WO2023190562A1 - 非水溶性多官能（メタ）アクリルアミド含有の硬化性組成物 - Google Patents

非水溶性多官能（メタ）アクリルアミド含有の硬化性組成物 Download PDF

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Publication number
WO2023190562A1
WO2023190562A1 PCT/JP2023/012610 JP2023012610W WO2023190562A1 WO 2023190562 A1 WO2023190562 A1 WO 2023190562A1 JP 2023012610 W JP2023012610 W JP 2023012610W WO 2023190562 A1 WO2023190562 A1 WO 2023190562A1
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Prior art keywords
meth
composition
curable composition
acrylamide
water
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PCT/JP2023/012610
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English (en)
French (fr)
Japanese (ja)
Inventor
晴香 古莊
一歩 岡田
篤史 安永
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KJ Chemicals Corp
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KJ Chemicals Corp
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Priority to CN202380041134.5A priority Critical patent/CN119234005A/zh
Priority to KR1020247035812A priority patent/KR20240169052A/ko
Priority to EP23780571.8A priority patent/EP4506387A4/en
Priority to US18/852,127 priority patent/US20250206865A1/en
Priority to JP2024512594A priority patent/JP7679126B2/ja
Publication of WO2023190562A1 publication Critical patent/WO2023190562A1/ja
Anticipated expiration legal-status Critical
Priority to JP2025073615A priority patent/JP2025109729A/ja
Ceased legal-status Critical Current

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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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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
    • C09J135/00—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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J135/00—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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J135/02—Homopolymers or copolymers of esters
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
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    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/26—Optical properties
    • A61K2800/262—Transparent; Translucent
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/81—Preparation or application process involves irradiation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/95—Involves in-situ formation or cross-linking of polymers
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    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625—Polyacrylic esters or derivatives thereof
    • C09K2200/0627—Nitrogen-containing polymers, e.g. polyacrylamide
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    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0642—Copolymers containing at least three different monomers

Definitions

  • the present disclosure relates to a water-insoluble polyfunctional (meth)acrylamide-containing curable composition.
  • N-substituted or N,N-disubstituted (meth)acrylamide having two or more (meth)acrylamide groups in the molecule is called polyfunctional (meth)acrylamide, and is highly resistant to ultraviolet (UV) radiation and thermosetting resins. Widely used as a compounding ingredient.
  • Polyfunctional (meth)acrylamide has a wide variety of structures depending on the type and number of its substituents, and its physical properties vary from liquid to solid, from hydrophilic (high polarity) to hydrophobic (low polarity), from low viscosity to high viscosity, etc.
  • UV curable resins It can cover a wide range of functions, including inks, adhesives, adhesives, various coating agents and paints, nail cosmetics and dental materials, cosmetics and medical materials such as contact lenses, and reactions for ultraviolet (UV) curable resins. It is used in a wide variety of fields, such as as a chemical diluent and as a crosslinking agent for thermal or photopolymerization.
  • aqueous curable compositions that do not contain organic solvents and use water as a solvent, and compositions that are curable with active energy rays such as UV or EB (electron beam) that do not contain organic solvents or water.
  • active energy rays such as UV or EB (electron beam)
  • aqueous curable compositions that use water as a solvent require an extremely large amount of energy to dry the water, whereas active energy ray curable compositions are highly promising because of their energy saving and low environmental impact. has been done.
  • water-soluble or water-dispersible water-based UV curable resins are irradiated with active energy rays and as the polymerization reaction (curing) progresses, water is evaporated by the amount of heat generated, and a small amount of water is evaporated due to the simultaneous progress of UV curing and drying. It is possible to quickly obtain a cured film even with the energy of .
  • the present disclosure has high curability and transparency, has good wettability and adhesion to various substrates, is a liquid at room temperature, has excellent handling properties, can be used in both aqueous and organic systems, and is UV curable. and/or provide a curable composition for thermal curing.
  • the present invention provides compositions, nail cosmetic compositions, dental material compositions, decorative coating agent compositions, and cured products and molded products thereof.
  • the curable composition of the present disclosure contains a water-insoluble polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), and has high curability. Due to the interaction between A and B, the potentially curable composition has high wettability and adhesion to various substrates, from low polarity resin materials to high polarity glass and metal materials, and has high wettability and adhesion to various substrates, from water and low polarity materials. It has good compatibility with organic solvents up to high polarity and a wide variety of general-purpose monomers, and has high transparency.
  • the curable composition is a liquid at room temperature, has good bundling properties, and its viscosity can be adjusted without limit from low to high viscosity depending on the application.
  • the curable composition of the present disclosure can be used in aqueous systems, organic systems, UV curing and/or heat curing, and can be used in printing inks for various methods such as inkjet printing, screen printing, offset printing, flexographic printing, and gravure printing. Used in compositions, three-dimensional modeling ink compositions, coating compositions, pressure-sensitive adhesive compositions, adhesive compositions, coating compositions, sealant compositions, nail cosmetics, decorative films and sheets, etc. It is suitably used for various purposes such as decorative coating agents and dental materials.
  • One embodiment of the present disclosure is a curable composition (D) containing a polyfunctional (meth)acrylamide (A) and a polymerizable compound (B).
  • Polyfunctional (meth)acrylamide (A) is a compound having two or more (meth)acrylamide groups in the molecule.
  • the number of (meth)acrylamide groups in A is preferably 6 or less. If the number of (meth)acrylamide groups exceeds 6, the acrylic equivalent will be small, the curable composition will shrink more during curing, and the resulting cured film will be more likely to deform and crack.
  • the viscosity and polarity of A increase due to the formation of hydrogen bonds between (meth)acrylamide groups, which may worsen the handling of A and the compatibility between A and the above-mentioned B.
  • the number of (meth)acrylamide groups in A is more preferably 4 or less.
  • polyfunctional (meth)acrylamide (A) is water-insoluble when used alone, it is a compound that has amphipathic properties. A becomes soluble in water by coexisting with the water-soluble polymerizable compound (B), and becomes soluble in low polar organic solvents by coexisting with the water-insoluble polymerizable compound (B). become. Therefore, the curable composition (D) containing A and B can be used in both aqueous and organic systems, and by adjusting the type, content, etc. of A and B, it can be made from water and low polarity to high polarity. It has good compatibility with organic solvents and a wide variety of general-purpose monomers, and has high transparency.
  • water-based curable composition such as water-based ink or water-based paint
  • it has good drying and curing properties, and it does not cause unevenness or cloudiness in the ink film (image) or paint film that evaporates water and dries. It has the effect of maintaining transparency, smoothness, and gloss without causing any stains.
  • the polyfunctional (meth)acrylamide (A) has one or more (meth)acrylamide groups in the molecule
  • the polymerizable compound (B) has one or more polymerizable groups in the molecule
  • a The curable composition (D) containing B is highly curable by active energy rays such as ultraviolet rays (UV) and electron beams (EB) and/or by heat, and the resulting cured product has excellent strength, hardness, heat resistance, etc. Also excellent.
  • the solubility parameter (SP value) of the polyfunctional (meth)acrylamide (A) is 8.8 to 11.0 (cal/cm 3 ) 1/2
  • the polyfunctional (meth)acrylamide (A) is polymerizable with A.
  • This is a curable composition (D) containing a compound (B) (excluding (A)).
  • the dissolved SP value in the present disclosure is calculated by the Fedors method described in Polymer Engineer Science, Vol. 14, P. 147, Y. 1974, and the unit is (cal/cm 3 ) 1/2 . The higher the SP value, the more hydrophilic the compound, and the lower the SP value, the more hydrophobic the compound.
  • the SP value of polyfunctional (meth)acrylamide (A) is within the range of 8.8 to 11.0 (units are omitted hereinafter), and A has amphipathic properties that exhibit both hydrophilicity and hydrophobicity. Due to the amphiphilic nature of (meth)acrylamide (A), the high cohesiveness derived from the (meth)acrylamide group, and the high adhesion to the substrate, the curable composition (D) can be made from a low polar resin material to a highly polar glass. It has high wettability, adhesion, and adhesion to various base materials, including aluminum and metal materials. Coating compositions, adhesive compositions, ink compositions, etc. containing the curable composition (D) have high wettability, adhesion, and tackiness, and adhesive compositions containing D have high adhesion. have power.
  • One embodiment of the present disclosure is the above-mentioned curable composition (D), wherein the polymerizable compound (B) (excluding polyfunctional (meth)acrylamide (A)) has an SP value of 8.5 to 14.5. It is.
  • the SP value of the polymerizable compound (B) is within this range, and B has hydrophilicity, hydrophobicity, or amphiphilicity of hydrophilicity and hydrophobicity depending on the type. Therefore, the polymerizable compound (B) and the polyfunctional (meth)acrylamide (A) have good compatibility, and the curable composition (D) containing A and B has high transparency, and can be obtained by curing D. The transparency of the cured product is also high.
  • the curable composition (D) has good solubility in water and various organic solvents, and is suitably used in both aqueous and organic systems.
  • aqueous and aqueous in a water-based curable composition, water-based ink composition, or water-based paint composition refer to water accounting for 60% by mass or more in the total mass of volatile components in various compositions.
  • organic curable composition, organic ink composition, or organic coating composition the organic component accounts for 60% by mass or more of the total mass of volatile components in various compositions. refers to something.
  • it refers to organic-based or organic.
  • curable composition (D) can be obtained either organically or aqueously, and in particular, in water-based ink compositions and water-based coating compositions, curable composition (D) ) has good pigment dispersibility, and the printing properties of the ink composition, such as ejection stability and print clarity, and the surface properties of the coating film obtained by curing the coating composition, such as surface smoothness and surface gloss, are excellent.
  • the various curable compositions (D) have an absolute value of the difference in SP value between the polyfunctional (meth)acrylamide (A) and the polymerizable compound (B) of 3.0 or less. be.
  • the absolute value of the difference between the SP values of A and B is preferably 2.5 or less, more preferably 1.5 or less.
  • Colorless, transparent clear type coating agent composition pressure-sensitive adhesive composition, adhesive composition, ink composition, ink composition for three-dimensional modeling, coating composition, sealing composition containing curable composition (D)
  • curable composition material compositions, nail cosmetics, dental materials, decorative coating agents, and colorless and transparent cured products and molded products thereof can be obtained, and can be suitably used as materials for optical members, electronic devices, etc.
