WO2022080493A1 - 重合性組成物、その重合物及びそれらを用いた成形品 - Google Patents

重合性組成物、その重合物及びそれらを用いた成形品 Download PDF

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Publication number
WO2022080493A1
WO2022080493A1 PCT/JP2021/038313 JP2021038313W WO2022080493A1 WO 2022080493 A1 WO2022080493 A1 WO 2022080493A1 JP 2021038313 W JP2021038313 W JP 2021038313W WO 2022080493 A1 WO2022080493 A1 WO 2022080493A1
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Prior art keywords
meth
acrylamide
polymerizable composition
polymer
polymerizable
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PCT/JP2021/038313
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English (en)
French (fr)
Japanese (ja)
Inventor
篤史 安永
優 楢崎
エルシャット ムハマトアリ
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KJ Chemicals Corp
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KJ Chemicals Corp
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Priority to KR1020237016075A priority Critical patent/KR20230088756A/ko
Priority to JP2022515695A priority patent/JP7325785B2/ja
Priority to CN202180069950.8A priority patent/CN116391002B/zh
Priority to US18/032,205 priority patent/US20230391937A1/en
Priority to EP21880228.8A priority patent/EP4230664A4/en
Application filed by KJ Chemicals Corp filed Critical KJ Chemicals Corp
Publication of WO2022080493A1 publication Critical patent/WO2022080493A1/ja
Anticipated expiration legal-status Critical
Priority to JP2023085966A priority patent/JP2023111929A/ja
Priority to JP2023085964A priority patent/JP2023123427A/ja
Priority to JP2023085965A priority patent/JP2023115013A/ja
Priority to JP2023085967A priority patent/JP7778385B2/ja
Priority to JP2025191673A priority patent/JP2026015457A/ja
Priority to JP2025197610A priority patent/JP2026020270A/ja
Ceased legal-status Critical Current

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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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/56—Acrylamide; Methacrylamide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of 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; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
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    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • 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
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • 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
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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    • C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—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
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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    • 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
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    • 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
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    • 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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    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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    • 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
    • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
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    • C09J2433/00—Presence of (meth)acrylic polymer

Definitions

  • the present invention relates to a polymerizable composition, a polymer thereof, and a molded product using them.
  • N-substituted (meth) acrylamide has been used as a pressure-sensitive adhesive, a pressure-sensitive adhesive for optical members, an active energy-curable adhesive for polarizing plates, an ink for inkjet, a resin composition for optical modeling, a sealing material for semiconductors and electronic materials, and glass. It has come to be widely applied as a raw material monomer for coating agents for resin molded products and the like (Patent Documents 1 to 4). In particular, it is often reported that it is used as a substitute for (meth) acrylic acid because it has high cohesive power of amide groups, excellent adhesion to various substrates, and is not corrosive to metals or metal oxides. (Patent Documents 5 to 7). However, it has been pointed out that general-purpose N-substituted (meth) acrylamide has a large amount of hydrophilic monomers soluble in water, and its water resistance is insufficient depending on its content and the use of the obtained molded product.
  • N-substituted (meth) acrylamide is often used as a constituent component of active energy ray-curable resins, but when blended in long-life products such as electronic materials and optical materials, there is still a method for improving water resistance. Not proposed.
  • Japanese Unexamined Patent Publication No. 2008-287207 Japanese Unexamined Patent Publication No. 2011-12201 Japanese Unexamined Patent Publication No. 2001-310918 Japanese Unexamined Patent Publication No. 2010-155889 Japanese Unexamined Patent Publication No. 2011-137181 Japanese Unexamined Patent Publication No. 2010-235646 Japanese Unexamined Patent Publication No. 2013-256552
  • the present invention has excellent wettability to various substrates such as an organic substrate, an inorganic substrate, and a substrate made of an organic / inorganic composite material, which has a wide range of polarities from low polarity to high polarity, and has high transparency.
  • the first object is to provide a polymerizable composition which has curability and can provide a cured product having excellent water resistance by being cured, a polymer of the polymerizable composition, and the like. Further, it contains the polymerizable composition and / or a polymer thereof, has adhesiveness and adhesiveness to various substrates, and has high transparency, water resistance, stain resistance, yellowing resistance and durability.
  • a second object is to provide a pressure-sensitive adhesive composition and a laminate of a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition and various base materials.
  • the present invention comprises the above-mentioned polymerizable composition and / or a polymer thereof, and various adhesive compositions for adhesion of the same or different materials having high adhesive strength, impact resistance and water resistance to various substrates.
  • a coating composition that has high wettability and adhesion to a substrate and exhibits high surface hardness and water resistance when cured, moisture resistance, smoothness, stickiness resistance, good texture and stability over time.
  • An oil-in-water emulsified cosmetic composition that does not show skin irritation, has excellent emulsion stability, usability and stability over time, has high adhesion to various substrates, and has pigment dispersibility. It has excellent printing characteristics such as surface drying property, ejection stability, and sharpness, and can accurately model inks with high curability, yellowing resistance, and water resistance, and three-dimensional shaped objects with high strength, heat resistance, and water resistance.
  • the third object is to provide an ink composition for three-dimensional modeling, which has excellent curing shrinkage resistance.
  • the present inventors have at least one chain-type or ring-type hydrocarbon group having 6 or more carbon atoms as a hydrophobic group, and a (meth) acrylamide group as a hydrophilic group.
  • the present invention has been completed by finding that a polymerizable composition containing an amphipathic N-substituted (meth) acrylamide having a specific structure can solve the above-mentioned problems.
  • R 1 represents a hydrogen atom or a methyl group
  • one of R 2 and R 3 represents a chain hydrocarbon group having 6 or more carbon atoms or a cyclic hydrocarbon group having 6 or more carbon atoms
  • the other indicates a cyclic hydrocarbon group.
  • N-substituted (meth) acrylamide is N-mono-substituted (meth) acrylamide and N, N-di-substituted (meth) acrylamide, and is a chain-like substituent having 6 or more carbon atoms and 36 or less carbon atoms.
  • the polymerizable composition according to (1) above which has one or more structures selected from the saturated structure and the unsaturated structure and the cyclic saturated structure and the unsaturated structure.
  • the polymerizable composition according to any one of (1) to (5) above which is a polymerization initiator and a compound having an unsaturated bond (however, N-substituted (meth) acrylamide (A)). And polymers using it), non-polymerizable oligomers and non-polymerizable polymers (excluding polymers using N-substituted (meth) acrylamide (A)), and the polymers according to (6) above.
  • a polymerizable composition further containing one or more selected from the above, (8) The polymerizable composition according to any one of (1) to (5) and (7), the polymer according to (6), or (1) to (5) and (7).
  • a laminate of the pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition according to (8) above and an organic-based and / or an inorganic-based base material, and the surface tension of the organic-based and / or inorganic-based base material is 22.
  • Laminated body of 6.6 to 59.0 mN ⁇ m-1 (10) The polymerizable composition according to any one of (1) to (5) and (7), or the adhesive composition containing the polymer and the cross-linking agent according to (6).
  • the polymerizable composition containing N-substituted (meth) acrylamide (A) having a specific structure has high transparency due to the well-balanced amphotericity of N-substituted (meth) acrylamide (A). While having good curability, it has excellent wettability to various substrates having a wide range of polarities from low polarity to high polarity consisting of organic base materials, inorganic base materials and organic / inorganic hybrid base materials. It is possible to obtain a composition, a polymer of the polymerizable composition, and the like.
  • a pressure-sensitive adhesive composition that exhibits adhesion and adhesive strength to various substrates by containing the obtained polymerizable composition and / or a polymer thereof, and has high transparency, stain resistance, yellowing resistance, and durability. It is possible to provide a laminate of a product, a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition, and various base materials. Further, the present invention is an adhesive composition for the same or different materials having high adhesive strength, impact resistance and water resistance to various substrates by containing the polymerizable composition and / or a polymer thereof, and moisture resistance.
  • the first embodiment of the present invention is a polymerizable composition.
  • the second embodiment is a polymer obtained by polymerizing the polymerizable composition of the first embodiment with active energy rays and / or heat.
  • the polymerizable composition of the first embodiment excludes a polymerization initiator, a compound having an unsaturated bond (provided that N-substituted (meth) acrylamide (A) and a polymer using the same are excluded. ), Non-polymerizable oligomers and non-polymerizable polymers (excluding polymers using N-substituted (meth) acrylamide (A)), and one or more selected from the polymers of the second embodiment. It is a polymerizable composition.
  • the polymer of the second embodiment is a polymerization initiator, a compound having an unsaturated bond (excluding N-substituted (meth) acrylamide (A) and a polymer using the same).
  • Non-polymerizable oligomers and non-polymerizable polymers excluding polymers using N-substituted (meth) acrylamide (A)
  • cross-linking agents with two or more reactive functional groups in the molecule unsaturated in the molecule
  • It is a polymerizable composition further containing one or more selected from (excluding compounds having two or more bonds).
  • the polymerizable composition according to the first embodiment of the present invention contains N-substituted (meth) acrylamide (A) represented by the following general formula [1].
  • R 1 represents a hydrogen atom or a methyl group
  • one of R 2 and R 3 represents a chain hydrocarbon group having 6 or more carbon atoms or a cyclic hydrocarbon group having 6 or more carbon atoms.
  • the other indicates a hydrogen atom, a chain hydrocarbon group having 1 or more carbon atoms or a cyclic hydrocarbon group having 3 or more carbon atoms
  • R 2 and R 3 are 6 members together with the nitrogen atom carrying them. It includes those having the above saturated rings.
  • the 6-membered or more saturated ring may or may not contain a heteroatom.
  • R 2 and R 3 may or may not contain a substituent containing a hetero atom, and when they are contained, the number of hetero atoms is 3 or less.
  • the hetero atom means an oxygen atom, a sulfur atom, a nitrogen atom or a boron atom.
  • the N-substituted (meth) acrylamide not included in the general formula [1] is also referred to as N-substituted (meth) acrylamide (B).
  • the polymer according to the second embodiment of the present invention is a polymer obtained by polymerizing the polymerizable composition of the first embodiment with active energy rays and / or heat.
  • the polymer is a soluble polymer having no crosslinked structure, and may be a homopolymer of any one monomer selected from the N-substituted (meth) acrylamide (A), and may be arbitrarily selected from A. It may be a copolymer of A obtained by copolymerizing two or more kinds of monomers in an arbitrary proportion, or one or more kinds of monomers arbitrarily selected from A may be arbitrarily proportional to a copolymerizable monomer other than A. It may be a copolymer obtained by copolymerizing with.
  • the content of A in the copolymer is preferably 1% by weight or more based on the total weight of the copolymer.
  • the N-substituted (meth) acrylamide (A) used in the first to fourth embodiments of the present invention (hereinafter, also referred to as the present embodiment) is homophilic and has a low polar substrate in the molecule.
  • a hydrophobic substituent capable of imparting wettability a chain hydrocarbon group having 6 or more carbon atoms, a cyclic hydrocarbon group having 6 or more carbon atoms, and a saturation of 6 or more members including a nitrogen atom carrying R2 and R3 are included. It has at least one substituent selected from the group consisting of rings and a hydrophilic (meth) acrylamide group capable of imparting wettability to a highly polar substrate.
  • the polymerizable composition according to the present embodiment has good compatibility with each component constituting the composition, can exhibit high transparency, and is organic. It has good wettability to various base materials such as a base material having a wide range of polarities from low polarity to high polarity, which is composed of a based base material, an inorganic base material, and an organic / inorganic hybrid base material.
  • N-substituted (meth) acrylamide (A) exhibits sufficient curability and polymerizable property with respect to active energy rays and / or heat
  • the polymerizable composition containing the N-substituted (meth) acrylamide (A) has high curability and polymerizable property.
  • a polymerizable composition containing N-substituted (meth) acrylamide (A) and / or the polymerizable composition due to the synergistic effect of good wettability to various substrates having a wide range of polarities and strong aggregating power between amide groups.
  • the pressure-sensitive adhesive composition and the adhesive composition formed from a polymer obtained by polymerizing the composition are excellent in adhesion to various substrates. .. Therefore, as a polymerizable composition and / or a molded product of the polymer, a pressure-sensitive adhesive composition having high adhesive strength and stain resistance (reworkability), and an adhesive having high adhesive strength, impact resistance and water resistance. The composition is obtained.
  • the polymerizable composition and / or the polymer thereof according to the present embodiment can be used not only in the pressure-sensitive adhesive composition and the adhesive composition, but also by utilizing the above-mentioned characteristics of N-substituted (meth) acrylamide (A). It can be applied to various applications such as a coating agent composition, a cosmetic composition, an ink composition, an ink composition for inkjet, and an ink composition used for three-dimensional modeling.
