕のいずれかに記載の粘着剤組成物。
〔12〕数基準で、ポリウレタン(A)に含まれるポリウレタン分子の末端の90~100%に(メタ)アクリロイル基が導入されている〔1〕~〔10〕のいずれかに記載の粘着剤組成物。
〔13〕〔1〕~〔12〕のいずれかに記載の光硬化性粘着剤組成物の硬化物を含む粘着層が基材上に形成された粘着シート。
本実施形態にかかる粘着剤組成物は、ポリオキシアルキレンポリオール由来の構造及びポリイソシアネート由来の構造を含む骨格を有するポリウレタン(A)と、ポリウレタン(A)以外の化合物であって、(メタ)アクリロイル基を複数有する多官能性単量体(B)と、ポリウレタン(A)以外であり、かつ多官能性単量体(B)以外である単量体であって、ポリウレタン(A)及び多官能性単量体(B)と重合可能な、その他の単量体(C)と光重合開始剤(D)と、を含む。前記ポリウレタン(A)が、ポリウレタン(a1)を含み、前記ポリウレタン(a1)は、ポリオキシアルキレンポリオール由来の構造及びポリイソシアネート由来の構造を含む骨格を有し、かつ、前記ポリウレタン(a1)の複数の末端に(メタ)アクリロイル基を有る。ポリウレタン(A)の重量平均分子量が30,000~200,000である。また、本実施形態にかかる粘着剤組成物は、必要に応じて、脂肪酸エステル等の添加剤を含んでもよい。さらに、本実施形態にかかる粘着剤組成物は、必要に応じて、溶媒を含んでいてもよい。以下、粘着剤組成物に含まれる各成分について説明する。なお、以下の説明において、ポリウレタン(A)、多官能性単量体(B)、及びその他の単量体(C)からなる成分を「成分(A)~(C)」と言うこともある。
ポリウレタン(A)は、ポリオキシアルキレンポリオール及びポリイソシアネート由来の構造を含む骨格を有する。ポリウレタン(A)は、ポリウレタン(a1)を含む。ポリウレタン(a1)は、ポリオキシアルキレンポリオール由来の構造及びポリイソシアネート由来の構造を含む骨格を有し、かつ、前記ポリウレタン(a1)の複数の末端に(メタ)アクリロイル基を有する。なお、ポリウレタンの末端の(メタ)アクリロイル基は、(メタ)アクリロイルオキシ基の一部であることが好ましい。また、ポリウレタン(A)は、ポリオキシアルキレンポリオール由来の構造及びポリイソシアネート由来の構造を含む骨格を有し、かつ1つの末端のみに(メタ)アクリロイル基を有するポリウレタン(a2)をさらに含んでいてもよい。ポリウレタン(A)にはポリウレタン(a1)、ポリウレタン(a2)以外の成分は含まれない。なお、ポリウレタンの末端の(メタ)アクリロイル基の数の調節方法は、ポリウレタン(A)の製造方法の項においてその一例を後述する。
多官能性単量体(B)は、粘着剤組成物の硬化物を用いた粘着層(粘着シート)の剥離強度を調整する。多官能性単量体(B)は、ポリウレタン(A)以外であって、(メタ)アクリロイル基を複数有しているが、(メタ)アクリロイル基の数が2個以上であれば特に制限はない。ただし、硬化性の観点から、多官能性単量体(B)は3個以上の(メタ)アクリロイル基を有することが好ましい。
その他の単量体(C)は、ポリウレタン(A)以外であり、かつ多官能性単量体(B)以外の化合物であって、ポリウレタン(A)及び多官能性単量体(B)と重合可能であれば特に限定されない。ただし、その他の単量体(C)は、ポリウレタン(A)及び多官能性単量体(B)と重合するための官能基として、ラジカル重合可能なエチレン性不飽和結合を有することが好ましく、その中でもビニル基または(メタ)アクリロイル基であることがより好ましく、(メタ)アクリロイル基であることがさらに好ましい。
光重合開始剤(D)としては、特に限定されないが、カルボニル系光重合開始剤、スルフィド系光重合開始剤、アシルホスフィンオキサイド類、キノン系光重合開始剤、スルホクロリド系光重合開始剤、チオキサントン系光重合開始剤等が挙げられる。