  • the curable composition uses two or more types of polyfunctional (meth)acrylamide (A) and/or polymerizable compound (B)
  • the SP value of A is a weighted average based on the weight ratio of all A.
  • the SP value of B is a weighted average value based on the weight ratio of all B, and if A or B has repeating units in its structure, their SP value is a weighted average value. .
  • One embodiment of the present disclosure is the various curable compositions (D) in which the polyfunctional (meth)acrylamide (A) has an acrylic equivalent of 180 or more.
  • the acrylic equivalent in the present disclosure is the molecular weight per (meth)acrylamide group, that is, the value obtained by dividing the molecular weight by the number of acrylic groups. When the acrylic equivalent is low, the density of (meth)acrylamide groups is high and the curability is high, but the curing shrinkage resistance is low. If the acrylic equivalent of polyfunctional (meth)acrylamide (A) is less than 180, the density of the (meth)acrylamide group, which is a hydrophilic functional group in the A molecule, is too high, and A may become solid at room temperature.
  • the acrylic equivalent of A is preferably 190 to 2,500, more preferably 200 to 2,000.
  • One embodiment of the present disclosure is the various curable compositions (D) in which the polyfunctional (meth)acrylamide (A) is a compound represented by the general formulas [1] to [4].
  • R 1 represents a hydrogen atom or a methyl group.
  • Both R 2 and R 3 represent a divalent chain hydrocarbon group having 3 carbon atoms, and may have a linear or branched structure, and may be the same or different.
  • R 4 represents a hydrogen atom or a chain hydrocarbon group having 1 to 2 carbon atoms.
  • n is an integer from 1 to 70
  • m is 0 or 1.
  • x1 and z1 are each independently an integer from 1 to 10
  • y1 is an integer from 1 to 40
  • x2, y2, and z2 are each independently an integer from 1 to 30, and s3, x3, y3, and z3 are each independently an integer from 1 to 30. It is an integer from 1 to 20.
  • the polyfunctional (meth)acrylamides (A) shown in general formulas [1] to [4] include polypropyleneoxydi(meth)acrylamide, polypropyleneoxypolyethyleneoxydi(meth)acrylamide, trimethylolpropane polypropyleneoxy Examples include tri(meth)acrylamide, pentaerythritol polypropylene oxytetra(meth)acrylamide, and the like.
  • the number of repeating units of propyleneoxy groups and ethyleneoxy groups in these compounds is 1 to 30, it is easy to adjust the balance between the acrylic equivalent of A and the viscosity. That is, it is preferable because it has a suitable acrylic equivalent weight, is liquid or waxy at room temperature, and has good handling properties. From these points of view, the number of repeating units is more preferably 1 to 20, particularly preferably 2 to 10.
  • polyfunctional (meth)acrylamide (A) is a compound having a structure shown in general formulas [1] to [4], it has many ether groups in the molecule and is susceptible to photoradical polymerization caused by oxygen. It is preferable because it has the effect of preventing inhibition. Further, by having a repeating unit of isopropyleneoxy, although A is hydrophilic, the cured product of the curable composition containing it can have sufficiently satisfactory water resistance. Furthermore, although the polyfunctional (meth)acrylamides (A) shown in general formulas [1] to [4] are water-insoluble, the combination of (A) and the water-soluble curable compound (B) makes them water-soluble or water-soluble. It is possible to prepare dispersible aqueous curable compositions.
  • (A) contains a large number of hydrophilic (meth)acrylamide groups and is therefore easily compatible with water-soluble B at the molecular level.
  • the polyfunctional (meth)acrylamide (A) of general formulas [3] and [4] is trifunctional and tetrafunctional, but since it has a branched structure, the difunctional (meth)acrylamide (A) of general formulas [1] and [2] is Similar to (A), it is characterized by low shrinkage upon curing.
  • the content of the polyfunctional (meth)acrylamide (A) is 1 to 95% by mass
  • the content of the polymerizable compound (B) is 5% by mass with respect to the total mass of the curable composition. ⁇ 99% by mass of the curable composition (D). If the contents of A and B are within these ranges, the resulting curable composition will have all the physical properties and characteristics such as low viscosity, low curing shrinkage, high transparency, high curability, high wettability and adhesion.
  • the curable composition (D) can be dissolved or dispersed in both organic solvents and water, and can be obtained in various forms such as organic type, aqueous type, and emulsion.
  • the polyfunctional (meth)acrylamide (A) is insoluble in water, it becomes soluble in water by coexisting with the water-soluble polymerizable compound (B), and a water-based curable composition can be easily obtained. I can do it.
  • being soluble in water means being able to dissolve 1 g or more in 100 g of water at 25° C. to obtain a stable aqueous solution.
  • the contents of A and B in D are as follows:
  • the amounts are preferably 2 to 90% by weight and 10 to 98% by weight, respectively, and more preferably 5 to 80% by weight and 20 to 95% by weight, respectively.
  • the polymerizable compound (B) has a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, a (meth)allyl ether group in the molecule.
  • the various curable compositions (D) have one or more polymerizable groups selected from the group consisting of a maleimide group, an ⁇ -substituted maleimide group, and an ⁇ , ⁇ -substituted maleimide group.
  • B is a compound other than polyfunctional (meth)acrylamide (A).
  • the polymerizable group of the polymerizable compound (B) has an ethylenically unsaturated bond and can be polymerized by applying energy such as light or heat, and can be crosslinked by a polymerization reaction with polyfunctional (meth)acrylamide (A).
  • a cured polymer can be obtained.
  • the polymerizable group of B is preferably a (meth)acrylate group, a (meth)acrylamide group, and a vinyl group.
  • One embodiment of the present disclosure is the various curable compositions (D) in which the polymerizable compound (B) contains a monofunctional polymerizable compound (b1) and/or a polyfunctional polymerizable compound (b2). .
  • the content of (b1) is 0 to 80% by mass and the content of (b2) is 0 to 40% by mass based on the total mass of the curable composition.
  • the product containing polyfunctional (meth)acrylamide (A) and polymerizable compound (B) has high curability and transparency, and has good wettability and adhesion to various substrates. Certain curable compositions can be obtained.
  • the content of b1 is preferably 5% by mass or more, more preferably 10% by mass or more, Particularly preferred is 20% by mass or more.
  • the content of b1 exceeds 80% by mass, the total of the polyfunctional (meth)acrylamide (A) and the polyfunctional polymerizable compound (b2) in the curable composition (D) becomes less than 20% by mass.
  • D may not be fully satisfactory in surface hardness and strength of the resulting cured product depending on the intended use.
  • the content of b2 is preferably 2% by mass or more, more preferably 5% by mass or more, and 10% by mass or more. Particularly preferred.
  • the content of b2 exceeds 40% by mass, the total of the polyfunctional (meth)acrylamide (A) and the polyfunctional polymerizable compound (b2) in the curable composition (D) exceeds 41% by mass. As a result, the curing shrinkage of D increases, and there is a possibility that the obtained cured product may be deformed or cracked.
  • the monofunctional polymerizable compound (b1) and the polyfunctional polymerizable compound (b2) have one or more polymerizable groups arbitrarily selected from the group of the various polymerizable groups described above. Further, from the viewpoint of high polymerizability, curability, and hydrophilicity, the polymerizable groups b1 and b2 are preferably (meth)acrylate groups or (meth)acrylamide groups. Further, in a water-based curable composition, it is particularly preferable to use water-soluble b1 and/or b2.
  • the monofunctional polymerizable compound (b1) is a monofunctional (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, or isobutyl.
  • the monofunctional polymerizable compound (b1) is a monofunctional (meth)acrylamide such as N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N- - N-alkyl (saturated or unsaturated linear or branched chain having 1 to 18 carbon atoms) (meth) such as butyl (meth)acrylamide, N-isobutyl (meth)acrylamide, N-hexyl (meth)acrylamide, etc.
  • monofunctional (meth)acrylamide such as N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N- - N-alkyl (saturated or unsaturated linear or branched chain having 1 to 18 carbon atoms) (meth) such as butyl (me
  • Acrylamide N-alkoxy (linear or branched chain with 1 to 6 carbon atoms) alkyl (straight or branched chain with 1 to 6 carbon atoms) (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-alkoxy (direct carbon number 1 to 6) such as N-ethoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-ethoxyethyl (meth)acrylamide, chain or branched structure chain) alkyl (straight chain or branched structure chain having 1 to 6 carbon atoms) (meth)acrylamide, N-isobutoxymethyl (meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N- (2-hydroxyethyl) (meth)acrylamide, N-(2-hydroxypropyl) (meth)acrylamide, N-(3-hydroxypropyl) (meth)acrylamide, etc.
  • (meth)acrylamide N-[3-(dimethylamino)]propylacrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-di-n -Propyl (meth)acrylamide, N,N-diisopropyl (meth)acrylamide, N,N-di-n-butyl (meth)acrylamide, N,N-diisobutyl (meth)acrylamide, N-(meth)acryloylmorpholine, Allyl Examples include (meth)acrylamide, 2-ethylhexyl (meth)acrylamide, diacetone acrylamide, and the like. These monofunctional polymerizable compounds (b1) may be used alone or in combination of two or more.
  • the polyfunctional polymerizable compound (b2) is a polyfunctional (meth)acrylate such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, or diethylene glycol di(meth)acrylate.
  • a polyfunctional (meth)acrylate such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, or diethylene glycol di(meth)acrylate.
  • the polyfunctional polymerizable compound (b2) is a polyfunctional (meth)acrylamide such as methylenebis(meth)acrylamide, ethylenebis(meth)acrylamide, N,N'-(2-methylpropane-1,1-diyl)di( meth)acrylamide, N,N'-cyclohexylmethylene di(meth)acrylamide, N,N'-(pentane-1,1-diyl)di(meth)acrylamide, N,N'-(3-methylbutane-1,1) -diyl)di(meth)acrylamide, 2-(meth)acrylamido-2-methylpropanesulfonic acid, 1,4-bis(acryloyl)piperazine, ditrimethylolpropane tetraacrylamide, dipentaerythritol hexamethacrylamide, and the like.