  • the carbon number of the chain hydrocarbon group or the cyclic hydrocarbon group in R2 and R3 in the general formula [ 1 ] is the wettability of the polymerizable composition according to the present embodiment to the low-polarity substrate. From the viewpoint of improving the above, 8 or more is preferable, 12 or more is more preferable, and 16 or more is further preferable.
  • the number of carbon atoms of the chain hydrocarbon group or the cyclic hydrocarbon group is not particularly limited, but the wettability of the polymerizable composition to the highly polar substrate is sufficiently maintained, that is, the low polar substrate. From the viewpoint of the balance of wettability with the highly polar substrate, it is usually 36 or less, preferably 24 or less, and more preferably 22 or less.
  • the number of saturated rings containing nitrogen atoms supporting R 2 and R 3 in the general formula [1] balances the wettability of the polymerizable composition to the low-polarity substrate and the high-polarity substrate. From the viewpoint of saturating, it is preferably 6 or more and 12 or less.
  • the N-substituted (meth) acrylamide (A) used in the present embodiment is N-mono-substituted (meth) acrylamide and N, N-di-substituted (meth) acrylamide, and as described above, the substituent has 6 or more carbon atoms. Moreover, it is preferable to have one or more structures selected from a chain-shaped saturated structure and an unsaturated structure and a cyclic saturated structure and an unsaturated structure of 36 or less. Further, it is more preferable that the N-substituted (meth) acrylamide (A) has at least one substituent having an unsaturated structure.
  • the N-substituted (meth) acrylamide (A) when the N-substituted (meth) acrylamide (A) is liquid at room temperature, the content of the N-substituted (meth) acrylamide (A) in the polymerizable composition of the present embodiment can be arbitrarily adjusted to some extent. Therefore, it is more preferable that the N-substituted (meth) acrylamide (A) contains one or more substituents having an unsaturated structure, which has an effect of lowering the melting point thereof.
  • the saturated water absorption rate of the cured product at room temperature is preferably 10% or less.
  • the normal temperature means 5 ° C to 35 ° C under atmospheric pressure.
  • the saturated water absorption rate of the cured product is the water absorption rate in the saturated water absorption state, and can be calculated by the method described later. Further, it suffices to be in a saturated water absorption state, and the method, conditions, etc. for reaching that state are not limited. If the saturated water absorption rate of the cured product is 10% or less, it has sufficient water resistance. The lower the saturated water absorption rate, the higher the water resistance of the cured product. Therefore, the saturated water absorption rate of the cured product is more preferably 7% or less, and particularly preferably 5% or less.
  • the surface tension of the N-substituted (meth) acrylamide (A) is preferably 24.0 to 46.0 mN ⁇ m -1 .
  • the surface tension of N-substituted (meth) acrylamide (A) is a calculated value at 23 ° C. obtained by the Meissner method (Chemical Engineering Handbook Revised 7th Edition, p. 66), and the average error is 3%. be.
  • the polymerizable composition containing the N-substituted (meth) acrylamide (A) is applied to a substrate having a different polarity.
  • Molecules can be arranged according to the polarity of the base material, and as a result, good wettability to various base materials showing the above-mentioned wide range of polarities is exhibited, and the polymerizable composition and / or a molded product of the polymer thereof is exhibited.
  • the adhesion of the pressure-sensitive adhesive composition, the adhesive composition, and the like is also improved.
  • the surface tension of N-substituted (meth) acrylamide (A) is more preferably 28.0 to 36.0 mN.m- 1 and 30.0 to 33.0 mN.m- 1 . It is particularly preferable to have.
  • the N-substituted (meth) acrylamide (A) is preferably in a liquid state at room temperature. Since the N-substituted (meth) acrylamide (A) is a liquid at room temperature, the content in the polymerizable composition according to the present embodiment can be arbitrarily adjusted to some extent without performing operations such as heating. And it is easy to maintain the transparency of the obtained polymerizable composition.
  • the N-substituted (meth) acrylamide (A) is more preferably liquid at 30 ° C. or lower, and even more preferably liquid at 25 ° C. or lower.
  • the term "liquid” includes a liquid state having fluidity and a wax state having no fluidity.
  • the content of N-substituted (meth) acrylamide (A) is 1% by weight or more and 100% by weight based on the total weight of the polymerizable composition. Also, the content of A can be appropriately adjusted according to the specific use of the polymerizable composition. If 1% by weight of N-substituted (meth) acrylamide (A) is contained, the polymerizable composition is curable to active energy rays and / or heat, and has wettability to various substrates exhibiting curability, polymerizable property, transparency and a wide range of polarities.
  • the content of N-substituted (meth) acrylamide (A) is 5 to 5 because the improving effect of N-substituted (meth) acrylamide (A) can be exhibited and the balance between curability, polymerizability, transparency and wettability can be better exhibited. It is more preferably 90% by weight, further preferably 10 to 80% by weight, and particularly preferably 20 to 70% by weight.
  • N-substituted (meth) acrylamide (A) has an aliphatic hydrocarbon group having 6 or more carbon atoms which does not contain an unsaturated bond as a substituent
  • the aliphatic hydrocarbon group may be linear, branched or cyclic. good.
  • N-substituted (meth) acrylamides include: n-hexyl (meth) acrylamide, sec-hexyl (meth) acrylamide, tert-hexyl (meth) acrylamide, n-heptyl (meth) acrylamide, sec.
  • the N-substituted (meth) acrylamide (A) has an aliphatic hydrocarbon group having 6 or more carbon atoms including an unsaturated bond as a substituent
  • the aliphatic hydrocarbon group may be linear, branched or cyclic. ..
  • Examples include the following N-substituted (meth) acrylamides: hexenyl (meth) acrylamide, heptenyl (meth) acrylamide, octenyl (meth) acrylamide, nonenyl (meth) acrylamide, decenyl (meth) acrylamide, undecenyl (meth).
  • octenyl (meth) acrylamide, nonenyl (meth) acrylamide, undecenyl (meth) acrylamide, and oleyl (meth) acrylamide are preferable from the viewpoint that industrial products can be easily obtained.
  • the polymerizable composition according to the present embodiment includes, in addition to N-substituted (meth) acrylamide (A), a polymerization initiator, a compound having an unsaturated bond (however, N-substituted (meth) acrylamide (A) and the like. (Excluding polymers using N-substituted (meth) acrylamide (A)), non-polymerizable oligomers and non-polymerizable polymers (excluding polymers using N-substituted (meth) acrylamide (A)), and polymers of the polymerizable composition. It may further contain one or more of the above.
  • the polymerizable composition further contains a polymerization initiator, the curability to active energy rays and / or heat is further improved, and when the polymerizable composition further contains a compound having an unsaturated bond, the pressure-sensitive adhesive composition, It can be more preferably used as an adhesive composition, a coating agent composition and various ink compositions. Further, when the polymerizable composition further contains a non-polymerizable oligomer and / or a non-polymerizable polymer, the viscosity of the polymerizable composition and the flexibility of the cured product thereof can be easily adjusted.
  • the polymerizable composition when the polymerizable composition further contains the polymer, the adhesive strength of the polymerizable composition or the pressure-sensitive adhesive composition which is a molded product of the polymer to various substrates, and various types of the adhesive composition. Adhesive strength to the substrate is improved.
  • the polymerizable composition shall represent both a polymerizable composition that does not contain the polymer and a polymerizable composition that contains the polymer.
  • Examples of the compound having an unsaturated bond include a monofunctional monomer having one unsaturated bond, a monofunctional oligomer, a polyfunctional monomer or polyfunctional oligomer having two or more unsaturated bonds, and a polymerizable polymer having an unsaturated bond. Can be mentioned.
  • the compounds having these unsaturated bonds are not limited because they depend on the specific use of the polymerizable composition, but the polymerizable polymer may be used for the purpose of adjusting the viscosity of the polymerizable composition to the low viscosity side by the monofunctional monomer.
  • the polyfunctional monomer For the purpose of adjusting the viscosity of the polymerizable composition to the high viscosity side, and for the purpose of adjusting the curability of the polymerizable composition and the cross-linking rate of the obtained cured product by the polyfunctional monomer, the polyfunctional oligomer and the polymerizable polymer, etc. Is used in.
  • the components other than the N-substituted (meth) acrylamide (A) in the polymerizable composition of the present embodiment may be added alone or in combination of two or more.
  • the respective contents may be appropriately adjusted according to the specific use, but the monofunctional monomer is 1 to 99% by weight and the polyfunctional monomer is 0.05 to 50% based on the total weight of the polymerizable composition.
  • the polyfunctional oligomer may be 0.05 to 50% by weight
  • the polymerizable or non-polymerizable polymer may be 0.01 to 10% by weight
  • the polymer of the polymerizable composition may be 0.01 to 10% by weight. preferable.
  • homopolymers or copolymers of various monomers having a weight average molecular weight (Mw) of 1,000 or more and less than 10,000 are oligomers, and those having a Mw of 10,000 or more are polymers. Classify as.
  • the polyfunctional monomer is a monomer having two or more unsaturated bonds selected from a (meth) acrylate group, a (meth) acrylamide group, a vinyl group, an allyl group, and a maleimide group in the molecule, and is a polyfunctional (meth). Examples thereof include acrylate and polyfunctional (meth) acrylamide. Generally, a polyfunctional monomer having 10 or less unsaturated bonds in the molecule is preferably used.
  • polyfunctional (meth) acrylate examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and tripropylene glycol di (meth).
  • Tetraethylene glycol di (meth) acrylate Tetraethylene glycol di (meth) acrylate, Ditetraethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, Polytetramethylene glycol di (meth) acrylate, Butylene glycol di (Meta) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,6-Hexanediol ethylene oxide-modified di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanedi
  • polyfunctional (meth) acrylamide examples include methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, diallyl (meth) acrylamide, N- [tris (3- (meth) acrylamide propoxymethyl) methyl] (meth) acrylamide, and N. , N-bis (2- (meth) acrylamide ethyl) (meth) acrylamide, 4,7,10-trioxa-1,13-tridecambis (meth) acrylamide, N, N'-1,2-ethandylbis [N-( 2- (Meta) acrylamide ethyl)] (meth) acrylamide and the like.
  • One of these polyfunctional monomers may be used alone, or two or more thereof may be used in combination.
  • the monofunctional monomer is a reactive double bond in the molecule such as monofunctional (meth) acrylate, monofunctional (meth) acrylamide, styrene, alkoxy radical-containing monomer, vinyl group-containing monomer, allyl group-containing monomer and maleimide group-containing monomer, and the like.
  • monofunctional (meth) acrylate monofunctional (meth) acrylamide
  • styrene alkoxy radical-containing monomer
  • vinyl group-containing monomer vinyl group-containing monomer
  • allyl group-containing monomer and maleimide group-containing monomer and the like.
  • examples thereof include radically polymerizable compounds having.
  • the monofunctional (meth) acrylate is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hydroxyethyl.
  • the monofunctional (meth) acrylamide is, for example, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide.
  • N-ethoxymethyl (meth) acrylamide N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N -(2-Hydroxyethyl) acrylamide, N- [3- (dimethylamino)] propylacrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, diacetone (meth) acrylamide, etc. Can be mentioned.
  • These monofunctional (meth) acrylamides are included in the above-mentioned N-substituted (meth) acrylamides (B).
  • vinyl group-containing monomer examples include N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, vinyl acetate, styrene, vinyl oxazoline and the like.
  • One of these monofunctional monomers may be used alone, or two or more thereof may be used in combination.
  • Examples of the monofunctional oligomer, the polyfunctional oligomer and the polymerizable polymer include linear and / or branched oligomers and polymers having a skeleton such as acrylic, ester, ether, urethane and amide, and have a main chain structure. Urethane-based, epoxy-based and acrylic-based are classified. When these are classified by weight average molecular weight (Mw), the above-mentioned oligomers composed of polyfunctional (meth) acrylate and / or polyfunctional (meth) acrylamide are exemplified as those having Mw of 1,000 or more and less than 10,000.
  • Mw weight average molecular weight
  • Examples of those having a Mw of 10,000 or more include the following polymerizable polymers: bifunctional polyurethane (meth) acrylate, polyfunctional polyurethane (meth) acrylate, bifunctional polyester (meth) acrylate. , Polyfunctional urethane (meth) acrylate, bifunctional polyester (meth) acrylate, polyfunctional polyester (meth) acrylate, bifunctional polyether (meth) acrylate, polyfunctional polyether (meth) acrylate, bifunctional polyamide (meth) acrylate , Polyfunctional polyamide (meth) acrylate, bifunctional poly (meth) acrylic acid ester (meth) acrylate, polyfunctional poly (meth) acrylic acid ester (meth) acrylate, bifunctional poly (meth) acrylic acid ester (meth) acrylamide.