粘着剤組成物には、得られる粘着シートのラミネート性(濡れ性)、泡抜け性(貼合時に挟み込んだ気泡の抜けやすさ)を向上させるため、必要に応じて、脂肪酸エステルを添加してもよい。脂肪酸エステルの例としては、炭素数が8~18の一塩基酸、あるいは多塩基酸と炭素数が18以下の分岐アルコールとのエステル、炭素数が14~18の不飽和脂肪酸、あるいは分岐鎖を有する酸と4価のアルコールとのエステル等が挙げられる。脂肪酸エステルとして好ましい具体的な例としては、ミリスチン酸イソプロピルが挙げられる。脂肪酸エステルの添加量としては、成分(A)~(C)の合計量100質量部に対して、1~30質量部が好ましく、3~20質量部がより好ましく、5~15質量部がさらに好ましい。
粘着剤組成物は、低分子量成分として、多官能性単量体(B)、その他の単量体(C)を含んでいるため、溶媒を加えなくとも塗布可能な粘度に調整することができるが、塗工時の粘度調整を目的として溶媒を添加してもよい。溶媒は粘着剤組成物に含まれるその他の成分等によって適宜選択可能であるが、有機溶媒が好ましい。用いられる有機溶媒としては、特に限定されないが、メチルエチルケトン、アセトン、酢酸エチル、テトラヒドロフラン、ジオキサン、シクロヘキサノン、n‐へキサン、トルエン、キシレン、n‐プロパノール、イソプロパノール等が挙げられる。これらの有機溶媒は単独で使用してもよく、また2種以上を混合して用いてもよい。溶媒は、粘着剤組成物を基材等に塗布した後、乾燥することにより除去し、その後に光硬化を行うことが好ましい。
なお、ここでは、ポリウレタン(A)の合成方法についてはその例を説明するが、多官能性単量体(B)及びその他の単量体(C)及び粘着剤組成物に含まれるその他の成分については用いる化合物の種類によって様々であるため合成方法の説明を省略する。
以下、本実施形態の粘着剤組成物に含まれるポリウレタン(A)の好ましい合成方法の一例について説明するが、ポリウレタン(A)の合成方法はこれに限られず、合成に用いる原料や設備等の条件によって適宜変更可能である。また、この例においては、ヒドロキシ基とイソシアナト基の反応は、いずれの工程においても、イソシアナト基に不活性な有機溶媒の存在下で、ジブチルスズジラウレート、ジブチルスズジエチルヘキソエート、ジオクチルスズジラウレート等のウレタン化触媒を用いて行われる。反応は、30~100℃で1~5時間継続して行われることが好ましい。ウレタン化触媒の使用量は、反応物の総質量に対して、50~500質量ppmであることが好ましい。
ポリウレタン(A)の合成方法の変形例について説明する。なお、この例においても、上記の例と同様、ヒドロキシ基とイソシアナト基の反応は、いずれの工程においても、イソシアナト基に不活性な有機溶媒の存在下で、ジブチルスズジラウレート、ジブチルスズジエチルヘキソエート、ジオクチルスズジラウレート等のウレタン化触媒を用いて行われる。反応は、30~100℃で1~5時間継続して行われることが好ましい。ウレタン化触媒の使用量は、反応物の総質量に対して、50~500質量ppmであることが好ましい。本変形例では、まず、ポリオキシアルキレンポリオールとポリイソシアネートを、ヒドロキシ基量がイソシアナト基量より多くなる割合で反応させて、末端にヒドロキシ基を有するポリウレタンを合成する。
ポリウレタン(A)と、多官能性単量体(B)と、その他の単量体(C)と、光重合開始剤(D)と、必要に応じて添加される脂肪酸エステル、その他の添加剤、及び有機溶媒とを混合することで、粘着剤組成物を製造される。混合方法は、特に限定されないが、例えば、ホモディスパー、パドル翼等の攪拌翼を取り付けた攪拌装置を用いて行うことができる。
<3-1.粘着シートの構成>
本実施形態にかかる粘着シートは、基材の片面に、上記粘着剤組成物の硬化物を含む粘着層が形成されている。粘着層の厚みは、3~100μmであることが好ましく、5~50μmであることがより好ましく、10~30μmであることがさらに好ましい。粘着層の膜厚が3μm以上であれば粘着層の強度が十分であり、膜厚が100μm以下であれば粘着層の膜厚の制御が容易である。
本実施形態にかかる粘着シートの製造方法は、例えば、基材に粘着剤組成物を塗布し、塗布した粘着剤組成物に紫外線を照射して光硬化させることにより得ることができる。