  • These polyfunctional polymerizable compounds (b2) may be used alone or in combination of two or more.
  • One embodiment of the present disclosure provides the various curable compositions described above, which further contain a polymerizable polymerization initiator (C) and contain 0.1 to 20% by mass of C based on the total mass of the curable composition.
  • the polymerizable polymerization initiator (C) is a polyfunctional (meth)acrylamide (A) and a polymerizable compound ( It is a compound other than B).
  • the polymerizable group of C is a (meth)acrylate group, (meth)acrylamide group, vinyl group, vinyl ether group, methyl vinyl ether group, allyl group, (meth)allyl ether group, maleimide group, ⁇ -substituted maleimide group, ⁇ , ⁇ -substituted One or more groups selected from the group consisting of maleimide groups.
  • the initiating group for C is not particularly limited as long as it generates radicals, cations, anions, etc. as growth active species upon irradiation with light or heating.
  • an intramolecular cleavage type that generates radicals by intramolecular cleavage after absorbing UV and other light
  • a hydrogen abstraction type that generates radicals by exchanging hydrogen and electrons.
  • electron donating type initiating groups More specifically, examples of the intramolecular cleavage type initiator group include benzoin derivatives, benzyl ketal, ⁇ -hydroxyacetophenone, ⁇ -aminoacetophenone, acylphosphine oxide, titanocenes, and o-acyloxime types.
  • Hydrogen abstraction type initiating groups include benzophenone derivatives having a diaryl ketone skeleton such as benzophenone, alkyldiaminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 2-hydroxythioxanthone.
  • Examples include thioxanthone derivatives having a thioxanthone skeleton such as. It is possible to use a compound in which one or more of these initiating groups are selected and combined with one or more of the above polymerizable groups.
  • hydrogen abstraction type initiating groups are preferred because they do not produce by-products of low-molecular-weight compounds after the radical generation reaction and do not remain in the cured product. Further, it is more preferable to have a structure in which a hydrogen abstraction type initiator group is combined with a (meth)acrylate group or a (meth)acrylamide group which is a highly polymerizable group. Further, in the water-based curable composition, it is particularly preferable to use a water-soluble or hydrophilic polymerization initiator (C).
  • the content of the polymerizable polymerization initiator (C) varies depending on the structure of the initiator group, the type of polymerizable group, the composition of the curable composition, etc., but is 0.1% by mass based on the total mass of the curable composition.
  • thermal polymerization, photopolymerization, active energy ray curing, etc. can be started immediately, and the curable composition can be sufficiently cured.
  • (C) has a polymerizable group, if its content is 20% by mass or less, the curable composition can be rapidly cured and the physical properties of the cured product will not deteriorate.
  • the content of the polymerizable polymerization initiator (C) with respect to the entire curable composition is preferably 0.5 to 15% by mass, and 1 to 10% by mass. % is more preferable.
  • a quaternary salt monomer is a compound other than polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), and is a compound that has both a polymerizable group and a quaternary salt structure in its molecule, and is monofunctional. It may be polyfunctional.
  • the polymerizable groups of the quaternary salt monomer are (meth)acrylate group, (meth)acrylamide group, vinyl group, vinyl ether group, methyl vinyl ether group, allyl group, (meth)allyl ether group, maleimide group, ⁇ -substituted maleimide group, ⁇ , ⁇ -substituted maleimide group.
  • the quaternary salt structure may be cationic, anionic, or amphoteric with cations and anions.
  • Quaternary salt monomers are from the group consisting of ammonium salts, imidazolium salts, choline salts, sulfonium salts, pyrazolium salts, oxazolium salts, pyridinium salts, pyrrolidinium salts, phosphonium salts, carboxylates, sulfonates, phosphates, etc.
  • a compound can be used in which one or more selected cationic groups and/or anionic groups are combined with one or more selected from the various polymerizable groups mentioned above. .
  • quaternary ammonium salt monomers are particularly preferred because they have antistatic properties and antibacterial properties, and have the effect of promoting dissolution and dispersion of pigments in the ink composition.
  • These quaternary salt monomers may be used alone or in combination of two or more.
  • the quaternary salt monomer is 0.1 to 30% by mass based on the total mass of the curable composition (D).
  • One embodiment of the present disclosure is a coating agent composition (hereinafter also referred to as a coating agent) containing the various curable compositions described above.
  • the polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the coating agent composition, can be brought in from the curable composition (D) according to each of the above embodiments, and if necessary, Depending on the situation, it can also be added when preparing the coating composition.
  • the content of A is preferably 1 to 60% by mass, and the content of B is preferably 20 to 99% by mass, based on the total mass of the coating composition.
  • a hydrophilic, hydrophobic, or amphipathic coating composition By combining amphipathic A and hydrophilic, hydrophobic, or amphipathic B, a hydrophilic, hydrophobic, or amphipathic coating composition can be obtained. Further, although A is water-insoluble, by combining it with water-soluble B, it is possible to obtain a water-soluble coating composition or a coating composition in the form of an emulsion that can be stably and uniformly dispersed in water. Such a coating agent composition has excellent compatibility with a wide range of compounds other than A and B, from hydrophobic to water-soluble, since the types and contents of A and B can be easily adjusted, and it has excellent compatibility with a wide range of compounds other than A and B, from organic to inorganic.
  • the cured film (coating film) obtained by curing the coating agent composition is even and uniform, and has high transparency and surface smoothness. Furthermore, since A has a large number of isopropyleneoxy groups, it is possible to impart water resistance to the resulting cured film, and the appearance and surface hardness of the cured film can also be adjusted depending on the application. For example, when A is used together with the monofunctional polymerizable compound (b1) as B, unevenness does not occur on the surface of the cured film and the appearance such as surface smoothness is improved, and as the polymerizable compound (B) By using it in combination with the polymerizable compound (b2), the surface hardness of the cured film is significantly improved.
  • Such coating agent compositions can be suitably used for various coating applications such as hard coats, vehicles, indoor or outdoor building materials, and the like.
  • One embodiment of the present disclosure is an adhesive composition (hereinafter also referred to as an adhesive) containing the various curable compositions described above.
  • (A) and the polymerizable compound (B), which are essential constituent components of the adhesive composition can be brought in from the curable composition (D) according to each of the above embodiments, and can be added to the adhesive composition as necessary. It can also be added when preparing.
  • the content of A is preferably 2 to 50% by mass, and the content of B is preferably 10 to 90% by mass, based on the total mass of the adhesive composition.
  • A is amphiphilic and has a plurality of (meth)acrylamide groups, and due to the interaction between the wettability derived from the amphipathic property and the cohesive property of the (meth)acrylamide groups, the adhesive composition can be applied to various substrates ( Excellent adhesion to organic materials to inorganic materials) and stain resistance (removable reworkability).
  • A is amphiphilic and has many (meth)acrylamide groups with high hydrolysis resistance and isopropyleneoxy groups with high water resistance and curing shrinkage resistance, and the combination of A and B
  • the adhesive layer or adhesive sheet obtained by curing the adhesive composition, or the laminate formed by laminating the adhesive layer through the adhesive layer has good yellowing resistance (including transparency) and durability (moisture heat resistance).
  • the adhesive composition of this embodiment contains polymerization initiators such as a polymerizable polymerization initiator, a non-polymerizable polymerization initiator, a photopolymerization initiator, a thermal polymerization initiator, various solvents from low polarity to high polarity, and It is possible to further contain general-purpose monomers and various additives, and the viscosity can be adjusted from low to high depending on the application.
  • Such an adhesive composition can also be suitably used in the optical field, such as adhesives for optical members, adhesive layers, and adhesive sheets.
  • the obtained adhesive layer and a laminate comprising the adhesive layer and various base materials can be applied as an adhesive film or adhesive sheet for electronic materials, optical members, and automobile parts.
  • the adhesive composition of the present embodiment can be applied or molded onto a separator or a base material, and then cured by active energy ray irradiation to form an adhesive layer.
  • the adhesive composition may be applied or molded onto a separator or base material, and cured while irradiating active energy and evaporating (drying) the organic solvent. It is preferable to perform active energy curing after drying by heating at a temperature of 120° C. for 1 to 30 minutes because a more transparent adhesive layer can be obtained.
  • the pressure-sensitive adhesive composition can be applied by a conventional coating film forming method such as a spin coating method, a spray coating method, a knife coating method, a dipping method, a gravure roll method, a reverse roll method, a screen printing method, or a bar coater method.
  • a conventional coating film forming method such as a spin coating method, a spray coating method, a knife coating method, a dipping method, a gravure roll method, a reverse roll method, a screen printing method, or a bar coater method.
  • a laminate can be obtained by laminating various base materials using an adhesive layer made of an adhesive composition.
  • the lamination method include a transfer method and a roll-to-roll method.
  • the thickness of the adhesive layer in the laminate is not particularly limited as it varies depending on the various uses, but it is usually 4 to 150 ⁇ m, and when used for automobile parts, it is about 20 to 120 ⁇ m, and it is used for electronic materials and optical parts. In some cases, a thickness of about 30 to 100 ⁇ m is appropriate.
  • the base material to be adhered to and the base material to be laminated may include organic materials ranging from low polarity materials to high polarity materials.
  • organic materials ranging from low polarity materials to high polarity materials.
  • materials can be used, such as organic base materials, inorganic base materials, and materials made of organic/inorganic composite materials.
  • polyolefin resins such as polyethylene and polypropylene
  • polyester resins such as polyethylene terephthalate and polycarbonate
  • ABS resins such as acrylonitrile-butadiene-styrene copolymers
  • acrylic resins such as polyimide resins, polyamide resins, and polymethyl methacrylate
  • steel, stainless steel
  • metals such as copper and aluminum, glasses, and hybrid materials in which fine silica particles, an inorganic material, are dispersed in polyimide, an organic material.
  • the uses of the various laminates obtained are not particularly limited, but examples include uses for electronic materials, optical members, and automobile parts.
  • One embodiment of the present disclosure is an adhesive composition (hereinafter also referred to as adhesive) containing the various curable compositions described above.
  • the polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the adhesive composition, can be brought in from the curable composition (D) according to each of the above embodiments, and if necessary, It can also be added when preparing the adhesive composition, if appropriate.