  • One of these oligomers or polymers may be used alone, or two or more thereof may be used in combination.
  • the monofunctional or polyfunctional oligomer is a commercially available product, and from the viewpoint of easy availability, the urethane acrylate is, for example, manufactured by Mitsubishi Chemical Co., Ltd., trade names UV-3200B, UV-3000B, UV-6640B, UV-3700B, UV-.
  • UV-7000B manufactured by Shin-Nakamura Chemical Industry, trade name U-4HA, U-200PA, manufactured by Daisel Cytec, trade name EBECRYL245, EBECRYL1259, EBECRYL8210, EBECRYL284, EBECRYL8402, SARTOMER, product name CN9 , CN9002, CN9029, Negami Kogyo Co., Ltd., trade names UN1255, UN-5507, Kyoei Co., Ltd., trade names AH-600, UA-306I, etc. can be used, and KJ Chemicals Co., Ltd., Quick Cure as a UV curable urethane oligomer can be used.
  • (Registered trademark) 6100, Quick Cure (registered trademark) 7100, Quick Cure (registered trademark) 8100 and the like can be used.
  • the compound having an unsaturated bond may be a monomer or an oligomer having an unsaturated bond, and is preferably the above-mentioned various monofunctional monomers, polyfunctional monomers, or oligomers.
  • the compound having an unsaturated bond contained in the polymerizable composition of the present embodiment is a monofunctional monomer having one unsaturated bond from the viewpoint of obtaining a thermoplastic polymer used for adjusting physical properties such as viscosity. It is preferable to have a monomer, and a monomer capable of introducing a cross-linking point is particularly preferable from the viewpoint of enhancing the cohesive force of the obtained polymer.
  • the content of these compounds having an unsaturated bond may be arbitrarily adjusted according to the specific use, but is 1 to 99 weight in total with respect to the total weight of the polymerizable composition according to the present embodiment. % Is preferable.
  • the monomer into which the cross-linking point can be introduced is a monomer having one or more reactive functional groups in the molecule, and is, for example, a hydroxyl group-containing (meth) acrylic monomer, a carboxyl group-containing (meth) acrylic monomer, or an amino group-containing monomer.
  • a hydroxyl group-containing (meth) acrylic monomer a hydroxyl group-containing (meth) acrylic monomer, a carboxyl group-containing (meth) acrylic monomer, or an amino group-containing monomer.
  • Acrylic monomer can be mentioned.
  • hydroxyl group-containing (meth) acrylic monomer examples include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate.
  • Hydroxyalkyl (meth) acrylates such as 8-hydroxyoctyl (meth) acrylates, hydroxyalkyl (meth) acrylamides such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, and others, 2- Primary hydroxyl group-containing (meth) acrylic monomers such as acryloyloxyethyl 2-hydroxyethylphthalic acid and N-methylol (meth) acrylamide, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- Secondary hydroxyl group-containing (meth) acrylic monomers such as hydroxy 3-phenoxypropyl (meth) acrylate, 3-chloro2-hydroxypropyl (meth) acrylate, 2-hydroxy 3-phenoxypropyl (meth) acrylate, 2,2- Examples thereof include tertiary hydroxyl group-containing (meth) acrylic monomers such as dimethyl 2-hydroxyethyl (
  • carboxyl group-containing (meth) acrylic monomer examples include monocarboxylic acids such as (meth) acrylic acid and crotonic acid, dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, and itaconic acid. And so on. Among these, (meth) acrylic acid is preferably used.
  • amino group-containing (meth) acrylic monomer examples include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and N, N-di-t-butylaminoethyl.
  • Aminoalkyl (meth) acrylates such as (meth) acrylates, N, N-diethylaminoethyl (meth) acrylates, N, N-dimethylaminoethyl (meth) acrylamides, N, N-diethylaminoethyl (meth) acrylamides, N, Examples thereof include aminoalkyl (meth) acrylamides such as N-dimethylaminopropyl (meth) acrylamide.
  • acetacetyl group-containing (meth) acrylic monomer examples include 2- (acetoxy) ethyl (meth) acrylate.
  • Examples of the glycidyl group-containing (meth) acrylic monomer include glycidyl (meth) acrylate, (meth) acrylamide glycidyl, N-hydroxyethyl (meth) acrylamide glycidyl ether, and N-methyl-N-hydroxyethyl (meth).
  • Examples of the oxazoline group-containing vinyl monomer include 2-vinyl-2-oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, and 4-ethyl-2-vinyl.
  • 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline and 4,4-dimethyl-2-vinyl-2-oxazoline having high reactivity are preferable, and 2-vinyl-2- Oxazoline is most preferred.
  • the monomer capable of introducing these cross-linking points is not limited to one type, and a plurality of types may be used in combination.
  • the cross-linking agent is a compound capable of introducing a cross-linking structure into a cured product of a polymerizable composition, and a monomer capable of introducing the above-mentioned cross-linking points and an oligomer capable of introducing a plurality of cross-linking points formed by polymerizing the above-mentioned cross-linking points.
  • examples thereof include polymers, compounds having two or more reactive functional groups in the molecule, polyfunctional monomers having two or more unsaturated bonds in the above-mentioned molecules, polyfunctional oligomers and polymerizable polymers.
  • the monomer capable of introducing the cross-linking point is a monofunctional monomer having one or more reactive functionalities in the molecule, it is treated as a monofunctional monomer.
  • the cross-linking method using a cross-linking agent in the present embodiment comprises (1) reacting the polymerizable composition or its polymer with a reactive functional group (for example, a hydroxyl group or an amino group) contained in the polymerizable composition or its polymer.
  • a reactive functional group for example, a hydroxyl group or an amino group
  • a compound having a functional group for example, an isocyanate group or a carboxyl group
  • the polymerizable composition or a polymer thereof contains a polyfunctional monomer, a polyfunctional oligomer or a polymerizable polymer.
  • the polymerizable composition or its polymer contains a cross-linking agent such as a polyfunctional monomer, a poly-functional oligomer or a polymerizable polymer, or a monomer capable of introducing a cross-linking point. Examples thereof include a method of cross-linking by irradiation with active energy rays and / or a reaction of a cross-linking agent.
  • the cross-linking method (3) is a method in which the cross-linking methods of (1) and (2) are appropriately combined.
  • the cross-linking agent (that is, the compound having a functional group that reacts with the reactive functional group contained in the polymerizable composition or the polymer thereof) includes an isocyanate compound, an epoxy compound, an aziridine compound, and a carboxyl. Examples thereof include compounds having a group and an oxazoline group.
  • Examples of the isocyanate compound include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate. More specifically, examples of the isocyanate compound include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate, 2,4.
  • -Aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Toso Co., Ltd., trade name: Coronate L), trimethylol propane / Hexamethylene diisocyanate trimer adduct (manufactured by Toso Co., Ltd., trade name: Coronate HL), isocyanurate form of hexamethylene diisocyanate (manufactured by Toso Co., Ltd., trade name: Coronate HX) and the like.
  • One of these isocyanate compounds may be used alone, or two or more thereof may be mixed and used.
  • Examples of the epoxy compound include polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, glycerin diglycidyl ether, diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N, N, N', N'-tetra.
  • Glycidyl-m-xylenediamine manufactured by Mitsubishi Gas Chemicals, trade name: TETRAD-X
  • 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane manufactured by Mitsubishi Gas Chemicals, trade name: TETRAD-C) Etc.
  • One of these compounds may be used alone, or two or more thereof may be mixed and used.
  • aziridine compound examples include commercial products such as trade name: HDU, trade name: TAZM, and trade name: TAZO (all manufactured by Mutual Pharmaceutical Co., Ltd.). One of these compounds may be used alone, or two or more thereof may be mixed and used.
  • Examples of the compound having a carboxyl group include phthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyetanedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid and the like.
  • Alicyclic dicarboxylic acids such as aromatic dicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, malonic acid, dimethylmalonic acid, succinic acid, 3,3 -Adicarboxylic acid, glycolic acid such as diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelli acid, azelaic acid, sebacic acid, suberic acid, etc.
  • hydroxycarboxyl group such as 3-hydroxybutyric acid, 4-hydroxyvaleric acid, hydroxypropionic acid, hydroxycaproic acid, hydroxybenzoic acid, and a dicarboxyl group derived from their ester-forming derivatives or their anhydrides.
  • Examples include compounds. One of these compounds may be used alone, or two or more thereof may be mixed and used.
  • Examples of the compound having an oxazoline group include alkylene bisoxazolines such as tetramethylenebisoxazoline and hexamethylenebisoxazoline, 1,3-phenylenebis (2-oxazoline), and 1,4-bis (4,5-dihydro-2-oxazoline). ) Examples thereof include aromatic bisoxazolines such as benzene, homopolymers of various oxazoline group-containing vinyl monomers described above, and compounds having an oxazoline group such as copolymers with compounds having unsaturated bonds. One of these compounds may be used alone, or two or more thereof may be mixed and used.
  • the content of the cross-linking agent (that is, the polymerizable composition or a compound having two or more functional groups in the molecule that reacts with the reactive functional groups contained in the polymer) in the cross-linking method (1) is the polymerizable composition.
  • it can be appropriately selected depending on the amount of the reactive functional group contained in the polymer and the balance with the molecular weight, and further depending on the specific use, but usually, it is 0. 1 to 15% by weight is preferable, 0.5 to 10% by weight is more preferable, and 1 to 5% by weight is particularly preferable.
  • the cross-linking by the cross-linking agent is insufficient, and when the molded product after the cross-linking reaction is a cured product of the pressure-sensitive adhesive composition and the adhesive composition, sufficient durability is obtained. It may not be obtained and may cause adhesive residue (contamination) in the pressure-sensitive adhesive composition. Further, when the molded product after the crosslinking reaction is a cured product of a coating agent, sufficient surface hardness cannot be obtained, and when the molded product after the crosslinking reaction is a cured product of a three-dimensional molding ink, that is, a three-dimensional molded product. , It may not be possible to obtain a model with sufficient hardness and tensile strength.
  • the crosslinking reaction in the crosslinking method (1) may be carried out at room temperature, but is preferably carried out at a temperature of about 40 ° C. to 120 ° C. in order to accelerate the reaction.
  • the above-mentioned one can be used as the crosslinking agent (that is, the polyfunctional monomer, the polyfunctional oligomer or the polymerizable polymer).
  • irradiation can be performed using various active energy rays described later.
  • ultraviolet rays UV, UV-LED, etc.
  • visible light it is preferable to use a photopolymerization initiator in combination.
  • an electron beam (EB) or an energy ray having a shorter wavelength than the electron beam is used as the active energy ray, high energy can be given, so that it is not necessary to contain a photopolymerization initiator.
  • polyfunctional oligomer or polymerizable polymer is a self-initiating functional group such as a maleimide group, an allyl ether group or a vinyl ether group, a photopolymerization initiator is contained. It does not have to be.
  • the content of the crosslinking agent (that is, the polyfunctional monomer, the polyfunctional oligomer or the polymerizable polymer) in the crosslinking method (2) is preferably 0.05 to 50% by weight based on the total weight of the polymerizable composition. From the viewpoint of a good balance between the adhesion of the cured product after crosslinking to various substrates and the hardness and strength of the obtained cured product, 0.1 to 30% by weight is more preferable, and 0.5 to 20% by weight is particularly preferable. preferable. If the content is less than 0.05% by weight, the cross-linking by the cross-linking agent is insufficient, and if the molded product after the cross-linking reaction is a pressure-sensitive adhesive composition and an adhesive composition, sufficient durability cannot be obtained.
  • the molded product after the crosslinking reaction is a cured product of the coating agent, sufficient surface hardness cannot be obtained, and the molded product after the crosslinking reaction is a cured product of the ink for a three-dimensional modeling model material, that is, a three-dimensional molded product. In some cases, it may not be possible to obtain a model with sufficient hardness and tensile strength.
  • the content exceeds 50% by weight, when the molded product after the crosslinking reaction is a cured product of the pressure-sensitive adhesive composition and the adhesive composition, shrinkage due to curing peculiar to active energy ray curing is likely to occur.
  • the content of the cross-linking agent (that is, the polyfunctional monomer, the polyfunctional oligomer or the polymerizable polymer, and the compound having two or more reactive functional groups in the molecule) in the cross-linking method (3) depends on the type of the cross-linking agent used. different.