検査工程においては、製品または部品に保護シートがラミネートされた状態で、製品または部品の細かい異物や傷を十分に発見、あるいは検出できることが要求されることがある。また、保護シートは、スマートフォン、パソコン、テレビ等の液晶ディスプレイなどに用いられる偏光板、波長板、位相差板、光学補償フィルム、反射シート、輝度向上フィルム等の光学部品として用いられるプラスチックフィルムの表面を保護する目的で好適に用いられることもある。
カラム:昭和電工株式会社製LF-804
カラム温度:40℃
試料:ポリウレタン(A)の0.2質量%テトラヒドロフラン溶液
流量:1ml/分
溶離液:テトラヒドロフラン
検出器:RI検出器(示差屈折率検出器)
(A-1)
温度計、撹拌器、滴下ロート、乾燥管付き冷却管を備えた反応器に、ジフェニルメタンジイソシアネートの水素添加物(デスモジュールW、住化コベストロウレタン製)を21mol(5.51kg)、及び水酸基価が56mgKOH/gのヒドロキシ基を末端に有するポリプロピレングリコールD-2000(三井化学製、数平均分子量2000)を20mol(40.1kg)仕込んだ。その後、この反応器を60℃まで昇温して4時間反応させ、イソシアナト基を両末端に有するポリウレタンを得た。
ジフェニルメタンジイソシアネートの水素添加物に代えてイソホロンジイソシアネート(デスモジュールI、住化コベストロウレタン製)21mol(4.67kg)を用いること以外はポリウレタン(A-1)の合成法と同様にして、アクリロイル基を全ての末端に有するポリウレタン(A-2)を得た。得られたポリウレタン(A-2)の重量平均分子量は、67,000であった。
ジフェニルメタンジイソシアネートの水素添加物を8mol(2.1kg)、及び水酸基価が56mgKOH/gのヒドロキシ基を末端に有するポリプロピレングリコールD-2000(三井化学製、数平均分子量2000)を7mol(14.0kg)に変えたこと以外はポリウレタン(A-1)の合成法と同様にして、アクリロイル基を全ての末端に有するポリウレタン(A-3)を得た。得られたポリウレタン(A-3)の重量平均分子量は、35,000であった。
ジフェニルメタンジイソシアネートの水素添加物を4mol(1.05kg)、水酸基価が56mgKOH/gのヒドロキシ基を末端に有するポリプロピレングリコールD-2000(三井化学製)を3mol(6.0kg)に変えたこと以外はポリウレタン(A-1)の合成法と同様にして、アクリロイル基を全ての末端に有するポリウレタン(A-3)を得た。得られたポリウレタン(A-3)の重量平均分子量は、12,000であった。
ポリウレタン樹脂(A)、多官能性単量体(B)、その他の単量体(C)、光重合開始剤(D)、及び添加剤を、表1~2に記載の組成で配合し、25℃でディスパーを用いて混合し、実施例1~14、比較例1~2にかかる粘着剤組成物を調製した。
実施例1~14
及び比較例1~2について同じ方法で、片面に光学用PETフィルムの基材を有する粘着シートを作製した。まず、アプリケーターを用いて、調整した粘着剤組成物を、厚さ50μmの光学用PETフィルム(東洋紡株式会社製A4300)上に塗布し、塗布された粘着剤組成物の上から、厚さ75μmの剥離PETフィルム(東洋紡株式会社製E7006)で覆った。次に、紫外線照射装置(アイグラフィックス株式会社製、UV照射装置3kW、高圧水銀ランプ)を用い、剥離PETフィルムで覆われたシートを、剥離PETフィルム側の面から紫外線を照射して粘着剤組成物を光硬化させた。紫外線の照射距離は25cm、ランプ移動速度は1.0m/分、照射量は1000mJ/cm2である。硬化後の粘着層の厚さはダイヤルゲージを用いて、粘着シートの厚さを測定した後、この測定値から基材の厚さ50μmを引いて算出した。ダイヤルゲージの測定面は、直径5mmの円形の平面で、測定力は0.8Nとした。実施例1~14、比較例1~2のいずれにおいても20μmであった。
実施例1~14及び比較例1~2にかかる粘着剤組成物及び粘着シートについて、ゲル分率、透明性、剥離強度、ラミネート性(濡れ性)、及び被着体への糊残りを以下に記載する方法により評価した。結果を表1~2に示した。