  • the content of A is preferably 2 to 70% by mass, and the content of B is preferably 20 to 90% by mass, based on the total mass of the adhesive composition.
  • A is amphiphilic and has multiple (meth)acrylamide groups, and due to the interaction between the wettability derived from the amphipathic property and the cohesive property of the (meth)acrylamide groups, the adhesive composition can be attached to various substrates ( It can evenly and evenly adhere to materials (from organic materials to inorganic materials), has high adhesive strength after curing, and can be suitably used for adhesion of the same type of materials as well as different types of materials.
  • A has many isopropyleneoxy groups and (meth)acrylamide groups, and the cured product of the adhesive composition containing A (adhesive layer, adhesive laminate, etc.) has good hydrolysis resistance and water resistance. has.
  • the viscosity of the adhesive composition can be easily adjusted, and a thin to thick adhesive layer can be produced depending on the application.
  • the heat resistance and cold shock resistance of the cured product can be significantly improved.
  • the adhesive composition containing amphiphilic A, various B, and a polymerizable or non-polymerizable polymerization initiator has high transparency, and the adhesive layer obtained by curing it also maintains high transparency. Therefore, such an adhesive composition can also be suitably used in the optical field, such as as an adhesive for optical members.
  • One embodiment of the present disclosure is an ink composition (hereinafter also referred to as ink) containing the various curable compositions described above.
  • the polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential constituent components of the ink composition, can be brought in from the curable composition (D) according to each of the above embodiments, and can be added as necessary. It can also be added when preparing the ink composition.
  • the content of A is preferably 3 to 50% by mass, and the content of B is preferably 20 to 85% by mass, based on the total mass of the ink composition.
  • A is amphiphilic, and when mixed with B of various polarities from hydrophilic to hydrophobic, it exhibits excellent dispersibility of various inorganic pigments and organic pigments, and excellent coating properties on various printing substrates.
  • the resulting printed matter has excellent print clarity.
  • the ink composition has high curability by containing A, and the resulting printed surface has good surface drying properties. Further, by using A and the polyfunctional polymerizable compound (b2) together, the surface drying properties of the printed surface obtained from the ink composition are further improved.
  • a in combination with the monofunctional polymerizable compound (b1) an ink composition with a viscosity ranging from low to high viscosity can be obtained.
  • the ink composition of this embodiment can suitably adjust the viscosity according to various uses and printing methods, and has high ejection stability and printing accuracy (including printing clarity) during printing.
  • the viscosity of the ink composition at 25° C. is preferably 1000 mPa ⁇ s or less, more preferably 500 mPa ⁇ s or less, and particularly preferably 100 mPa ⁇ s or less from the viewpoint of suitability for use in an inkjet system.
  • the quaternary salt monomer has excellent compatibility with the pigment, dissolution and dispersion of the pigment is promoted by including the quaternary salt monomer in the ink composition.
  • the ink composition should have an A of 3 to 50. It is preferable to contain b1 in an amount of 30 to 80% by mass and b2 in an amount of 5 to 40% by mass.
  • Such an ink composition can be suitably used in various printing methods such as inkjet printing, offset printing, screen printing, and flexographic printing.
  • offset printing is a printing method that takes advantage of the property of an oil-based offset printing ink composition that is repellent to water, but by containing A and hydrophobic B, the ink composition has high hydrophobicity and curability. This enables high-speed and high-precision printing. Further, even in an ink composition containing A having a large number of isopropyleneoxy groups and a hydrophilic B, the water resistance of the obtained printed matter is sufficiently satisfactory.
  • One embodiment of the present disclosure is an aqueous ink composition (hereinafter also referred to as an aqueous ink) containing the various curable compositions described above.
  • the polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential constituent components of the ink composition can be brought in from the curable composition (D) according to each of the above embodiments, and can be added as necessary. It can be additionally added when preparing the aqueous ink composition. It is preferable that the content of A is 1 to 60% by weight, the content of B is 5 to 89% by weight, and the content of water is 10 to 50% by weight, based on the total weight of the aqueous ink composition.
  • A is water-insoluble but amphiphilic, it has good compatibility with water-soluble B, and the curable composition obtained by mixing with water-soluble B can be used as an aqueous ink composition.
  • Such an ink composition exhibits excellent solubility or compatibility with water, and also exhibits good solubility or dispersibility for water-soluble pigments, etc., and is suitable as a clear ink that does not contain pigments.
  • the aqueous ink composition contains A, it has high curability, and the resulting printed surface has excellent water resistance.
  • ink compositions there are various types of ink compositions depending on the purpose, such as ink compositions that have high compatibility between A and B and D containing A and B with water and additives such as water-soluble pigments, and have a viscosity range suitable for inkjet printing.
  • a wide variety of inks can be prepared.
  • the ejection stability of the ink composition during inkjet printing is also good, and high printing characteristics can be exhibited.
  • the solubility of A in water is significantly improved, and the above-mentioned various properties of the aqueous ink composition and its cured product are further improved. ,preferable.
  • the aqueous ink composition of the present embodiment may be in the form of an aqueous solution that dissolves in water, or may be in the form of an aqueous dispersion such as an emulsion that is dispersed in water. Further, the content of water is 10% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass or more, based on the total mass of the aqueous ink composition.
  • the water is preferably water that does not contain ionic impurities, such as ion-exchanged water or distilled water.
  • One embodiment of the present disclosure is a three-dimensional modeling ink composition (hereinafter also referred to as a modeling ink composition or modeling ink) containing the various curable compositions described above.
  • the polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the modeling ink composition, can be brought in from the curable composition (D) according to each of the above embodiments, and are necessary. It can be additionally added when preparing the modeling ink composition depending on the situation.
  • the content of A is preferably 1 to 60% by mass, and the content of B is preferably 20 to 99% by mass, based on the total mass of the modeling ink composition.
  • A has a plurality of (meth)acrylamide groups and isopropyleneoxy groups, and the curability of the modeling ink composition is high, and the strength, toughness (impact resistance), and water resistance of the obtained modeled object (cured product) are improved. is good.
  • the monofunctional polymerizable compound (b1) as B the viscosity of the modeling ink composition can be suitably adjusted according to the specifications of the apparatus used for modeling, and handling properties are also improved.
  • the polyfunctional polymerizable compound (b2) as B the curability of the modeling ink composition, the strength, hardness, etc. of the resulting model can be further improved.
  • the compatibility between A and B is high, and the transparency of the modeling ink composition and the ink ejection stability during modeling are high. Further, when the acrylic equivalent of A is 180 or more, the curing shrinkage resistance of the modeling ink composition is higher, and a modeled object with excellent modeling accuracy can be obtained.
  • the modeling ink composition is formed into a predetermined shape pattern and is cured by active energy ray irradiation or heat at the same time or immediately after the formation to form a thin film, and by laminating the thin films, a three-dimensional model is created. Can be obtained.
  • the modeling method is not particularly limited, for example, a stereolithography method in which the material is ejected by an inkjet method and cured by irradiation with active energy rays can be mentioned.
  • the viscosity of the 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 modeling ink composition contains 5 to 60% by mass of A, 10 to 70% by mass of b1, and 5 to 5% of b2. It is more preferable to contain 50% by mass.
  • One embodiment of the present disclosure is a water-based paint composition (hereinafter also referred to as a water-based paint) containing the various curable compositions described above.
  • the polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the water-based coating composition can be brought in from the curable composition (D) according to each of the above embodiments, and if necessary It can be additionally added when preparing the aqueous coating composition, depending on the situation. It is preferable that the content of A is 1 to 50% by weight, the content of B is 5 to 79% by weight, and the content of water is 20 to 80% by weight, based on the total weight of the aqueous coating composition.
  • A is water-insoluble but amphiphilic, it has good compatibility with water-soluble B, and the curable composition obtained by mixing with water-soluble B can be used as a water-based paint composition.
  • Such a coating composition exhibits excellent solubility or compatibility with water, and also exhibits good solubility or dispersibility for water-soluble pigments, etc., and is suitable as a clear ink that does not contain pigments. High storage stability; high pigment dispersibility and storage stability for a pigment-containing ink.
  • the water-based paint composition contains A, it has high curability, and the resulting coating film has excellent water resistance.
  • the compatibility of A and B and the compatibility of D containing A and B with additives such as water and water-soluble pigments are high, and A also has multiple (meth)acrylamide groups and isopropyleneoxy groups. It has high wettability and adhesion to various base materials such as wood, metal, concrete, rubber, ceramics, plastic, paper, fiber, and nonwoven fabric, and is used for coating multi-materials. Furthermore, when containing 0.1% by mass or more of a quaternary salt monomer, the solubility of A in water is significantly improved, and the various properties described above are further improved in the water-based coating composition and the coating film that is the cured product thereof.
  • the aqueous coating composition of this embodiment may be in the form of an aqueous solution that dissolves in water, or may be in the form of an aqueous dispersion such as an emulsion that is dispersed in water. Further, the content of water is 20% by mass or more, preferably 30% by mass or more, and more preferably 50% by mass or more, based on the total mass of the aqueous coating composition.
  • the water is preferably water that does not contain ionic impurities, such as ion-exchanged water or distilled water.
  • the water-based coating composition of the present embodiment may contain an organic solvent if necessary, and the content thereof is 40% by mass or less based on the total mass of volatile components (the total of organic solvent and water). Moreover, it is preferably 30% by mass or less, more preferably 20% by mass or less.
  • active energy such as UV or EB
  • the aqueous coating composition can be applied using conventional coating film forming methods such as spin coating, spray coating, knife coating, dipping, dipping, gravure roll, reverse roll, screen printing, and bar coater methods. It is also suitable for manual painting with roller brushes, brushes, spatulas, etc.
  • One embodiment of the present disclosure is a sealant composition (hereinafter also referred to as a sealant).
  • the polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential constituent components of the sealant composition, can be brought in from the curable composition (D) according to each of the above embodiments, and are necessary. It can be additionally added when preparing the sealant composition depending on the situation.
  • the content of A is preferably 1 to 60% by mass, and the content of B is preferably 10 to 99% by mass, based on the total mass of the sealant composition.
  • the (meth)acrylamide group of A has high curability to both active energy rays and heat, and the sealant composition obtained by using A and B in combination also exhibits high curability.