  • the content of the polyfunctional monomer, the polyfunctional oligomer or the polymerizable polymer is preferably 0.05 to 30% by weight based on the total weight of the polymerizable composition, and two reactive functional groups are contained in the molecule.
  • the content of the compound having the above is preferably 0.1 to 10% by weight based on the total weight of the polymerizable composition.
  • the total content of these cross-linking agents is polymerizable. It is preferably 0.15 to 40% by weight, more preferably 0.2 to 35% by weight, and particularly preferably 0.5 to 30% by weight, based on the total weight of the composition. If the total content is less than 0.15% by weight, the cross-linking by the cross-linking agent is insufficient, and if the molded product after the cross-linking reaction is a cured product of the pressure-sensitive adhesive composition and the adhesive composition, sufficient durability is sufficient.
  • the property may not be obtained, and it also tends to cause adhesive residue (contamination) in the pressure-sensitive adhesive composition.
  • the molded product after the crosslinking reaction is a cured product of a coating agent, sufficient surface hardness cannot be obtained, and when the molded product after the crosslinking reaction is a cured product of a three-dimensional molding ink, that is, a three-dimensional molded product. , It may not be possible to obtain a model with sufficient hardness and tensile strength.
  • the total content exceeds 40% by weight, and the molded product after the cross-linking reaction is a cured product of the pressure-sensitive adhesive composition and the adhesive composition, the adhesion to the substrate also decreases as the flexibility decreases.
  • the molded product after the crosslinking reaction is a cured product of the three-dimensional modeling ink, that is, a three-dimensional modeled product, there is a possibility that a modeled product having sufficient elongation at break cannot be obtained.
  • the polymerizable composition according to the present embodiment is a non-polymerizable oligomer having a weight average molecular weight (Mw) of 1,000 or more and less than 10,000 and / or a non-polymerizable polymer having Mw of 10,000 or more. May be further contained.
  • Mw weight average molecular weight
  • examples of the non-polymerizable oligomer and the non-polymerizable polymer include thermoplastic resins, rosin-based resins, and mixtures thereof.
  • thermoplastic resin examples include (meth) acrylic resin, cyclic polyolefin resin, cellulose resin, polyester resin, polyurethane resin, polysulfonic acid resin, ABS resin which is a copolymer of acrylonitrile and butadiene and styrene, polycarbonate resin, and polyamide. Examples thereof include resin and polyimide resin.
  • the rosin-based resin includes natural rosin such as gum rosin, hydrogenated rosin obtained by modifying natural rosin, disproportionated rosin, rosin-modified phenol resin, maleic acid-modified rosin resin, maleated rosin, and esterified gum. Examples include rosin resin. These non-polymerizable oligomers and non-polymerizable polymers may be used alone or in combination of two or more.
  • the polymerizable composition according to the present embodiment may further contain a polymerization initiator and / or a compound having an unsaturated bond.
  • the polymerizable composition is more curable and polymerizable due to active energy rays and / or heat, and the active energy rays and / or thermosetting adhesive composition, adhesive composition, and coating agent composition. It can be suitably used as a product, an ink composition, or the like.
  • a pressure-sensitive adhesive layer can be formed by applying a polymerizable composition to a separator or various substrates described later and then curing the pressure-sensitive adhesive composition with active energy rays.
  • polymerizing a polymerizable composition by active energy rays and heat is also referred to as hybrid polymerization.
  • the polymerization may be carried out in the order of the active energy ray and the heat, or the polymerization may be carried out in the order of the heat and the active energy ray.
  • the active energy ray is defined as an energy ray capable of decomposing a compound (photopolymerization initiator) that generates an active species to generate an active species.
  • active energy rays include visible light, ultraviolet rays, infrared rays, ⁇ rays, ⁇ rays, ⁇ rays, X-rays, electron beams (EB) and the like.
  • EB electron beams
  • ultraviolet rays, visible light or the like it is preferable to use a photopolymerization initiator.
  • the irradiation of the active energy rays is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas or an atmosphere in which the oxygen concentration is lowered, but the polymerizable composition according to the present embodiment is N-substituted ( Since it has meta) acrylamide (A), it has good curability and can be sufficiently cured even in a normal air atmosphere.
  • the irradiation temperature of the active energy ray is preferably 10 ° C. to 200 ° C., and the irradiation time is preferably 1 second to 60 minutes.
  • the photopolymerization initiator is a substance that generates radicals by irradiating with ultraviolet rays having an appropriate wavelength that can trigger the polymerization reaction, depending on the type of the active energy ray-reactive component (that is, a photoradical polymerization initiator). It should be.
  • the photopolymerization initiator may be appropriately selected from ordinary ones such as acetophenone type, benzoin type, benzophenone type and thioxanthone type, and as a commercial product, IGM Resins B.I. V.
  • the photoradical polymerization initiator is not particularly limited, and is, for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and anisole methyl ether, 4- (2-hydroxyethoxy) phenyl ( 2-Hydroxy-2-propyl) Ketone, ⁇ -Hydroxy- ⁇ , ⁇ '-dimethylacetophenone, methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-cyclohexylacetophenone, 2,2- Acetphenones such as diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 2-hydroxy-2-methylpropio Pheny
  • Examples thereof include acylphosphine oxides such as 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphenylphosphine oxide, benzyl, dibenzosverone, ⁇ -acyloxime ester, and the like.
  • the content of these photopolymerization initiators is usually 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the polymerizable composition according to the present embodiment. , 0.5 to 3% by weight, more preferably. If the content of the photopolymerization initiator is less than 0.1% by weight, sufficient curability cannot be obtained, and if it exceeds 10% by weight, the performance such as the strength of the cured product may deteriorate.
  • the thermal polymerization of the polymerizable composition according to the present embodiment can be carried out by a known method in the presence of a thermal polymerization initiator, and for example, an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, a bulk polymerization method and the like.
  • a thermal polymerization initiator for example, an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, a bulk polymerization method and the like.
  • the solvent that can be used is not particularly limited as long as it is a solvent that dissolves the polymer obtained by polymerization, and for example, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene, and hexane.
  • solvents may be used alone or in combination of two or more.
  • ethyl acetate, methyl ethyl ketone, acetone or the like having a low boiling point.
  • the temperature and time of thermal polymerization vary depending on the thermal polymerization method adopted and the thermal polymerization initiator used, but are usually calculated from the half-life of the initiator, and the temperature is usually preferably 60 ° C to 120 ° C.
  • the time is usually preferably 2 hours to 20 hours, more preferably 5 hours to 10 hours.
  • thermal polymerization initiators examples include thermal radical polymerization initiators, which include azo compound-based catalysts such as azobisisobutyronitrile, azobisvaleronitrile, and azobis (isobutyric acid) dimethyl, benzoyl peroxide, and hydrogen peroxide.
  • a peroxide-based catalyst such as hydrogen, a persulfate-based catalyst such as ammonium persulfate or sodium persulfate, or the like can be used.
  • the content of the thermal polymerization initiator is about 0.01 to 10% by weight with respect to the total weight of the polymerizable composition.
  • ordinary radical polymerization techniques such as adjustment of molecular weight by a chain transfer agent can be applied.
  • the polymer obtained by polymerizing the polymerizable composition according to the present embodiment by the above-mentioned various methods may be further contained as a component of the polymerizable composition.
  • the molecular weight of the polymer of the polymerizable composition according to the present embodiment is usually 1,000 to 2,000,000, preferably 5,000 to 1,000,000 in terms of weight average molecular weight (Mw). It is particularly preferably 10,000 to 500,000.
  • Mw weight average molecular weight
  • Mw weight average molecular weight
  • the solution viscosity at 25 ° C. is usually 10 to 100,000 mPa ⁇ s, preferably 500 to 10,000 mPa ⁇ s, and 1 It is more preferably 5,000 to 5,000 mPa ⁇ s.
  • the viscosity can be measured according to the JIS K5600-2-3 cone plate viscometer method.
  • a fifth embodiment of the present invention is a pressure-sensitive adhesive composition (hereinafter, also referred to as a pressure-sensitive adhesive).
  • the pressure-sensitive adhesive composition according to the fifth embodiment contains the polymerizable composition or the polymer thereof according to the first to fourth embodiments, or the polymerizable composition or the polymer thereof and a cross-linking agent. Since the polymerizable composition according to the first to fourth embodiments or a polymer thereof contains N-substituted (meth) acrylamide (A), it has sufficient cohesive strength, adhesive strength, and various groups as a pressure-sensitive adhesive composition. In addition to adhesion to the material and stain resistance, it has durability and yellowing resistance.
  • the polymerizable composition or a polymer thereof can be used as it is as a pressure-sensitive adhesive composition.
  • the stain resistance and durability are further improved.
  • Excellent pressure-sensitive adhesive compositions can also be obtained.
  • the pressure-sensitive adhesive composition according to the fifth embodiment can be used as it is as a pressure-sensitive adhesive layer after being applied or molded on a separator or a base material.
  • it can also be used as an active energy ray and / or a thermosetting pressure-sensitive adhesive composition to form a pressure-sensitive adhesive layer by being cured by active energy rays and / or heat.
  • the pressure-sensitive adhesive composition contains an organic solvent, it is applied or molded on a separator or a base material, and then dried at a temperature of 60 to 120 ° C. for 1 to 30 minutes.
  • a conventionally known method can be used, for example, a spin coating method, a spray coating method, a knife coating method, a dipping method, a gravure roll, a reverse roll method, etc.
  • a normal coating film forming method such as a screen printing method or a bar coater method is used.
  • a laminated body can be obtained by laminating the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition according to the fifth embodiment and various base materials.
  • Examples of the method of laminating the adhesive layer and various base materials include a transfer method and a roll-to-roll method.
  • the thickness of the adhesive layer in the laminated body is not particularly limited because it varies depending on various uses, but is usually 4 ⁇ m to 150 ⁇ m, and when used for automobile members, about 20 ⁇ m to 120 ⁇ m is used for electronic materials and optical members. If this is the case, about 30 ⁇ m to 100 ⁇ m is appropriate.
  • the base material examples include various base materials having a wide range of polarities from low polarity to high polarity, such as an organic base material, an inorganic base material, and a base material made of an organic / inorganic composite material, depending on the application.
  • the materials thereof include, for example, polyolefins such as polyethylene and polypropylene, polyethylene terephthalate, polycarbonate, ABS resin which is an acrylonitrile-butadiene-styrene copolymer, polyimide, polyamide and acrylic resins such as polymethylmethacrylate, steel and stainless steel.
  • a hybrid material in which silica fine particles, which are inorganic materials, are dispersed in polyimide, which is an organic material can be mentioned.
  • the use of the various base materials is not particularly limited, and examples thereof include those for electronic materials, optical members, and automobile members.
  • the pressure-sensitive adhesive layer constituting the laminate according to the fifth embodiment is formed from a polymerizable composition containing N-substituted (meth) acrylamide (A) or a polymer thereof, and is N-substituted (meth) acrylamide.
  • A has a hydrophobic substituent showing wettability to a low-polarity substrate and a hydrophilic (meth) acrylamide group showing wettability to a high-polarity substrate in the molecule, and is high from a low-polarity substrate. Good adhesion can be imparted to polar substrates. Further, by exhibiting a strong cohesive force derived from hydrogen bonds between amide groups between the molecules of A, high adhesive force and stain resistance can be provided.
  • the pressure-sensitive adhesive layer obtained from the polymerizable composition or polymer also has high transparency and yellowing resistance, and can be used as an adhesive for optical members, a pressure-sensitive adhesive sheet, or the like. It is also suitably used in the optical field.
  • a laminate composed of an adhesive layer having such characteristics and various base materials can be applied as an adhesive film or an adhesive sheet for electronic materials, optical members, and automobile members.
  • the N-substituted (meth) acrylamide (A) contained in the pressure-sensitive adhesive composition can be brought in from the polymerizable composition containing A, and the polymerizable composition can be brought in.
  • A can also be brought in as a structural unit from the polymer of the above and the polymer of N-substituted (meth) acrylamide (A).
  • the total content of N-substituted (meth) acrylamide (A) and the structural unit of A in the pressure-sensitive adhesive is 0.1 to the total weight of the pressure-sensitive adhesive composition (excluding the solvent (the same applies hereinafter)).
  • the surface tension of N-substituted (meth) acrylamide (A) is preferably 24.0 to 46.0 mN ⁇ m -1 .
  • a polymerization initiator further contained, a compound having an unsaturated bond, and a non-polymerizable component
  • the non-polymerizable oligomer, the non-polymerizable polymer and the polymer according to the second embodiment of the present invention are preferably hydrophobic.