まず、アプリケーターを用いて、実施例1~14及び比較例1~2のそれぞれにかかる粘着剤組成物を、硬化後の粘着層の厚さが50μmとなるように50μm厚の剥離PETフィルム(東山フィルム株式会社製HY-S10)に塗布した。なお、粘着層の厚さの確認方法は、粘着シートの作製の項で上記した測定方法と同様である。
ゲル分率(質量%)=[A/B]×100 (1)
A:測定用サンプルのトルエン浸漬後における乾燥質量(トルエンの質量は含まない)
B:測定用サンプルのトルエン浸漬前の質量
実施例1~14及び比較例1~2のそれぞれで作製した粘着シートを50mm×50mmの大きさに切り取り、剥離PETフィルムを剥離した。その後、露出した粘着剤層の全面を、ガラス板にラミネートして、質量2kg(荷重19.6N)のゴムローラー(直径:85mm、幅:50mm)を1往復させて、測定用サンプルを作製した。この測定用サンプルについて、ヘイズメーター(NM-150(株式会社村上色彩技術研究所製))を用いてヘイズ値の測定を行った。ヘイズ値(%)は拡散透過率を全光線透過率で除し、100を乗じて算出した。なお、測定は同じサンプルで3箇所行い、それらの平均値をヘイズ値とした。
実施例1~14及び比較例1~2のそれぞれで作製した粘着シートを25mm×150mmの大きさに切り取り、剥離PETフィルムを剥がした。その後、露出した粘着剤層の全面を、ガラス板にラミネートして、質量2kg(荷重19.6N)のゴムローラー(直径:85mm、幅:50mm)を1往復させて、測定用サンプルを作製した。
得られた測定用サンプルを、温度23℃及び相対湿度50%の環境下に1時間放置した。その後、JIS K 6854-2に準じて、剥離速度0.3m/分、及び30m/分で180°方向の引張試験を行って、保護フィルムのガラス板に対する剥離強度(g/25mm)を測定した。
図1は、粘着シート10のラミネート性評価方法を示した平面図であり、図2は、図1におけるA-A断面図である。粘着シート10を20mm×100mmの大きさに切り取り、剥離PETフィルムを剥がす。次に、粘着シート10の長手方向の一端から15mmまでの範囲で粘着層12をガラス基板30に貼り合わせ、粘着部分をガラス基板30に固定し、図2に示すように、粘着シート10の他端を持ち上げる。粘着部分の固定方法としては、図1に示すように粘着シート10の上記一端から15mmまでの範囲で粘着シート10の上面を、かつ粘着シート10の幅方向の両方の外側においてはガラス基板30を覆うようにセロハンテープ20が貼り付けられる。
(ラミネート性の評価基準)
◎:密着するまで5秒未満
○:密着するまで5秒以上、10秒未満
△:密着するまで10秒以上、15秒未満
×:密着するまで15秒以上、または密着しない
粘着シートを50mm×50mmの大きさに切り取り、剥離PETフィルムを剥がした。次に露出した粘着面をガラス板にラミネートし、これをサンプルとした。このサンプルを85℃、相対湿度85%で3日間放置した後、ガラス板から粘着シートを剥がし、ガラス板の表面への糊残りを目視で確認し、下記基準で評価した。
(糊残りの評価基準)
○:ガラス板の表面が貼り合せ前と比較して変化なし。
△:ガラス板の表面に糊残りがわずかに確認される。
×:ガラス板の表面に糊残りがはっきりと確認される。
以上の実施例及び比較例によれば、ポリウレタン(A)として、重量平均分子量が12000のポリウレタン(A-4)を用いた比較例1の組成物は、ラミネート性が不十分で、糊残りも見られた。また、多官能性単量体(B)を含まない比較例2の組成物は、剥離強度が高すぎ、ラミネート性も不十分であった。
20…セロハンテープ
30…ガラス基板
12…粘着層
14…基材。
Claims (13)
- ポリオキシアルキレンポリオール由来の構造及びポリイソシアネート由来の構造を含む骨格を有するポリウレタン(A)と、
ポリウレタン(A)以外の化合物であって、(メタ)アクリロイル基を複数有する多官能性単量体(B)と、