  • A is polyfunctional, there is very little uncured polymerizable compound (residual monomer) in the cured product such as the sealing layer or sealant obtained by curing the sealant composition, and the cured product is It has high outgas resistance, resistance to moist heat yellowing, corrosion resistance, etc., and can exhibit excellent sealing effects as a sealant.
  • the compatibility between A and B is high, and the sealant composition and the cured product such as a sealing layer obtained by curing the same have good transparency and are suitably used for optical applications.
  • the large number of isopropyleneoxy groups in A have the effect of imparting water resistance and curing shrinkage resistance to the obtained cured product, and furthermore, the combination of A and the monofunctional polymerizable compound (b1) improves the sealant composition. Handling properties are improved, and the combined use of A and the polyfunctional polymerizable compound (b2) improves the curability of the sealant composition and the strength and heat-sealing resistance of the resulting cured product.
  • One embodiment of the present disclosure is a nail cosmetic composition (hereinafter also referred to as nail cosmetic).
  • the polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the nail cosmetic composition, can be brought in from the curable composition (D) according to each of the above embodiments, and are also necessary. It can be additionally added when preparing a nail cosmetic composition depending on the situation.
  • the content of A is preferably 1 to 40% by mass, and the content of B is preferably 10 to 99% by mass, based on the total mass of the nail cosmetic composition.
  • A has a plurality of (meth)acrylamide groups
  • the resulting nail cosmetic composition has high curability and adhesion to nails
  • the resulting cured product also referred to as cured film or nail
  • the compatibility between A and B and the compatibility between A and B and other components such as pigments are high, nail cosmetic compositions that do not contain pigments and their cured films have high transparency and surface gloss.
  • the nail cosmetic composition contained therein had high pigment dispersibility (uniformity), the resulting cured film had high surface gloss, and there was almost no occurrence of unevenness in the cured film due to overcoating or repair work.
  • the nail cosmetic composition has better curing shrinkage resistance, no unevenness occurs on the surface of the cured film, and the appearance of the nails is good.
  • various bases such as natural nails, artificial nails, nail films and nail chips can be formed.
  • a nail cosmetic composition that can be used as a material can be obtained.
  • One embodiment of the present disclosure is a dental material composition (hereinafter also referred to as dental material).
  • the polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the dental material composition, can be brought in from the curable composition (D) according to each of the above embodiments, and if necessary, Additional additions can be made when preparing the dental material composition as required.
  • the content of A is preferably 0.5 to 50% by mass, and the content of B is preferably 5 to 99% by mass, based on the total mass of the dental material composition.
  • A has a plurality of (meth)acrylamide groups, has high curability and adhesiveness of the dental material composition, and can obtain high adhesive strength when used as an adhesive dental material.
  • the dental material composition has high curing shrinkage resistance, no deformation over time or surface irregularities after curing, and good surface smoothness.
  • A is used in combination with the monofunctional polymerizable compound (b1), the viscosity of the dental material composition can be easily adjusted, and the handling properties can be improved.
  • a is used in combination with the polyfunctional polymerizable compound (b2) the curability of the dental material composition becomes higher, and the hardness of the resulting cured product also becomes higher.
  • One embodiment of the present disclosure is a decorative coating agent composition (hereinafter also referred to as a decorative coating agent).
  • the polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential constituent components of the decorative coating agent composition can be brought in from the curable composition (D) according to each of the above embodiments, or If necessary, it can be additionally added when preparing the decorative coating agent composition.
  • the content of A is preferably 1 to 50% by mass, and the content of B is preferably 20 to 99% by mass, based on the total mass of the decorative coating agent composition.
  • A has a plurality of (meth)acrylamide groups, the resulting decorative coating agent composition has high curability, and the resulting cured products such as decorative coats, decorative films, and decorative films have high surface hardness and scratch resistance. is good. Further, A has a large number of isopropyleneoxy groups, and the obtained cured product exhibits flexibility, and the decorative coat, decorative film, and decorative film have excellent bending resistance. A is amphiphilic and has high compatibility with B, and it is possible to further dissolve oligomers, polymers, etc. in D containing A and B, and the elongation of the cured product obtained from such a composition is rate will be higher.
  • the curable composition (D) may contain components other than the above as optional components, if necessary.
  • organic solvents and various additives can be used as necessary.
  • Organic solvents include alcohols such as ethyl alcohol, n-propyl alcohol, and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, alkylene glycols, polyalkylene glycols, glycol ethers, glycol esters, benzene, and toluene.
  • aromatic hydrocarbons such as ethbenzene and xylene
  • aliphatic hydrocarbons such as hexane, heptane, octane, decane, and cyclohexane
  • esters such as ethyl acetate, butyl acetate, and 2-hydroxyethyl acetate, acetonitrile, N,N- Dimethylformamide is mentioned.
  • organic solvents can be used alone or in combination of two or more.
  • low boiling point ethyl acetate, methyl ethyl ketone, acetone, etc. are more preferable from the viewpoint of easy removal by drying or other methods during coating, film formation, molding, or after molding.
  • low boiling point water-soluble ethyl alcohol, n-propyl alcohol, isopropyl alcohol and the like are more preferred.
  • the content thereof is preferably 1.0 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the curable composition. Within this range, there is no risk of adversely affecting the properties expected of the compositions of the embodiments of the present disclosure and the cured products obtained by curing them.
  • Additives used in the present disclosure include polymerization initiators (excluding polymerizable polymerization initiators (C)), thermal polymerization inhibitors, antioxidants, antioxidants, ultraviolet sensitizers, preservatives, and phosphate esters. and other flame retardants, surfactants, wetting and dispersing agents, antistatic agents, colorants, plasticizers, surface lubricants, leveling agents, softeners, pigments, organic fillers, inorganic fillers, silica particles, and the like.
  • the amount of these additives added is not particularly limited as long as it does not adversely affect the expected properties of the composition of each embodiment of the present disclosure and the cured product obtained by curing them, and it is based on the total mass of the curable composition. It is preferably 5% by mass or less, more preferably 2% by mass or less.
  • a non-polymerizable component can be further contained as necessary.
  • the non-polymerizable component is a compound that does not contain the above-mentioned polymerizable group in its molecule.
  • Mw weight average molecular weight
  • non-polymerizable components are classified into non-polymerizable oligomers when Mw is 1,000 or more and less than 10,000, and non-polymerizable oligomers when Mw is 10,000 or more. It should be a non-polymerizable polymer.
  • the non-polymerizable oligomer and non-polymerizable polymer include thermoplastic resins, rosin 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, butadiene, and styrene, polycarbonate resin, and polyamide.
  • resin and polyimide resin examples include resin and polyimide resin.
  • Rosin resins include 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, esterified gum, etc. Examples include rosin resin. These non-polymerizable oligomers and non-polymerizable polymers may be used alone or in combination of two or more.
  • the content of the non-polymerizable component is preferably 0.1 to 20% by mass based on the total mass of the curable composition.
  • the non-polymerizable component has the function of adjusting the viscosity of the curable composition, improving the adhesion of the adhesive composition to the base material, improving the adhesive strength of the adhesive layer and adhesive, and coating. It has the effect of imparting toughness to cured products of agent compositions, ink compositions, and three-dimensional modeling ink compositions, sealant compositions, and cured products of decorative coating agent compositions. From these viewpoints, the content of the non-polymerizable component is more preferably 0.5 to 15% by mass, particularly preferably 1 to 10% by mass.
  • the curable composition according to each embodiment of the present disclosure can be cured by active energy rays such as UV and EB and/or heat, and a cured product that can be suitably used for various purposes can be obtained.
  • active energy rays such as UV and EB and/or heat
  • an adhesive layer can be formed by applying a curable composition to a separator or various base materials and then curing it with active energy rays.
  • curing the curable composition using active energy rays and heat is also referred to as hybrid curing.
  • curing may be performed in the order of active energy rays and heat, or curing may be performed in order of heat and active energy rays, and thermal curing using the amount of heat generated by active energy ray curing, that is, active energy rays Simultaneous curing with heat and heat may be performed.
  • the active energy ray is defined as an energy ray that can decompose a compound (photopolymerization initiator) that generates active species to generate active species.
  • active energy rays include visible light, ultraviolet rays, infrared rays, ⁇ rays, ⁇ rays, ⁇ rays, X rays, and electron beams (EB).
  • EB electron beams
  • Irradiation with active energy rays is preferably performed in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide, or in an atmosphere with a reduced oxygen concentration. Since it contains functional (meth)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.
  • Non-polymerizable photopolymerization initiators include substances that generate radicals by irradiation with ultraviolet rays of an appropriate wavelength that can cause a polymerization reaction, depending on the type of active energy ray-reactive component (i.e., photoradical polymerization initiators). ).
  • photopolymerization initiators may be appropriately selected from common ones such as acetophenone, benzoin, benzophenone, and thioxanthone, and commercially available products include IGM Resins B. V.
  • These non-polymerizable photopolymerization initiators may be used alone or in combination of two or more.
  • the non-polymerizable photoradical polymerization initiator is not particularly limited, and includes, for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 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-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, and other acetophenones, 2-hydroxy-2- Propi
  • the content of the non-polymerizable photoinitiator is 0.1 to 20% by mass, and 0.5 to 10% by mass, based on the total mass of the curable composition according to each embodiment of the present disclosure.
  • the amount is preferably 1 to 5% by weight, and more preferably 1 to 5% by weight. If the content of the non-polymerizable photopolymerization initiator is less than 0.1% by weight, sufficient curability cannot be obtained, and if it exceeds 20% by weight, performance such as strength of the cured product may deteriorate.
  • a polymerizable photoinitiator (C) and a non-polymerizable photoinitiator can be used together.
  • Thermal curing of the curable composition according to each embodiment of the present disclosure can be carried out by a known method in the presence of a thermal polymerization initiator, such as emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method, etc.
  • a thermal polymerization initiator such as emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method, etc.
  • a method such as a polymerization method can be used to obtain a crosslinkable cured product.
  • the solvents that can be used are aromatic hydrocarbons such as toluene, ethylbenzene, and xylene, aliphatic hydrocarbons such as hexane, heptane, octane, decane, and cyclohexane, ethyl acetate, butyl acetate, and acetic acid.