  • the content of the monofunctional monomer excluding N-substituted (meth) acrylamide (A) is the content of the pressure-sensitive adhesive composition with respect to the total weight of the pressure-sensitive adhesive composition.
  • the total content of the cross-linking agent containing the polyfunctional monomer is preferably 1 to 30% by weight, more preferably 2 to 20% by weight, and 5 to 15% by weight, based on the total weight of the pressure-sensitive adhesive composition. % Is particularly preferable.
  • the total content of the non-polymerizable component is preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, and 1 to 10% by weight, based on the total weight of the pressure-sensitive adhesive composition. It is particularly preferable that it is contained in% by weight.
  • Such an adhesive composition has high adhesion to various substrates, and the adhesive layer formed from the adhesive has high adhesive strength, and has excellent transparency, water resistance, stain resistance, yellowing resistance and durability. It is possible to obtain a pressure-sensitive adhesive composition having the pressure-sensitive adhesive composition, and a laminate of a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition and various base materials.
  • a sixth embodiment of the present invention is an adhesive composition (hereinafter, also referred to as an adhesive).
  • the adhesive composition according to the sixth embodiment contains the polymerizable composition according to the first to fourth embodiments, a polymer thereof, and a cross-linking agent.
  • the adhesive composition contains an N-substituted (meth) acrylamide (A) and a cross-linking agent, and thus has a wide range of polarities from low polarity to high polarity, such as an organic base material, an inorganic base material, and an organic base material. Since it exhibits high adhesive strength and impact resistance to various substrates such as a substrate made of an inorganic composite material, it can be used as an adhesive composition for the same or different materials.
  • the same kind of material means that it is the same kind of material among various materials such as the above-mentioned resins, metals, glasses and hybrid materials. It is preferable that the surface tension of each material at 23 ° C. is 22.6 mN ⁇ m -1 to 59.0 mN ⁇ m -1 . If the same type of material has a surface tension within the above range, high adhesive strength can be obtained.
  • the surface tension of each of the materials at 23 ° C. can be measured by JIS K 6768, and the minimum surface tension that can be measured by this method is 22.6 mN ⁇ m -1 .
  • the surface tension of a material whose surface tension value measured by this method is less than 22.6 mN ⁇ m -1 is 22. Expressed as 6mN ⁇ m -1 .
  • the dissimilar material refers to a different kind of material among various materials such as the above-mentioned resins, metals, glasses and hybrid materials.
  • the dissimilar materials preferably have an absolute value of the difference in surface tension between the two dissimilar materials bonded via the adhesive composition at 23 ° C. of 37.0 mN ⁇ m -1 or less. Since different materials may have the same surface tension even when the materials are different, the absolute value of the difference in surface tension is 0.0 mN ⁇ m -1 or more. Good adhesiveness can be obtained if different materials have an absolute value of the difference in surface tension within the above range.
  • the N-substituted (meth) acrylamide (A) contained in the adhesive composition can be brought in from the polymerizable composition containing A, and the polymerizable composition can be brought in.
  • A can also be brought in as a structural unit from the polymer of the above and the polymer of N-substituted (meth) acrylamide (A).
  • the total content of N-substituted (meth) acrylamide (A) and structural units of A in the adhesive is preferably 1 to 95% by weight based on the total weight of the adhesive (excluding the solvent). It is more preferably 10 to 85% by weight, and particularly preferably 2 to 80 parts by weight.
  • the surface tension of N-substituted (meth) acrylamide (A) is preferably 24.0 to 46.0 mN ⁇ m -1 . ..
  • a polymerization initiator further contained, a compound having an unsaturated bond, and a non-polymerizable component.
  • the non-polymerizable oligomer, the non-polymerizable polymer, and the polymer according to the second embodiment of the present invention are preferably hydrophobic. Further, in order to adjust the balance between hydrophilicity and hydrophobicity of the adhesive composition and improve the cohesive force, the content of the monofunctional monomer (excluding N-substituted (meth) acrylamide (A)) is the adhesive composition.
  • the content of the (meth) acrylate-based monomer as the monofunctional monomer is most preferably less than 50% by weight in order to sufficiently maintain the cohesive force derived from the (meth) acrylamide-based monomer.
  • the total content of the cross-linking agent containing the polyfunctional monomer is preferably 1 to 50% by weight, preferably 5 to 30% by weight, based on the total weight of the adhesive composition. It is more preferably%, and particularly preferably 10 to 25% by weight. If the content is less than 1% by weight, the cross-linking by the cross-linking agent may be insufficient, and the cohesive force of the adhesive may be insufficient to obtain sufficient impact resistance and heat resistance. On the other hand, when the content exceeds 50% by weight, the cross-linking density of the adhesive after cross-linking is too high, so that the adhesion to the substrate is lowered due to shrinkage, and as a result, the adhesive strength tends to be lowered.
  • the cross-linking reaction using a cross-linking agent can be carried out by the above-mentioned cross-linking methods (1) to (3).
  • the total content of the non-polymerizable component is preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, and 0, based on the total weight of the adhesive composition. It is particularly preferably .5 to 8% by weight.
  • Such an adhesive composition has high adhesive strength, impact resistance and water resistance to various substrates, and is suitably used for bonding the same or different materials.
  • the N-substituted (meth) acrylamide (A) used in the invention has a high resistance to yellowing
  • the adhesive composition according to the sixth embodiment can be used as an adhesive for an optical film laminate such as a retardation film or a polarizing plate. Can also be used.
  • a seventh embodiment of the present invention is a cosmetic composition (hereinafter, also referred to as cosmetic).
  • the cosmetic composition according to the seventh embodiment contains the polymerizable composition according to the first to fourth embodiments or a polymer thereof.
  • the cosmetic composition can be used as a cosmetic composition having moisture resistance by containing N-substituted (meth) acrylamide (A). It can also be used as a cosmetic composition having emulsion stability due to the well-balanced amphipathicity of N-substituted (meth) acrylamide (A).
  • the surface tension of N-substituted (meth) acrylamide (A) is preferably 24.0 to 46.0 mN ⁇ m -1 .
  • the cosmetic composition according to the seventh embodiment may further contain other components depending on the intended use and dosage form, and the other components are not particularly limited.
  • various polymerization initiators polyalkylene oxide macromonomer such as polyethylene oxide macromonomer
  • oil-in-water emulsified cosmetics are produced as other components.
  • Hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, liquid fats and oils, solid fats and oils, waxes, oil phase components such as fragrances, and aqueous phase components such as water, water-soluble alcohols, and thickeners can be mentioned. can.
  • the cosmetic composition When the cosmetic composition is used as a hair spray type hair cosmetic, examples of other components include a polymerization initiator, a polymer surfactant, a basic compound and the like.
  • the cosmetic composition has better solubility in LPG (liquefied petroleum gas), so that aerosol products such as hair sprays that use LPG as hair cosmetics.
  • LPG liquefied petroleum gas
  • aerosol products such as hair sprays that use LPG as hair cosmetics.
  • the N-substituted (meth) acrylamide (A) contained in the cosmetic composition can be brought in from the polymerizable composition containing A, and the polymerizable composition can be brought in.
  • A can also be brought in as a structural unit from the polymer of the above and the polymer of N-substituted (meth) acrylamide (A).
  • the total content of N-substituted (meth) acrylamide (A) and structural units of A in the cosmetic composition is preferably 1 to 80% by weight based on the total weight of the cosmetic composition. More preferably, it is ⁇ 70% by weight. It is particularly preferably 10 to 60% by weight.
  • Such a cosmetic composition does not show skin irritation, has moisture resistance or emulsification stability and stability over time, and is used for smoothness, stickiness resistance, texture, firmness, quickness of familiarity and the like. Excellent feeling.
  • the eighth embodiment of the present invention is a coating agent composition (hereinafter, also referred to as a coating agent).
  • the coating agent composition according to the eighth embodiment contains the polymerizable composition according to the first to fourth embodiments or a polymer thereof.
  • the coating agent composition is composed of an organic base material, an inorganic base material, and an organic / inorganic composite material having a wide range of polarities from low polarity to high polarity. It has high wettability to various base materials such as the base material.
  • a method for applying the coating agent composition to the substrate a conventionally known method can be used.
  • the coating agent composition is applied to the substrate and then cured by the above-mentioned active energy rays and / or heat.
  • the thickness when the coating agent composition is applied to the substrate is not particularly limited, but is preferably a thickness that is sufficiently cured by active energy rays and / or heat, and is generally 1 to 100 ⁇ m. ..
  • the obtained cured product (coating layer) has adhesion to the above-mentioned various substrates, and exhibits high pencil hardness and water resistance.
  • the N-substituted (meth) acrylamide (A) contained in the coating agent composition can be brought in from the polymerizable composition containing A, and the polymerizable composition can be brought in.
  • A can also be brought in as a structural unit from the polymer of the above and the polymer of N-substituted (meth) acrylamide (A).
  • the total content of N-substituted (meth) acrylamide (A) and structural units of A in the coating agent is 1 to 80% by weight based on the total weight of the coating agent (excluding the solvent).
  • the surface tension of N-substituted (meth) acrylamide (A) is preferably 24.0 to 46.0 mN ⁇ m -1 .
  • the coating agent composition according to the eighth embodiment preferably further contains the above-mentioned cross-linking agent, in which case the pencil hardness and water resistance of the coating layer are improved.
  • the content of the cross-linking agent in the total weight of the coating agent composition is preferably 5 to 70% by weight, more preferably 10 to 60% by weight, and more preferably 20 to 50% by weight.
  • the coating agent composition may contain the above-mentioned photopolymerization initiator, monofunctional monomer and oligomer, non-polymerizable oligomer and polymer as other components.
  • the content of the other components may be as long as it does not impair the above-mentioned characteristics of the coating agent composition, and is usually 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymerizable composition.
  • a coating agent composition has high wettability and adhesion to various substrates, and by using it, a coating film such as a coating film exhibiting high surface hardness and water resistance can be obtained by being cured.
  • a ninth embodiment of the present invention is an ink composition (hereinafter, also referred to as ink).
  • the ink composition according to the ninth embodiment contains the polymerizable composition according to the first to fourth embodiments or a polymer thereof.
  • the ink composition has high curability by containing N-substituted (meth) acrylamide (A).
  • A N-substituted (meth) acrylamide
  • As a method of applying the ink composition to the substrate a conventionally known method can be used.
  • the ink viscosity at 25 ° C. is preferably less than 500 mPa ⁇ s, and more preferably less than 100 mPa ⁇ s from the viewpoint of being able to be applied to a substrate by an inkjet method.
  • the ink composition After being applied to the substrate, the ink composition is cured by the above-mentioned active energy rays and / or heat to form an ink layer.
  • the surface tension of the N-substituted (meth) acrylamide (A) of the obtained ink layer is 24.0 to 46.0 mNm- 1 from the viewpoint of further improving the adhesion to various substrates. preferable.
  • the N-substituted (meth) acrylamide (A) contained in the ink composition can be brought in from the polymerizable composition containing A, and the polymerization of the polymerizable composition can be carried out.
  • A can also be brought in as a structural unit from a product and a polymer of N-substituted (meth) acrylamide (A).
  • the total content of N-substituted (meth) acrylamide (A) and structural units of A in the ink is preferably 5 to 90% by weight, preferably 10 to 85% by weight, based on the total weight of the ink (excluding the solvent). It is more preferably by weight%, and particularly preferably 15 to 80% by weight.
  • the ink composition according to the ninth embodiment may further contain the above-mentioned cross-linking agent, in which case the curability, surface drying property and water resistance of the ink layer are improved.
  • the content of the cross-linking agent in the total weight of the ink composition is preferably 1 to 50% by weight, more preferably 5 to 45% by weight, and particularly preferably 10 to 40% by weight. preferable.
  • the ink composition may further contain the above-mentioned photopolymerization initiator, monofunctional monomer and oligomer, non-polymerizable oligomer and polymer as other components.
  • the content of the other components may be as long as it does not impair the above-mentioned characteristics of the ink composition, and is usually 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymerizable composition.
  • Such an ink composition has high adhesion to various substrates, is excellent in printing characteristics such as pigment dispersibility, surface drying property, ejection stability, and sharpness, and by using it, it has high curability and resistance. It is possible to obtain an ink having yellowing and water resistance.
  • a tenth embodiment of the present invention is an ink composition for three-dimensional modeling.
  • the three-dimensional modeling ink composition according to the tenth embodiment contains the polymerizable composition or the polymer thereof according to the first to fourth embodiments, or the polymerizable composition or the polymer thereof and a cross-linking agent. .. Since the polymerizable composition according to the first to fourth embodiments or a polymer thereof contains N-substituted (meth) acrylamide (A), the three-dimensional modeling ink composition has high curability and curing shrinkage resistance. The cured product has high strength and water resistance and is excellent in molding accuracy.