ポリウレタン(A)以外であり、かつ多官能性単量体(B)以外の化合物であって、ポリウレタン(A)及び多官能性単量体(B)と重合可能な、その他の単量体(C)と、
光重合開始剤(D)と、を含み、
前記ポリウレタン(A)が、ポリウレタン(a1)を含み、
前記ポリウレタン(a1)は、ポリオキシアルキレンポリオール由来の構造及びポリイソシアネート由来の構造を含む骨格を有し、かつ、前記ポリウレタン(a1)の複数の末端に(メタ)アクリロイル基を有し、
ポリウレタン(A)の重量平均分子量が30,000~200,000であることを特徴とする粘着剤組成物。 - ポリウレタン(A)、多官能性単量体(B)、及びその他の単量体(C)の合計量に対して、ポリウレタン(A)を30~60質量%、多官能性単量体(B)を10~20質量%、その他の単量体(C)を20~50質量%含む請求項1に記載の粘着剤組成物。
- ポリウレタン(A)に含まれるポリオキシアルキレンポリオール由来の構造は、数平均分子量500~5,000のポリオキシアルキレンポリオール由来の構造である請求項1または2に記載の粘着剤組成物。
- ポリウレタン(A)の骨格は、ポリオキシアルキレングリコール及びジイソシアネートとの共重合体である請求項1~3のいずれか1項に記載の粘着剤組成物。
- ポリウレタン(A)の骨格は、ポリプロピレングリコール及びジフェニルメタンジイソシアネートの水素添加物との共重合体である請求項4に記載の粘着剤組成物。
- ポリウレタン(A)における、(メタ)アクリロイル基は、(メタ)アクリロイルオキシ基の一部である請求項1~5のいずれか1項に記載の粘着剤組成物。
- 多官能性単量体(B)は、(メタ)アクリロイル基を3個以上有する請求項1~6のいずれか1項に記載の粘着剤組成物。
- 多官能性単量体(B)は、トリメチロールプロパントリアクリレートである請求項7に記載の粘着剤組成物。
- その他の単量体(C)は、(メタ)アクリロイル基を有する請求項8に記載の粘着剤組成物。
- その他の単量体(C)は、(メタ)アルキルアクリレートを含む請求項9に記載の粘着剤組成物。
- ポリウレタン(A)は、ポリウレタン(a2)をさらに含み、
前記ポリウレタン(a2)は、ポリオキシアルキレンポリオール由来の構造及びポリイソシアネート由来の構造を含む骨格を有し、かついずれか1つ末端のみに(メタ)アクリロイル基を有する請求項1~10のいずれか1項に記載の粘着剤組成物。 - 数基準で、ポリウレタン(A)に含まれるポリウレタン分子の末端の90~100%に(メタ)アクリロイル基が導入されている請求項1~10のいずれか1項に記載の粘着剤組成物。
- 請求項1~12のいずれか1項に記載の光硬化性粘着剤組成物の硬化物を含む粘着層が基材上に形成された粘着シート。
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WO2020066866A1 (ja) * | 2018-09-26 | 2020-04-02 | 昭和電工株式会社 | 表面保護シート用粘着剤組成物及び表面保護シート |
WO2021044833A1 (ja) * | 2019-09-05 | 2021-03-11 | 昭和電工株式会社 | バックグラインドテープ |
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CN111164176B (zh) | 2022-03-08 |
KR20200042916A (ko) | 2020-04-24 |
CN111164176A (zh) | 2020-05-15 |
JP7145868B2 (ja) | 2022-10-03 |
KR102253912B1 (ko) | 2021-05-20 |
TW201923011A (zh) | 2019-06-16 |
TWI695873B (zh) | 2020-06-11 |
JPWO2019069746A1 (ja) | 2020-09-10 |
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