  • aromatic hydrocarbons such as toluene, ethylbenzene, and xylene
  • aliphatic hydrocarbons such as hexane, heptane, octane, decane, and cyclohexane
  • ethyl acetate ethyl acetate
  • butyl acetate acetic acid
  • esters such as 2-hydroxyethyl, aliphatic alcohols such as ethyl alcohol, n-propyl alcohol, and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, acetonitrile, and N,N-dimethylformamide. .
  • These solvents may be used alone or in combination of two or more.
  • the temperature and time of thermal polymerization vary depending on the thermal polymerization method employed 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 initiator examples include thermal radical polymerization initiators, such as azobisisobutyronitrile, azobisvaleronitrile, azobis(isobutyrate) dimethyl, 2,2'-azobis[N-(2-carboxylate) ethyl)-2-methylpropionamidine] tetrahydrate, 2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis[2-(2-imidazoline-2 Azo compound-based catalysts such as [-yl)propane], peroxide-based catalysts such as benzoyl peroxide and hydrogen peroxide, and persulfate-based catalysts such as ammonium persulfate and sodium persulfate can be used.
  • the content of the thermal polymerization initiator is approximately 0.01 to 10% by mass based on the total mass of the curable composition.
  • ordinary radical polymerization techniques such as molecular weight adjustment using a chain transfer agent can be applied.
  • E2-1 Ethyl acetate
  • E2-2 Methyl ethyl ketone
  • E2-3 Toluene
  • E2-4 Acryloylaminopropyl trimethylammonium p-toluenesulfonate
  • E2-5 Acryloyloxyethyl Trimethylammonium bis(trifluoromethanesulfonyl)imide
  • F-3 N,N'-[oxybis(2,1-ethanediyloxy-3,1-propanediyl)]bisacrylamide (mol
  • Examples 1 to 15 and Comparative Examples 1 to 6 preparation and evaluation of curable compositions
  • the polyfunctional (meth)acrylamide (A), the polymerizable compound (B), and other components were weighed in the mass ratio shown in Table 1, and mixed at 35°C for 1 hour to cure 1 to 15 and Comparative Examples 1 to 6.
  • a sexual composition was prepared.
  • the transparency (compatibility) and active energy ray curability of the obtained curable composition were evaluated by the following methods, and the results are shown in Table 1. Further, Table 1 summarizes the SP values of A and B and the absolute values of the differences between the SP values of A and B.
  • ⁇ Tack disappeared when the cumulative light amount was 1000 mJ/cm 2 or more and less than 2000 mJ/cm 2 .
  • ⁇ Tack remained even when the cumulative light amount was 2000 mJ/cm 2 or more.
  • the curable composition (D) containing a water-insoluble polyfunctional (meth)acrylamide (A) and a polymerizable compound (B) other than A has both transparency and curability. was also excellent.
  • A is water-insoluble, since it exhibits amphipathic properties, it can be made compatible with B, which is hydrophobic, hydrophilic, and water-soluble.
  • the SP value of A is 8.8 to 11.0
  • the SP value of B is 8.5 to 14.5, and the difference between the SP values of A and B is 3.0 or less, the resulting transparent D sex was higher.
  • the content of A is 1 to 95% by mass and the content of B is 5 to 99% by mass with respect to the total mass of D
  • B is a monofunctional polymerizable compound (b1) and/or a polyfunctional polymerizable compound ( By containing b2), both the transparency and curability of D are good, and in particular, when the total content of A and b2 exceeds 15% by mass, the curability of D becomes higher.
  • the transparency of the curable composition was poor because A or B had insufficient compatibility with the polymerization initiator.
  • Examples 16 to 21 and Comparative Examples 7 and 8 preparation and evaluation of coating agent composition
  • the curable composition obtained in Table 1, polyfunctional (meth)acrylamide (A), polymerizable compound (B), and other components were weighed at the mass ratio shown in Table 2, and mixed at 35 ° C. for 1 hour, Coating compositions of Examples 16 to 21 and Comparative Examples 7 and 8 were prepared.
  • the wettability of the resulting coating composition to various substrates and resistance to curing shrinkage upon curing with active energy rays were evaluated by the following methods.
  • a coating film (also referred to as a cured film or a coating film) was prepared on a PET film using the coating agent composition by the following method, and the tack resistance, appearance, and surface hardness of the obtained coating film were evaluated by the following method.
  • the evaluation was carried out by Table 2 shows various evaluation results.
  • the obtained coating film was cut into 10 cm square pieces, and the average lifting of the four corners was measured to evaluate curing shrinkage resistance (curling resistance). The greater the lift, the greater the curl, and the lower the curing shrinkage resistance.
  • ⁇ There is a lifting of 0.5 mm or less.
  • ⁇ There is a lifting of 1 mm or less.
  • ⁇ There is a lifting of 3 mm or less.
  • ⁇ Large curl.
  • the curing shrinkage resistance was A coating film was prepared in the same manner as in the curling property evaluation.
  • the surface of the obtained coating film was hit with a silicone rubber stopper and the degree of stickiness (surface tackiness) was evaluated according to the following criteria, and the results are shown in Table 1. The more sticky it is, the lower the tack resistance. ⁇ : No stickiness at all. ⁇ : There is some stickiness, but no marks remain on the surface. ⁇ : There is stickiness and marks remain on the surface. ⁇ : Very sticky, and the rubber stopper sticks to the surface.
  • a coating film with a thickness of 10 ⁇ m was prepared in the same manner as in the evaluation of cure shrinkage resistance (curl resistance).
  • the surface smoothness and transparency of the obtained coating film were visually observed, and the appearance of the coating film was evaluated according to the following criteria. The higher the surface smoothness and the more transparent the coating, the better the appearance.
  • ⁇ The surface was smooth and the coating film was transparent.
  • ⁇ The surface was smooth, and the coating film was entirely transparent with a slight cloudy part.
  • ⁇ The surface was uneven or the coating film had cloudy parts.
  • x The surface was uneven and the coating film was cloudy.
  • the coating agent composition of the example contains a polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), and has high curability and curing shrinkage resistance. , showed good wettability on various substrates ranging from plastic substrates (PET, PVC, ABS) to metals (aluminum).
  • the coating film obtained from the coating agent composition of the example had a good appearance, and the tack resistance and surface hardness of the coating film were both high. These effects are due to the interaction of A and B. Comparative coating compositions that did not contain A and B at the same time did not exhibit similar characteristics.
  • Examples 22 to 27 and Comparative Examples 9 and 10 (Preparation and evaluation of adhesive composition)
  • the curable composition obtained in Table 1, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photopolymerization initiator (C) and other components were weighed at the mass ratio shown in Table 3, The mixture was mixed at 35° C. for 1 hour to prepare adhesive compositions of Examples 22 to 27 and Comparative Examples 9 and 10.
  • a pressure-sensitive adhesive layer and a pressure-sensitive adhesive sheet were prepared by the following method, and the curability of the pressure-sensitive adhesive composition, the adhesion to various substrates, and the adhesive strength and transparency of the obtained pressure-sensitive adhesive layer were evaluated. , stain resistance (reworkability), yellowing resistance and moist heat resistance were evaluated, and the results are shown in Table 3.
  • the adhesive composition was cured by overlapping and irradiating with a UV LED lamp having a wavelength of 385 nm and an output of 100 mW/cm 2 so that the cumulative amount of light was 3000 mJ/cm 2 .
  • the cured product (adhesive layer) obtained by removing the peelable PET films on both sides was touched with a finger, and the curability was evaluated in three stages according to the following criteria.
  • Good A cured product that can maintain its shape is obtained, and although tack is observed when the cured product is touched, there is no adhesion of liquid uncured material.
  • ⁇ A cured product that can maintain its shape is obtained, and tackiness is observed when the cured product is touched, but liquid uncured material is still attached.
  • Curing is insufficient, a cured product that can maintain its shape cannot be obtained, and a large amount of liquid residue is observed.
  • Adhesive sheet production and adhesion evaluation The adhesive compositions of each example and comparative example were coated on various plate-shaped substrates (substrates), and placed on the table with a light release separator (silicone coated PET film) to prevent air bubbles from entering. Using a roll-type laminator machine (RSL-382S manufactured by Royal Sovereign), the adhesive layers were laminated to a thickness of 5 ⁇ m and irradiated with ultraviolet light (equipment: I-Graphics inverter type conveyor device ECS-4011GX, metal halide lamp: M04-L41 manufactured by Eye Graphics, UV illuminance: 700 mW/cm 2 , cumulative light amount: 5000 mJ/cm 2 ).
  • a light release separator silicone coated PET film
  • the easy release separator was peeled off to obtain an adhesive sheet consisting of an adhesive layer and a substrate.
  • an adhesive sheet consisting of an adhesive layer and a substrate.
  • the adhesiveness was evaluated according to the following criteria. The greater the number of remaining squares, the higher the adhesion. ⁇ : The number of squares remaining was 100. ⁇ : The number of remaining squares was 95 to 99. ⁇ : The number of remaining squares was 70 to 94. ⁇ : The number of remaining squares was 0 to 69.
  • Adhesive force evaluation Under conditions of a temperature of 23°C and a relative humidity of 50%, the above-mentioned adhesive layer was transferred to various film-like or plate-like base materials, and the pressure was applied by moving it back and forth twice using a pressure roller weighing 2 kg. Then, it was left to stand for 30 minutes under the same atmosphere. Thereafter, the 180° peel strength (N/25 mm) was measured at a peel rate of 300 mm/min according to JIS Z0237 using a tensile tester (equipment name: Tensilon RTA-100 manufactured by ORIENTEC). The higher the peel strength, the higher the adhesive force.
  • the adhesive composition of the example contains a polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), and due to their interaction, the adhesive composition has a high It exhibited curability, and the adhesive layer obtained by curing it had high transparency.
  • the adhesive compositions of Examples had good adhesion and tackiness (adhesive strength) to various materials ranging from general-purpose plastics to inorganic glasses.
  • the cured product (adhesive layer) obtained from the adhesive composition of the example maintains high transparency, and has good stain resistance when the cured product is peeled from the substrate, as well as yellowing resistance and moisture resistance of the cured product. Thermal properties were also good.