  • the three-dimensional modeling ink composition is formed into a thin film by being cured by irradiation with active energy rays and / or heat at the same time as or immediately after being formed into a predetermined shape pattern, and the thin films are laminated.
  • the modeling method is not particularly limited, and examples thereof include a stereolithography method in which the ink jet method is used to eject and cure by irradiation with active energy rays.
  • the viscosity of the three-dimensional modeling ink composition at 25 ° C. is preferably 1 to 200 mPa ⁇ s, and the ejection temperature is preferably in the range of 20 to 100 ° C.
  • the surface tension of N-substituted (meth) acrylamide (A) is 24.0 to 46.0 mN ⁇ m -1 from the viewpoint that the obtained three-dimensional model can exhibit good appearance such as glossiness and fineness. Is preferable.
  • the N-substituted (meth) acrylamide (A) contained in the three-dimensional modeling ink composition can be brought in from the polymerizable composition containing A.
  • A can also be brought in as a structural unit from the polymer of the polymerizable composition and the polymer of N-substituted (meth) acrylamide (A).
  • the total content of N-substituted (meth) acrylamide (A) and structural units of A in the three-dimensional modeling ink composition may be 1 to 80% by weight based on the total weight of the three-dimensional modeling ink. It is preferably 2 to 70% by weight, more preferably 5 to 60 parts by weight, and particularly preferably 5 to 60 parts by weight.
  • the ink composition for three-dimensional modeling according to the tenth embodiment preferably further contains the above-mentioned cross-linking agent, and in this case, it is possible to form a three-dimensional model having excellent strength, water resistance and heat resistance.
  • the content of the cross-linking agent in the total weight of the three-dimensional modeling ink composition is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, and 10 to 30% by weight. Is particularly preferable.
  • the ink composition for three-dimensional modeling may further contain the above-mentioned photopolymerization initiator, monofunctional monomer and oligomer, non-polymerizable oligomer and polymer as other components.
  • the content of the other components may be as long as it does not impair the above-mentioned characteristics of the three-dimensional modeling ink composition, and is usually 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymerizable composition. From such an ink composition for three-dimensional modeling, it is possible to accurately model a three-dimensional model having high strength, heat resistance and water resistance.
  • Additives include thermal polymerization inhibitors, antioxidants, UV sensitizers, preservatives, phosphoric acid ester-based and other flame retardants, surfactants, antistatic agents, pigments, colorants such as dyes, fragrances, etc. Examples thereof include defoaming agents, fillers, silane coupling agents, surface tension modifiers, plasticizers, surface lubricants, leveling agents, softeners, organic fillers, inorganic fillers, silica particles and the like. One of these additives may be used alone, or two or more of these additives may be used in combination.
  • the content of these additives is not particularly limited as long as it does not adversely affect the characteristics developed by the polymerizable composition or various molded products of the polymer, but 5 with respect to the total weight of the polymerizable composition. It is preferably 0% by weight or less.
  • Additives include thermal polymerization inhibitors, antioxidants, UV sensitizers, preservatives, phosphoric acid ester-based and other flame retardants, surfactants, antistatic agents, pigments, colorants such as dyes, fragrances, etc. Examples thereof include defoaming agents, fillers, silane coupling agents, surface tension modifiers, plasticizers, surface lubricants, leveling agents, softeners, organic fillers, inorganic fillers, silica particles and the like. One of these additives may be used alone, or two or more of these additives may be used in combination.
  • the content of these additives is not particularly limited as long as it does not adversely affect the characteristics developed by the various molded products obtained from the various compositions, but is 30% by weight or less based on the total weight of the composition. Is preferable.
  • water, an organic solvent and a mixture thereof can be used as a solvent or a diluent.
  • the content of such a solvent is not particularly limited as long as it does not adversely affect the characteristics developed by the various molded products obtained from the various compositions, but is 95% by weight or less based on the total weight of the composition. Is preferable.
  • N-substituted (meth) acrylamide (A) CHAA: N-cyclohexylacrylamide (registered trademark "Kohsylmer”) (solid at room temperature, surface tension: 32.3 mNm- 1 ) CHMAA: N-cyclohexyl-N-methylacrylamide (registered trademark "Kohsylmer”) (liquid at room temperature, surface tension: 32.5 mN ⁇ m -1 )
  • ACP N-acryloylpiperidin (registered trademark "Kohsylmer”) (liquid at room temperature, surface tension: 35.7 mNm- 1 )
  • ICMP N-acryloyl-4-methylpiperidine (registered trademark "Kohshylmer”) (liquid at room temperature, surface tension: 31.6 mNm- 1 )
  • ACDMP N-acryloyl-3,5-dimethylpiperidine (registered trademark "Kohshylmer”) (liquid at
  • PETA Pentaerythritol Triacrylate
  • DPHA Dipentaerythritol Hexaacrylate
  • HDDA 1,6-Hexanediol Diacrylate
  • TPGDA Tripropylene Glycol Diacrylate
  • UV-3000B Bifunctional Urethane Acrylate (Shikou, manufactured by Mitsubishi Chemical Co., Ltd.)
  • UV-6640B Bifunctional urethane acrylate (Shikou, manufactured by Mitsubishi Chemical Corporation)
  • Quick Cure 7100 UV curable urethane oligomer (registered trademark "Quick Cure", manufactured by KJ Chemicals)
  • Quick Cure 8100 UV curable urethane oligomer (registered trademark "Quick Cure", manufactured by KJ Chemicals)
  • O-184 Omnirad 184 (photopolymerization initiator, manufactured by IGM Resins B.V.)
  • O-1173 Omnirad 1173 (photopolymerization initiator, manufactured by IGM Resin
  • Example 1 (Production and evaluation of polymer of N-substituted (meth) acrylamide (A)) CHAA 30 g, 2EHA 44 g, "NIPAM" 20 g, HEA 5 g, AIBN 1 g, solvent as N-substituted (meth) acrylamide (A) in a 500 mL flask equipped with a thermometer, stirrer, reflux condenser and nitrogen introduction tube. As a result, 100 g of ethyl acetate was added, and the mixture was uniformly mixed at room temperature, followed by nitrogen substitution for 30 minutes, the temperature of the reaction solution was raised to 70 ° C., and the polymerization reaction was carried out for 8 hours.
  • ethyl acetate was added to the reaction solution to prepare a polymer solution having a solid content of 30%.
  • a cone plate type viscometer (RE550 type manufactured by Toki Sangyo Co., Ltd.)
  • the viscosity of the polymer solution at 25 ° C. was measured according to JIS K5600-2-3, and the viscosity was 4250 mPa ⁇ s.
  • 30 g of the polymer solution was taken out, and the volatile components in the solution were completely removed to obtain a polymer.
  • the obtained polymer was dissolved in tetrahydrofuran (THF) to prepare a THF solution of the polymer having a concentration of 0.5% by weight, and the mixture was allowed to stand overnight. Then, the THF solution of the polymer was filtered through a 0.45 ⁇ m membrane filter, and gel permeation chromatography (GPC) measurement was performed using a filtrate (Prominence GPC system manufactured by Shimadzu Corporation, Shodex KF-806L column, eluent THF), and polystyrene. From the converted value, it was calculated that the weight average molecular weight (Mw) of the polymer was 960,000.
  • Mw weight average molecular weight
  • the saturated water absorption rate was calculated according to the following formula, the water resistance of the polymer was evaluated in four stages as follows, and the results are shown in Table 1.
  • Saturated water absorption rate (%) (weight in saturated water absorption state-weight in dry state) / weight in dry state x 100% ⁇ : Saturated water absorption rate is 5% or more.
  • ⁇ The saturated water absorption rate exceeds 5%, but is 7% or less.
  • ⁇ Saturated water absorption rate exceeds 7%, but is 10% or less.
  • X Saturated water absorption rate exceeds 10%.
  • Examples 2 to 12 and Comparative Examples 1 to 3 (Production of N-substituted (meth) acrylamide (A) polymer and other polymers)
  • the types and contents of N-substituted (meth) acrylamide, monofunctional monomer, and polymerization initiator were changed as shown in Table 1, and the polymerization reactions of Examples 2 to 12 and Comparative Examples 1 to 3 were carried out in the same manner as in Example 1.
  • Example 1 was carried out to obtain a polymer solution having a solid content of 30%.
  • Table 1 shows the results of measuring the viscosity of the obtained polymer solution and the molecular weight of the polymer in the same manner as in Example 1.
  • Examples 13-28 and Comparative Examples 4-7 Preparation and evaluation of polymerizable composition
  • the N-substituted (meth) acrylamide (A) used in this embodiment and other components are weighed in the proportions shown in Table 2 and mixed uniformly at room temperature to prepare the polymerizable compositions of Examples and Comparative Examples. bottom.
  • the transparency of the obtained polymerizable composition and the wettability with respect to various substrates were evaluated by the following methods, and the results are shown in Table 2.
  • the polymerizable compositions of Examples 15, 16, 18 and 21 are polymerizable resin compositions for thermal polymerization, respectively, which are Examples 4, 2, 8 and 3 shown in Table 1, respectively.
  • the properties of the polymer are shown in Table 1.
  • the polymerizable resin composition other than that for thermal polymerization is a polymerizable resin composition for active energy ray curing, and the curability and the water resistance of the obtained cured product were evaluated by the following methods, and the results are shown in Table 2.
  • Example 14 is a method of irradiating an electron beam (EB) instead of ultraviolet rays to cure.
  • EB electron beam
  • Curetron EBC-200-AA3 manufactured by Nissin High Voltage Co., Ltd. was used (acceleration voltage: 200 kV, irradiation dose 20 kGy).
  • Tack disappears when the integrated light amount is less than 200 mJ / cm 2
  • Tack disappears when the integrated light amount is 200 mJ / cm 2 or more and less than 500 mJ / cm 2
  • Disappearance ⁇ Tack disappears when the integrated light intensity is 1000 mJ / cm or more (including the case where the tack does not disappear)
  • a silicone spacer (length 30 mm x width 15 mm x thickness 1 mm) is set on a glass plate (length 50 mm x width 50 mm x thickness 5 mm), and the active energy rays prepared in each example and comparative example are inside the spacer.
  • a curing polymerizable resin composition was poured and cured by ultraviolet irradiation (700 mW / cm 2 , 2000 mJ / cm 2 ) to prepare a cured sheet. The obtained sheet was cut into 3 cm squares, dried under a vacuum of 60 ° C. for 24 hours, and accurately weighed as a dried sheet to obtain the weight of the cured product in a dried state.
  • the dried sheet was immersed in deionized water at 30 ° C., and after 24 hours and 48 hours had passed, the weight immediately after being taken out from the deionized water was weighed, and it was confirmed that the sheet reached a saturated water absorption state and cured.
  • the weight of the saturated water absorption condition of the object was used.
  • the saturated water absorption rate was calculated according to the following formula, and the water resistance of the cured product was evaluated in four stages as follows.
  • Saturated water absorption rate (%) (weight in saturated water absorption state-weight in dry state) / weight in dry state x 100%
  • Saturated water absorption rate is 5% or more.
  • ⁇ The saturated water absorption rate exceeds 5%, but is 7% or less.
  • ⁇ Saturated water absorption rate exceeds 7%, but is 10% or less.
  • X Saturated water absorption rate exceeds 10%.
  • Examples 29 to 70 and Comparative Examples 8 to 20 (preparation and evaluation of pressure-sensitive adhesive composition) (Examples 29 to 40 and Comparative Examples 8 to 10)
  • a heavy peel separator (silicone coated PET film) was coated so that the thickness after drying was 25 ⁇ m, and the temperature was 90 ° C. for 2 minutes. It was dried to form a pressure-sensitive adhesive layer. Then, it was left in an environment with a temperature of 23 ° C. and a relative humidity of 50% for one day to obtain a test adhesive sheet (type a-1).
  • test pressure-sensitive adhesive sheets of Examples 30, 35, 38 and Comparative Example 10 are irradiated with ultraviolet rays (they have an unsaturated bond derived from an oleyl group).
  • Example 41 to 48 and Comparative Example 11 The polymer solutions obtained in Examples 1, 4, 6, 8 and 12 and HDI as a cross-linking agent were weighed so as to have the solid content shown in Table 4 and mixed uniformly. Similarly to the above, the film was applied to a PET film so that the thickness after drying was 25 ⁇ m, and dried at 90 ° C. for 2 minutes to form an adhesive layer. Then, it was aged in a constant temperature bath at 40 ° C. for 3 days and left in an environment with a temperature of 23 ° C. and a relative humidity of 50% for 1 day to obtain a test adhesive sheet (type b-1).
  • polymer solutions obtained in Examples 7, 9 and 10 and polyacrylic acid (PAAc, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., average molecular weight 5,000) as a cross-linking agent are used to obtain the solid content shown in Table 4. Weighed in and mixed uniformly. Similarly to the above, it was applied to a PET film having a thickness of 25 ⁇ m after drying, and dried at 90 ° C. for 2 minutes to form an adhesive layer. Then, it was aged in a constant temperature bath at 40 ° C. for 3 days and left in an environment with a temperature of 23 ° C. and a relative humidity of 50% for 1 day to obtain a test adhesive sheet (type b-2).
  • PAAc polyacrylic acid
  • Examples 49 to 53 and Comparative Examples 12 and 13 Weigh the polymer solutions obtained in Examples 2, 4, 5, 7, 8 and 11 and Comparative Examples 2 and 3, and weigh a monofunctional monomer, a polyfunctional monomer and / or a polyfunctional oligomer as a cross-linking agent, and photopolymerization.
  • the initiator and other components were weighed in the prescribed amounts shown in Table 5 and mixed uniformly. Similarly to the above, it was applied to a PET film having a thickness of 25 ⁇ m after drying, and dried at 90 ° C. for 2 minutes to form an adhesive layer.
  • Examples 54 to 65 and Comparative Examples 14 to 17 Using the polymerizable compositions obtained in Examples 13, 14, 17, 19, 20, 22 to 28 and Comparative Examples 4 to 7, a heavy release separator (silicone coated PET film) was coated with a light release separator. Using a desktop roll-type laminator machine (RSL-382S manufactured by Royal Sovereign) so as not to bite air bubbles with (silicone coated PET film), the adhesive layers are bonded so that the thickness is 25 ⁇ m, and ultraviolet rays are irradiated (device:).
  • RSL-382S manufactured by Royal Sovereign desktop roll-type laminator machine
  • Inverter type conveyor device ECS-4011GX made by iGraphic, metal halide lamp: M04-L41 made by igraphics, ultraviolet illuminance: 700mW / cm 2 , integrated light amount: 1000mJ / cm 2 ), transparent adhesive sheet for optical (type d) was produced.
  • Example 66 to 72 and Comparative Examples 18 to 20 Polymer solutions or polymerizable compositions obtained in Examples 1, 6, 8, 12-14, 19, 24 and Comparative Examples 1, 4, 5 and HDI or polyfunctional monomers and / or polyfunctional oligomers as cross-linking agents. , The photopolymerization initiator and other components were weighed in the predetermined amounts shown in Table 7 and mixed uniformly.
  • a pressure-sensitive adhesive sheet was prepared in the same manner as in the case of type c (when a polymer was used) or type d (when a polymerizable composition was used), and cured by ultraviolet rays. Then, it was aged in a constant temperature bath at 40 ° C. for 3 days and left in an environment with a temperature of 23 ° C. and a relative humidity of 50% for 1 day to obtain a test adhesive sheet (type e).
  • the active energy ray-curable pressure-sensitive adhesive composition prepared above is applied onto various plate-shaped substrates (bases), and a table-top roll type is used with a light release separator (silicone-coated PET film) so as not to bite air bubbles.
  • a laminator machine Royal Sovereignn RSL-382S
  • the adhesive layer is bonded so that it has a thickness of 5 ⁇ m, and is irradiated with ultraviolet rays (device: Inverter type conveyor device ECS-4011GX made by Eye Graphics, metal halide lamp: Eye graphic).
  • Adhesive strength evaluation Under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, the adhesive layer was transferred to various film-shaped or plate-shaped substrates, and pressure-bonded by two reciprocating movements using a pressure-bonding roller weighing 2 kg, and the same atmosphere was obtained. It was left underneath for 30 minutes. Then, using a tensile tester (device name: Tensilon RTA-100 manufactured by ORIENTEC), 180 ° peel strength (N / 25 mm) was measured at a peel rate of 300 mm / min according to JIS Z0237.
  • a tensile tester device name: Tensilon RTA-100 manufactured by ORIENTEC
  • An adhesive sheet was prepared in the same manner as in the above-mentioned measurement of adhesive strength, and after holding for 100 hours under the conditions of a temperature of 85 ° C. and a relative humidity of 85%, the presence or absence of floating or peeling of the adhesive layer, bubbles, and cloudiness was visually observed. ,evaluated. ⁇ : It is transparent and does not float, peel off, or generate bubbles. ⁇ : There is very slight cloudiness, but no floating, peeling, or air bubbles are generated. ⁇ : Slight cloudiness, floating or peeling, and air bubbles. X: Extremely cloudy, floating, peeling, or air bubbles.
  • Examples 73 to 82 and Comparative Examples 21 to 24 (preparation and evaluation of adhesive composition) Polymers obtained in Comparative Examples 1 and 2 with Examples 1 to 4, 6, 8, 9, 11 and / or Polymerization obtained with Examples 13, 14, 19, 20, 25 to 27 and Comparative Examples 4, 5
  • the sex composition, the cross-linking agent and other components were weighed so as to have the solid content shown in Table 8 and mixed uniformly at room temperature to obtain a uniform mixture.
  • the mixture was uniformly applied to any one of two sheets of the same or different plate-like substrates having a length of 100 mm, a width of 25 mm and a thickness of 1 mm.
  • the solvent was contained in the mixture, a large amount of the mixture was applied so that the thickness after drying would be the same as that in the case of no solvent, and the mixture was dried at 90 ° C. for 2 minutes.
  • the other plate-shaped base material is placed on the mixture after coating, and the overlapping area is bonded so that the length is 12.5 mm ⁇ width 25 mm, and the adhesive is used by using a spacer.
  • the thickness of the layer was adjusted to 100 ⁇ m, and a bonded test piece was prepared. Then, UV or EB irradiation was performed from the upper surface of the bonded transparent or translucent base material in the same manner as in the preparation of the adhesive layer.
  • the test pieces after irradiation with UV rays and EB rays were used as the adhesive test pieces, respectively.
  • the test pieces after irradiation with UV rays and EB rays are further heated at 40 ° C. for 72 hours, and the obtained test pieces are subjected to an adhesive test. Used as a piece.
  • the prepared test piece was heated at 40 ° C. for 72 hours without irradiation with UV rays or EB rays, and the obtained test piece was used as an adhesive test piece. .. Further, using the obtained adhesive test piece, the adhesive strength and impact resistance were evaluated by the following method, and the results are shown in Table 8.
  • Tensilon RTA-100 manufactured by ORIENTEC was used as a testing machine according to JIS K 6850, and the tensile shear strength was measured under the condition of a tensile speed of 10 mm / min.
  • ⁇ The tensile shear strength is 20 MPa or more.
  • ⁇ The tensile shear strength is 15 MPa or more and less than 20 MPa.
  • ⁇ The tensile shear strength is 10 MPa or more and less than 15 MPa.
  • X The tensile shear strength is less than 10 MPa.
  • Impact peeling adhesive strength is 20 KJ / m 2 or more.
  • the impact peeling adhesive strength is 15 KJ / m 2 or more and less than 20 KJ / m 2 .
  • the impact peeling adhesive strength is 10 KJ / m 2 or more and less than 15 KJ / m 2 .
  • X The impact peeling adhesive strength is less than 10 KJ / m 2 .
  • Examples 83-97 and Comparative Examples 25-28 (manufacturing and evaluation of cosmetic composition)
  • Examples 83-89 and Comparative Examples 25 and 26 (Production and evaluation of hair cosmetic composition)
  • Curl retention (%) ⁇ (L-Lt) / (L-L0) ⁇ x 100
  • L Length when the test hair is stretched
  • Lt Tip position of the test hair after leaving it in a constant temperature and humidity chamber
  • L0 Tip position of the test hair before putting it in the constant temperature and humidity chamber
  • ⁇ 80 % Or more ⁇ : 65% or more and less than 80% ⁇ : 50% or more and less than 65% ⁇ : Less than 50%
  • Examples 90 to 97 and Comparative Examples 27 and 28 (manufacturing and evaluation of cosmetic composition for skin) 100 g of a water-ethanol mixed solvent (weight ratio 75:25) was added to a 1-liter three-necked flask equipped with a reflux tube and a nitrogen introduction tube, and the results were obtained in Table 1 according to the proportion shown in Table 10 (solid content conversion).
  • the polymer, the polymerizable composition obtained in Table 2 and other components were added. After sufficient dissolution or dispersion, nitrogen substitution was performed for 20 minutes to remove dissolved oxygen. Then, the polymerization reaction was carried out by keeping the temperature at 65 to 70 ° C. for 8 hours in an oil bath with stirring.
  • the dispersion obtained by returning the polymerization liquid to room temperature was used as a raw material for cosmetics.
  • 1 g of the aqueous phase component carboxyvinyl polymer and 0.6 g of potassium hydroxide were added to the ion-exchanged water and mixed, and 100 g of the cosmetic raw material separately dispersed in the ion-exchanged water was added and mixed by stirring.
  • the total amount of ion-exchanged water used was 500 g.
  • Example 13 in Example 90 The polymerizable composition of Example 13 in Example 90, the polymerizable composition of Example 17 in Example 91, the polymerizable composition of Example 19 in Example 95, and Example 28 in Example 97.
  • the polymerizable composition was used except for the polymerization initiator.
  • Emsification stability (emulsified particles) evaluation
  • the emulsified particles of the sample were observed with an optical microscope.
  • ⁇ The emulsified particles were uniform, and no coalescence or aggregation was observed.
  • ⁇ The emulsified particles were almost uniform, but no coalescence or aggregation was observed.
  • ⁇ The emulsified particles were almost uniform, but slight coalescence and aggregation were observed.
  • X The emulsified particles were not uniform, and remarkable coalescence and aggregation were observed.
  • the evaluation criteria for the "skin irritation test” are as follows. ⁇ : The average value of 10 panels is 0 or more and less than 0.15 ⁇ : The average value of 10 panels is 0.15 or more and less than 0.2 ⁇ : The average value of 10 panels is 0.2 or more and less than 0.3 ⁇ : The average value of 10 panels is 0.3 or more
  • Examples 98-105 and Comparative Examples 29 and 30 Preparation and evaluation of coating agent composition
  • Table 11 in terms of solid content
  • the polymer obtained in Table 1 the polymerizable composition obtained in Table 2 and other components are weighed, mixed uniformly at room temperature, and coated.
  • the agent composition was prepared.
  • a coating test piece (coating film) was prepared by the following method, and the wettability to various substrates (substrates), the pencil hardness of the coating film, and the adhesion were evaluated, and the results are shown in Table 11.
  • the coating agent composition was dropped in a band shape on the tip ends of various substrates (substrates), applied with a bar coater (RDS 3), and dried at 90 ° C. for 2 minutes. Then, it was cured by the curing method (UV, EB, heat, UV heat, EB heat) shown in Table 11 to form a coating layer on the substrate (substrate). Then, it was left in an environment with a temperature of 23 ° C. and a relative humidity of 50% for one day to obtain a coating test piece for evaluation.
  • UV, EB, heat, UV heat, EB heat shown in Table 11
  • the UV curing method is to irradiate ultraviolet rays with the coated surface facing upward (device: ECS-4011GX, an inverter type conveyor device manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, UV illuminance: 700 mW / cm 2 , Integrated light amount: 1000 mJ / cm 2 )
  • ECS-4011GX an inverter type conveyor device manufactured by Eye Graphics
  • metal halide lamp M04-L41 manufactured by Eye Graphics
  • UV illuminance 700 mW / cm 2
  • Integrated light amount 1000 mJ / cm 2
  • EB curing is a method of irradiating an electron beam instead of ultraviolet rays to cure.
  • Curetron EBC-200-AA3 manufactured by Nissin High Voltage Co., Ltd. was used (acceleration voltage: 200 kV, irradiation dose 20 kGy).
  • UV thermosetting is a method in which after UV curing, aging is further performed at 40 ° C. for 72 hours to complete the cross-linking reaction with a cross-linking agent.
  • EB thermosetting is a method in which after EB curing, aging is further performed at 40 ° C. for 72 hours to complete the cross-linking reaction with a cross-linking agent.
  • the coating composition was applied to various substrates with a bar coater (RDS 3), and the degree of repelling of the coating liquid was visually observed.
  • ⁇ A uniform coating film with no repellency.
  • ⁇ The coating film is almost uniform, although there are very few repellents.
  • ⁇ Although there are some repellents, the coating film is almost uniform as a whole.
  • X The coating film is uneven with many repellents.