  • the composition of the comparative example was found to have low curability, low adhesion and tackiness to various materials, and low transparency, stain resistance, yellowing resistance, and moist heat resistance of the cured product.
  • Examples 28 to 33 and Comparative Examples 11 and 12 (Preparation and evaluation of adhesive composition)
  • the curable composition obtained in Table 1, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photopolymerization initiator (C) and other components were weighed at the mass ratio shown in Table 4,
  • Adhesive compositions of Examples 28 to 33 and Comparative Examples 11 and 12 were prepared by mixing at 35° C. for 1 hour.
  • the transparency of the obtained adhesive composition was evaluated by the following method.
  • plate-like substrates of the same or different types were adhered by the following method to prepare adhesive test pieces, and the adhesive strength, water resistance, and impact resistance were evaluated. The evaluation was performed and the results are shown in Table 4.
  • Adhesive Test Piece Two plate-like substrates of the same or different types measuring 100 mm long x 25 mm wide x 1 mm thick were used, and the adhesive composition was uniformly applied to any one of them. In addition, when the adhesive composition contained a solvent, a large amount of the mixture was applied so that the thickness after drying was approximately the same as when no solvent was used, and the mixture was dried at 90° C. for 2 minutes. Then, in accordance with JIS K 6850, place the other plate-like base material on the applied adhesive composition, and bond them together so that the overlapping area is 12.5 mm long x 25 mm wide, using a spacer. The thickness of the adhesive layer was adjusted to 100 ⁇ m, and a bonded test piece was prepared.
  • UV irradiation equipment I-Graphics inverter type conveyor device ECS-4011GX, metal halide lamp: I-Graphics M04-L41, ultraviolet illuminance: 700 mW/ cm 2 , cumulative light amount: 5000 mJ/cm 2
  • the test piece after irradiation was used as an adhesive test piece.
  • Impact resistance evaluation of adhesive test piece Using the obtained adhesive test piece, impact tester No. 1 was tested according to JIS K6855. 511 (manufactured by Mize Test Instruments Co., Ltd.) to measure the impact peel adhesion strength. Note that the higher the impact peel adhesion strength, the higher the impact resistance.
  • ⁇ : Impact peel adhesion strength is 20 KJ/m 2 or more.
  • ⁇ : Impact peel adhesion strength is 15 KJ/m 2 or more and less than 20 KJ/m 2 .
  • Impact peel adhesion strength is 10 KJ/m 2 or more and less than 15 KJ/m 2 .
  • Impact peel adhesion strength is less than 10 KJ/m 2 .
  • the adhesive compositions of Examples contained polyfunctional (meth)acrylamide (A) and polymerizable compound (B) and exhibited high transparency. Furthermore, the adhesive composition of the example was used to bond various materials of the same or different types, from plastic substrates (PET, PMMA, PC, PVC, ABS) to metals (aluminum), and sufficiently satisfactory adhesive strength was obtained. . This is because the adhesive composition had excellent wettability to various materials and at the same time, the adhesive obtained after curing had high adhesive strength. In addition, by having A containing a large number of isopropyleneoxy groups, the water resistance and impact resistance of the adhesive obtained in the example are good, and in particular, the adhesive obtained in the example has good water resistance and impact resistance. In Examples 29 to 31, further improvements in water resistance and impact resistance were confirmed. On the other hand, adhesive compositions of comparative examples that do not contain A and B at the same time, and adhesives obtained from them, were not confirmed to have similar properties.
  • Examples 34 to 39 and Comparative Examples 13 and 14 (Preparation and evaluation of curable ink compositions)
  • the curable composition obtained in Table 1, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photopolymerization initiator (C) and other components were weighed at the mass ratio shown in Table 5, The mixture was mixed at 35° C. for 1 hour to prepare ink compositions of Examples 34 to 39 and Comparative Examples 13 and 14.
  • the viscosity was measured by the following method, and the transparency in the case of not containing a pigment (clear ink) and the pigment dispersibility in the case of containing a pigment were evaluated.
  • the curability of the ink composition and the ejection stability during inkjet printing were evaluated, and the sharpness of the resulting printed matter was evaluated. The results of these evaluations are summarized in Table 5.
  • Viscosity measurement and evaluation of ink composition The viscosity of the obtained ink composition at 25°C was measured using a cone plate viscometer (RE550 viscometer manufactured by Toki Sangyo Co., Ltd.) according to JIS K5600-2-3. It was measured. As an ink composition for inkjet printing, the viscosity was evaluated in four stages as shown below. ⁇ : 5 or more, less than 100 mPa ⁇ s ⁇ : 100 or more, less than 500 mPa ⁇ s ⁇ : 500 or more, less than 2000 mPa ⁇ s ⁇ : 2000 mPa ⁇ s or more
  • Inkjet printing and ink ejection stability evaluation The ink composition was filled into a commercially available inkjet printer (LuxelJet U V350GTW manufactured by Fuji Film Co., Ltd.), a solid image was printed using coated paper, and the printing condition of the obtained printed matter was visually observed.
  • the discharge stability was evaluated according to the following criteria. ⁇ : There was no nozzle omission and the printing was good. ⁇ : There is a slight nozzle missing. ⁇ : Nozzle missing in a wide range. ⁇ : Non-ejection occurred.
  • the ink compositions of Examples contain highly compatible polyfunctional (meth)acrylamide (A) and polymerizable compound (B), and have high transparency (clear ink) or It had pigment dispersibility.
  • the ink composition containing A and B has high curability, and can be prepared with a low viscosity as an ink composition for inkjet printing, and the printed matter with good ejection stability and good print clarity. Ta.
  • the ink compositions of Comparative Examples all had low viscosity, transparency, pigment dispersibility, curability, or ejection stability, and the print clarity of the resulting printed matter was not satisfactory.
  • Examples 40 to 45 and Comparative Examples 15 and 16 (Preparation and evaluation of water-based ink compositions)
  • the curable composition obtained in Table 1, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photoinitiator (C), water, and other components were weighed at the mass ratios shown in Table 6.
  • the mixture was mixed at 35° C. for 1 hour to prepare aqueous ink compositions of Examples 40 to 45 and Comparative Examples 15 and 16.
  • the compatibility with water (clear ink) and the dispersibility of the water-soluble pigment were evaluated by the following method.
  • the initial viscosity was measured to evaluate the viscosity suitability as an ink composition for inkjet printing.
  • Viscosity fluctuation rate (%) (viscosity after storage - initial viscosity) / initial viscosity x 100%
  • Pigment dispersibility evaluation of aqueous ink composition The obtained aqueous pigment-containing aqueous ink composition was placed in a transparent screw tube, the initial state was visually observed, and the composition was allowed to stand in the dark at room temperature for 24 hours. Thereafter, the state of the aqueous pigment-containing aqueous ink composition after standing was visually observed, and the pigment dispersibility was evaluated according to the following criteria. ⁇ : No pigment precipitation was observed either initially or after standing. ⁇ : No pigment precipitation was observed initially, but slight pigment precipitation was observed after standing. ⁇ : Slight precipitation of pigment was observed at the initial stage, and clear precipitation of pigment was observed after standing. ⁇ : Clear precipitation of pigment was observed even in the initial stage.
  • Viscosity measurement and evaluation of aqueous ink composition The viscosity of the obtained aqueous ink composition was measured using a cone plate viscometer (RE550 viscometer manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K5600-2-3. did.
  • Viscosity suitability was evaluated according to the following criteria. ⁇ : 5 mPa ⁇ s or more and less than 100 mPa ⁇ s ⁇ : 100 Pa ⁇ s or more and less than 500 mPa ⁇ s ⁇ : 500 Pa ⁇ s or more and less than 2000 mPa ⁇ s ⁇ : 2000 mPa ⁇ s or more
  • the aqueous ink compositions of Examples had low viscosity, high compatibility or pigment dispersibility, and good ejection stability in inkjet printing. Furthermore, the aqueous ink compositions of Examples had good storage stability and high curability. The reason why such results are obtained is that the water-based ink composition of the example contains a water-insoluble polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), and the compatibility between A and B is extremely high. This is because it has excellent pigment dispersibility and water solubility. It was confirmed that the printed matter obtained by curing the aqueous ink composition of the example had excellent surface drying properties and print clarity. On the other hand, in the aqueous ink compositions of Comparative Examples and their printed matter, multiple characteristic evaluations were not satisfactory.
  • A water-insoluble polyfunctional (meth)acrylamide
  • B polymerizable compound
  • Examples 46 to 51 and Comparative Examples 17 and 18 (Preparation and evaluation of ink composition for three-dimensional modeling)
  • the curable composition obtained in Table 1, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photoinitiator (C) and other components were weighed at the mass ratio shown in Table 7,
  • Three-dimensional modeling ink compositions of Examples 46 to 51 and Comparative Examples 17 and 18 were prepared by mixing at 35° C. for 1 hour.
  • a three-dimensional model was produced by the following method, and the curing shrinkage resistance of the three-dimensional modeling ink composition, the strength, impact resistance, and water resistance of the obtained cured product were evaluated. The performance and modeling accuracy were evaluated, and the evaluation results are shown in Table 7.
  • a 75 ⁇ m thick heavy release PET film (manufactured by Toyobo Co., Ltd., polyester film E7001) was placed in close contact with a horizontally placed glass plate, and the inside was 1 mm thick and conformed to JIS K6251.
  • a spacer punched in the shape of a No. 2 dumbbell was installed, and the inside of the spacer was filled with the three-dimensional modeling ink compositions obtained in each example and comparative example, and then a light release PET with a thickness of 50 ⁇ m was placed on top of the spacer.
  • the tensile strength was measured using a tabletop precision universal testing machine (Autograph AGS-X manufactured by Shimadzu Corporation) under the conditions of a tensile speed of 10 mm/min and a distance between chucks of 50 mm in a temperature environment of 25°C. The strength was evaluated based on the following criteria. ⁇ : Tensile strength was 40 MPa or more. Good: Tensile strength was 30 MPa or more and less than 40 MPa. ⁇ : Tensile strength was 20 MPa or more and less than 30 MPa. ⁇ : Tensile strength was less than 20 MPa.