  • Examples 106 to 113 and Comparative Examples 31 to 33 According to the proportion shown in Table 12, the polymer obtained in Table 1, the polymerizable composition obtained in Table 2 and other components are weighed and uniformly mixed at room temperature to form an ink.
  • the composition was prepared. The viscosity of the prepared ink composition was measured, and the dispersibility of the raw material was evaluated. Inkjet printing was performed using the prepared ink composition, and the physical properties of the obtained printed matter were evaluated.
  • the pigment and the pigment dispersant were not blended, and in the black ink composition, the pigment Pignent Black 7 was blended, and the pigment dispersant Azisper PB821 was blended and the black ink composition was not blended. Was done.
  • the results of the evaluation are summarized in Table 12.
  • Viscosity measurement and evaluation The viscosity of the ink composition was measured by a cone plate type viscometer (RE550 type viscometer manufactured by Toki Sangyo Co., Ltd.) according to JIS K5600-2-3. As an ink composition for inkjet printing, the viscosity was evaluated in four stages as described below. ⁇ : less than 5 to 100 mPa ⁇ s ⁇ : less than 100 to 500 mPa ⁇ s ⁇ : less than 500 to 2000 mPa ⁇ s ⁇ : 2000 mPa ⁇ s or more
  • the obtained ink composition is applied to a PET film having a thickness of 100 ⁇ m with a bar coater (RDS12) (thickness after drying is 10 ⁇ m), and is irradiated with ultraviolet rays (inverter manufactured by Eye Graphics Co., Ltd.).
  • RDS12 bar coater
  • a printed matter was produced by curing with a type conveyor device ECS-4011GX, metal halide lamp M04-L41).
  • the obtained ink composition is applied to various substrates and irradiated with ultraviolet rays (device: ECS-4011GX, an inverter type conveyor device manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, UV illuminance: 700 mW / cm. 2. Integrated light intensity: 1000 mJ / cm 2 ) to completely cure.
  • the obtained cured film was evaluated by counting the number of squares in which the cured film remained on the substrate side when 100 1 mm square squares were prepared by a grid test method, cellophane tape was attached, and the cured film was peeled off at once.
  • ⁇ Number of remaining squares 100
  • Number of remaining squares 50 or more and less than 90 Number of remaining squares less than 50
  • the ink composition prepared above was filled in a commercially available inkjet printer (LuxelJet U V350GTW manufactured by Fuji Film Co., Ltd.), a solid image was printed using coated paper, and the printability of the ink was evaluated by the following method.
  • the substrate (# 125-E20) was coated with a bar coater (RDS12) so as to have a film thickness of 10 ⁇ m, and cured with a metal halide lamp in the same manner as described above.
  • ⁇ E hue after heating-hue before heating.
  • Examples 114-122 and Comparative Examples 34, 35 According to the proportion shown in Table 13, the polymer obtained in Table 1, the polymerizable composition obtained in Table 2 and other components are weighed, mixed uniformly at room temperature, and tertiary. The original modeling ink composition was prepared. By the following method, the curing shrinkage rate of the three-dimensional modeling ink composition was measured, and the strength, heat resistance, water resistance, and modeling accuracy of the cured product of the three-dimensional modeling ink composition were measured. The evaluation results are shown in Table 13.
  • the curing shrinkage rate was determined according to JIS K5600 2-4 by the density change before and after curing of the three-dimensional modeling ink composition as shown in the following calculation formula (1).
  • the density of the ink composition for three-dimensional modeling before and after curing was measured by an electronic hydrometer (MDS-300 manufactured by Alpha Mirage Co., Ltd.) according to JIS K7112.
  • a 75 ⁇ m-thick heavy-release PET film (polyester film E7001 manufactured by Toyobo Co., Ltd.) is adhered to a horizontally installed glass plate, and a spacer with a thickness of 1 mm and the inside is punched into a No. 2 dumbbell type conforming to JIS K6251. After installing and filling the inside of the spacer with the three-dimensional modeling ink composition obtained in each example and comparative example, a light peeling PET film having a thickness of 50 ⁇ m (polyester film manufactured by Toyobo Co., Ltd.) is further formed thereon.
  • E7002 is layered and irradiated with ultraviolet rays from both sides (device: Eye Graphics, inverter type conveyor device ECS-4011GX, metal halide lamp: Eye Graphics M04-L41, ultraviolet illuminance 200mW / cm 2 , integrated light amount 1000mJ / cm 2 ) ), And the three-dimensional modeling ink composition was cured. Then, the peeled PET films on both sides were removed to obtain test pieces of a cured product for Examples and a cured product for Comparative Examples.
  • a desktop precision universal testing machine (Autograph AGS-X manufactured by Shimadzu Corporation) is used to obtain tensile strength under the conditions of a tensile speed of 10 mm / min and a chuck distance of 50 mm in a temperature environment of 25 ° C. The measurement was performed and the strength was evaluated according to the criteria shown below.
  • ⁇ Tensile strength 40 MPa or more
  • ⁇ Tensile strength 30 MPa or more and less than 40 MPa
  • ⁇ Tensile strength 20 MPa or more and less than 30 MPa
  • a 75 ⁇ m-thick heavy-release PET film (polyester film E7001 manufactured by Toyobo Co., Ltd.) is adhered to a horizontally installed glass plate, and a spacer with a thickness of 10 mm and an inside of 10 cm ⁇ 1 cm is installed, and 1 mm inside the spacer.
  • the three-dimensional modeling ink compositions obtained in each of the thick examples and the comparative examples were filled with each other, and the surface was smoothed by keeping the temperature at 60 ° C. for 30 seconds, and then irradiated with ultraviolet rays (device: eye graphics).
  • a 75 ⁇ m-thick heavy-release PET film (polyester film E7001 manufactured by Toyobo Co., Ltd.) is adhered to a horizontally installed glass plate, and a spacer with a thickness of 10 mm and an inside of 10 ⁇ 10 mm is installed, and 1 mm inside the spacer.
  • the surface was smoothed by keeping the temperature at 60 ° C. for 30 seconds, and then irradiated with ultraviolet rays (device: eye graphic).
  • ⁇ Height is 10 mm ⁇ 0.1 mm or more and less than ⁇ 0.2 mm, or there is very slight unevenness on the side surface.
  • ⁇ Height is 10 mm ⁇ 0.2 mm or more and less than ⁇ 0.3 mm, or there is slight unevenness on the side surface.
  • X Height is 10 mm ⁇ 0.3 mm or more, or there is obvious unevenness on the side surface.
  • the polymerizable composition containing N-substituted (meth) acrylamide (A) having a specific structure according to the present invention is a well-balanced amphipathic medium of A.
  • substrates with a wide range of polarities from low polarity to high polarity consisting of machine-based substrates, inorganic substrates, and organic / inorganic hybrid substrates, while having higher transparency and good curability due to their properties. It can be seen that the polymer or cured product has excellent wettability and is excellent in water resistance due to the influence of the hydrophobic substituent of A.
  • the pressure-sensitive adhesive composition containing the polymerizable composition and / or the polymer thereof, and the laminate of the pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition and various substrates show adhesion and adhesive strength to various substrates.
  • the adhesive composition containing the polymerizable composition and / or a polymer thereof has high adhesive strength, impact resistance and water resistance to various substrates, and can be used as an adhesive composition for the same or different materials. ..
  • the cosmetic composition containing the polymerizable composition and / or a polymer thereof and the like is a hair cosmetic having moisture resistance, smoothness, stickiness resistance, good texture and stability over time, or skin irritation.
  • the coating agent composition containing the polymerizable composition and / or a polymer thereof has high wettability and adhesion to various substrates, and when cured, exhibits high surface hardness and water resistance, and is an ink. It is clear that the composition has high adhesion to various substrates, is excellent in printing characteristics such as pigment dispersibility, surface drying property, ejection stability, and sharpness, and has high curability and yellowing resistance. Further, the three-dimensional modeling ink composition containing the polymerizable composition and / or a polymer thereof can accurately form a three-dimensional model having high strength, heat resistance and water resistance.
  • a pressure-sensitive adhesive composition obtained by using a polymerizable composition containing no N-substituted (meth) acrylamide (A) and / or a polymer thereof.
  • A N-substituted (meth) acrylamide
  • various molded products such as compositions, ink compositions and ink compositions for three-dimensional modeling are inferior in the effects of the above-mentioned polymerizable compositions containing A and / or various molded products obtained from the polymers thereof. Is.
  • the polymerizable composition of the present invention contains a specific N-substituted (meth) acrylamide (A), and thus has high transparency and good curability, while having low polarity to high polarity.
  • the polymer has excellent water resistance as well as excellent wettability to various substrates having a wide range of polarities up to polarity. Therefore, the polymerizable composition and / or the polymer thereof is used as a pressure-sensitive adhesive composition that can be polymerized and cured by active energy rays and / or heat in a wide range of fields such as industrial use, medical use, and household use. It can be used for adhesive-related products.
  • the pressure-sensitive adhesive composition has good adhesion to various substrates showing a wide range of polarities, and is in the form of a film of, for example, a polyolefin such as polyethylene or polypropylene, a polycarbonate, an acrylonitrile-butadiene-styrene copolymer, or a resin such as polyimide or polymethylmethacrylate.
  • a polyolefin adhesive sheet or a polyimide adhesive sheet can be obtained.
  • a glass adhesive sheet and a metal adhesive sheet can be obtained.
  • a pressure-sensitive adhesive sheet for an electronic material provided with a base material and an adhesive layer used for an electronic device a pressure-sensitive adhesive sheet for an optical member provided with a base material and a pressure-sensitive adhesive layer used for an optical member, and a base material and a pressure-sensitive adhesive layer used for an automobile are provided. It is possible to easily obtain an adhesive sheet for automobiles.
  • the adhesive composition composed of the pressure-sensitive adhesive composition and the cross-linking agent of the present invention is very effective for bonding the same kind of materials and various different materials from plastics to metals, and is very effective for bonding electronic materials, optical parts, semiconductors, etc. It can be widely used for solar cells and the like.
  • cosmetics having excellent moisture resistance and emulsion stability and having a good usability
  • coating agents capable of providing a coating layer having excellent adhesion to various substrates and having high surface hardness and water resistance, and high adhesion to various substrates.
  • Ink with high curability and yellowing resistance, excellent printing characteristics such as pigment dispersibility, surface dryness, ejection stability, sharpness, and three-dimensional modeling with high strength, heat resistance, and water resistance. It can be used as a three-dimensional modeling ink with excellent curing shrinkage resistance that enables accurate modeling of objects.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Dermatology (AREA)
  • Inorganic Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Graft Or Block Polymers (AREA)
  • Cosmetics (AREA)
  • Laminated Bodies (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
PCT/JP2021/038313 2020-10-15 2021-10-15 重合性組成物、その重合物及びそれらを用いた成形品 Ceased WO2022080493A1 (ja)

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KR1020237016075A KR20230088756A (ko) 2020-10-15 2021-10-15 중합성 조성물, 그 중합물 및 그것들을 사용한 성형품
JP2022515695A JP7325785B2 (ja) 2020-10-15 2021-10-15 重合性組成物、その重合物及びそれらを用いた成形品
CN202180069950.8A CN116391002B (zh) 2020-10-15 2021-10-15 聚合性组合物、其聚合物以及利用其得到的成形品
US18/032,205 US20230391937A1 (en) 2020-10-15 2021-10-15 Polymerizable composition, product of polymerization of same, and molded article obtained using these
EP21880228.8A EP4230664A4 (en) 2020-10-15 2021-10-15 POLYMERIZABLE COMPOSITION, POLYMERIZATION PRODUCT THEREOF, AND MOLDED ARTICLE OBTAINED USING THE SAME
JP2023085966A JP2023111929A (ja) 2020-10-15 2023-05-25 Ｎ－置換（メタ）アクリルアミドを含有するコーティング剤組成物
JP2023085967A JP7778385B2 (ja) 2020-10-15 2023-05-25 Ｎ－置換（メタ）アクリルアミドを含有する化粧料組成物
JP2023085965A JP2023115013A (ja) 2020-10-15 2023-05-25 Ｎ－置換（メタ）アクリルアミドを含有するインク組成物
JP2023085964A JP2023123427A (ja) 2020-10-15 2023-05-25 Ｎ－置換（メタ）アクリルアミドを含有する粘接着剤組成物
JP2025191673A JP2026015457A (ja) 2020-10-15 2025-11-12 重合物およびこれを含有する組成物
JP2025197610A JP2026020270A (ja) 2020-10-15 2025-11-18 Ｎ－置換（メタ）アクリルアミドを含有するコーティング剤組成物

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