  • Post-curing was performed at a wavelength of 405 nm, an illumination intensity (UV-V) of 50 mW/cm 2 , and an integrated light amount of 5,000 mJ/cm 2 ) to completely cure the film. Thereafter, using the obtained cured product as a test piece, Izod impact strength (with notch) was measured according to JIS K-7110, and the impact resistance was evaluated as follows. Note that an Izod-Charpy impact tester "Model No. 195-R" manufactured by Yasuda Seiki Seisakusho Co., Ltd. was used. The higher the impact strength, the higher the impact resistance. ⁇ : 40 J/m or more ⁇ : 30 J/m or more and less than 40 J/m ⁇ : 20 J/m or more and less than 30 J/m ⁇ : less than 20 J/m
  • Water absorption rate (%) (weight after immersion - weight before immersion) / weight before immersion x 100% ⁇ : Water absorption rate is less than 2% ⁇ : Water absorption rate is 2% or more and less than 2.5% ⁇ : Water absorption rate is 2.5% or more and less than 3% ⁇ : Water absorption rate is 3% or more
  • Evaluation of modeling accuracy Prepare a spacer with a thickness of 10 mm and an internal size of 10 x 10 mm in the same way as the test piece for the strength evaluation above, and place a 1 mm thick spacer inside the spacer for three-dimensional modeling obtained in each example and comparative example. After filling the ink composition, the surface was smoothed by keeping it warm at 60° C. for 30 seconds, and then similarly irradiated with ultraviolet rays to cure the three-dimensional modeling ink composition. Thereafter, the obtained cured product was filled with a three-dimensional modeling ink composition to a thickness of 1 mm, and curing was repeated 10 times in total to obtain a cured product measuring 10 ⁇ 10 ⁇ 10 mm.
  • the height of the obtained cured product was measured, the side surface was visually observed, and the modeling accuracy was evaluated according to the following criteria.
  • ⁇ Height less than 10 mm ⁇ 0.1 mm and no unevenness on the side surface.
  • ⁇ Height is 10 mm ⁇ 0.1 mm or more and less than ⁇ 0.2 mm, or there is slight unevenness on the side surface.
  • ⁇ Height 10 mm ⁇ 0.2 mm or more and less than ⁇ 0.3 mm, or the side surface is slightly uneven.
  • the height is 10 mm ⁇ 0.3 mm or more, or there are obvious irregularities on the side surface.
  • the three-dimensional modeling ink composition of the example contains the water-insoluble polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), and the resulting Strength, impact resistance, water resistance, and molding accuracy were all good.
  • the curing shrinkage resistance of the ink composition for three-dimensional modeling and the water resistance and impact resistance of the obtained model were further improved. was confirmed.
  • the curing shrinkage resistance of the ink composition for three-dimensional modeling was low, and various physical properties of the obtained model were also poor.
  • Examples 52 to 57 and Comparative Examples 19 and 20 preparation and evaluation of water-based coating compositions
  • the curable composition obtained in Table 1, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photopolymerization initiator (C), and other components were weighed at the mass ratio shown in Table 8, The mixture was mixed at 35° C. for 1 hour to prepare aqueous coating compositions of Examples 52 to 57 and Comparative Examples 19 and 20.
  • the obtained water-based coating composition was applied onto an ABS substrate using a bar coater (No. 12) (film thickness after drying: 10 ⁇ m), and dried at 80° C. for 10 minutes using a hot air dryer.
  • Example 52 to 56 and Comparative Examples 19 and 20 were irradiated with ultraviolet light (the same i-Graphics inverter type conveyor device as above, the same metal halide lamp as above, ultraviolet illuminance: 300 mW/cm 2 , A UV-cured cured product (cured coating film) was obtained. Further, the dried coating film obtained in Example 57 was heated and cured in a hot air dryer at 120° C. for 10 minutes to obtain a thermosetting cured product (cured coating film). The appearance, adhesion, hot water resistance, and chemical resistance of the obtained cured product were evaluated by the following methods, and the results are shown in Table 8.
  • Paint film appearance ⁇ : The surface was smooth and the coating film was transparent. ⁇ : The surface was smooth, and the coating film was entirely transparent with slight cloudy areas. ⁇ : The surface was uneven or the coating film had cloudy parts. ⁇ : The surface was uneven and the coating film was cloudy.
  • the water-based coating compositions of Examples have high adhesion, can be cured by UV (active energy rays) and heat, and have high transparency and high surface smoothness. A cured coating film with an excellent appearance was obtained. Moreover, the obtained cured coating film had good hot water resistance and chemical resistance.
  • Examples 58 to 62 and Comparative Examples 21 and 22 preparation and evaluation of sealant composition
  • the curable composition obtained in Table 1, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photoinitiator (C) and other components were weighed at the mass ratio shown in Table 9, The mixture was mixed at 35° C. for 1 hour to prepare sealant compositions of Examples 58 to 62 and Comparative Examples 21 and 22.
  • a cured sealant material was produced by the method described below, and the physical properties of the obtained sealing layer were evaluated as follows.
  • cured sealant (sealing layer)
  • a silicone spacer (30 mm long x 15 mm wide x 3 mm thick) was set on a glass plate (50 mm long x 50 mm wide x 5 mm thick), and a silicone spacer (30 mm long x 15 mm wide x 3 mm thick) was placed inside the spacer.
  • a copper foil (5 mm long x 5 m wide x 80 ⁇ m thick) was placed, and the prepared curable sealant composition was injected.
  • the sealant was irradiated with ultraviolet light (the same i-Graphics inverter conveyor device as above, the same metal halide lamp as above, ultraviolet illuminance: 700 mW/cm 2 , cumulative light amount: 1000 mJ/cm 2 ).
  • ultraviolet light the same i-Graphics inverter conveyor device as above, the same metal halide lamp as above, ultraviolet illuminance: 700 mW/cm 2 , cumulative light amount: 1000 mJ/cm 2 ).
  • a cured product was obtained.
  • the properties of the obtained cured product were evaluated by the following method, and the results are shown in Table 9.
  • Transparency evaluation of cured encapsulant The part without copper foil was cut out from the obtained cured encapsulant and left to stand for 24 hours in an atmosphere with a temperature of 23°C and a relative humidity of 50%.
  • the transmittance of the cured product was measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., NDH-2000), and the transparency was evaluated according to the following criteria. The higher the transmittance, the higher the transparency.
  • ⁇ Transmittance is 85% or more and less than 90%
  • Transmittance Transmittance is 50% or more and less than 85%
  • Transmittance Transmittance is less than 50%
  • Water absorption rate (%) (weight after water absorption - weight before water absorption) / weight before water absorption x 100% ⁇ : Water absorption rate is less than 1.0% ⁇ : Water absorption rate is 1.0% or more and less than 2.0% ⁇ : Water absorption rate is 2.0% or more and less than 3.0% ⁇ : Water absorption rate is 3 .0% or more
  • outgas generation rate (weight after test - weight before test) / weight before test x 100% ⁇ : Incidence rate is less than 0.1% ⁇ : Incidence rate is 0.1% or more and less than 0.3% ⁇ : Incidence rate is 0.3% or more and less than 1.0% ⁇ : Incidence rate is 1 .0% or more
  • Moisture heat yellowing resistance evaluation After the obtained cured sealant was allowed to stand for 24 hours in an atmosphere with a temperature of 23°C and a relative humidity of 50%, the transmission spectrum of the cured product was measured using a dedicated transmission color measurement machine (TZ-6000). (manufactured by Nippon Denshoku Kogyo Co., Ltd.) and used as the initial b value. Thereafter, the cured product was left standing in a constant temperature and humidity machine set at 85° C. and 85% relative humidity for 500 hours, and an accelerated test for moisture and heat yellowing resistance was conducted. The cured product after the test was similarly allowed to stand for 24 hours in an atmosphere with a temperature of 23° C.
  • TZ-6000 dedicated transmission color measurement machine
  • the transmitted color was measured, and the b value was determined after moist heat.
  • the moist heat yellowing resistance of the cured product was evaluated according to the following criteria. ⁇ : Both the initial b value and the b value after moist heat are 0.2 or less, and ⁇ b is 0.1 or less. ⁇ : Either or both of the initial b value and the b value after moist heat exceed 0.2, but both are 0.5 or less, and ⁇ b is 0.2 or less.
  • ⁇ One or both of the initial b value and the b value after moist heat exceed 0.5, but both are 1.0 or less, and ⁇ b is 0.3 or less.
  • ⁇ Either or both of the initial b value and the b value after moist heat exceed 1.0, or ⁇ b exceeds 0.3.
  • the sealant composition of the example contains a water-insoluble polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), and a large number of isopropyleneoxy groups in A. and (meth)acrylamide groups, the resulting cured sealant had high water resistance, generated little outgas, and had good resistance to moist heat yellowing, heat cycle resistance, and corrosion resistance. Moreover, since the compatibility between A and B was high, the transparency of the cured sealant was also high. On the other hand, the cured product obtained from the curable composition of the comparative example could not satisfy any of these physical properties.
  • the sealant composition of the present disclosure can be suitably used as a sealant for optical members, electrical equipment, and the like.
  • Examples 63 to 67 and Comparative Examples 23 and 24 (Preparation and evaluation of hardening nail cosmetics)
  • the active energy ray-curable composition obtained in Table 1, (meth)acrylamide (A), polymerizable compound (B), photopolymerization initiator (C), and other components were weighed at the mass ratios shown in Table 10. , and mixed at 35° C. for 1 hour to prepare nail cosmetics of Examples and Comparative Examples.
  • curability and physical properties of the obtained cured film were evaluated by the following method, and the results are shown in Table 10.
  • the obtained hardenable nail cosmetics was coated onto a nylon 6 test piece (“SHT-N6 (NC)” manufactured by Toray Plastics Seiko Co., Ltd.) using a bar coater (No. 12). It was applied to a thickness of 10 ⁇ m, and then irradiated with ultraviolet light using a UV-LED lamp (manufactured by Beauty Nailer, wavelength 405 nm, 48 W) for gel nails, and the time taken for the tack to disappear when the surface of the cured film was touched was measured.
  • the curing properties of the nail cosmetics were evaluated according to the following criteria. The shorter the time required for the tack to disappear, the higher the curability. ⁇ : Tack disappears in less than 1 minute. ⁇ : Tack disappears in 1 minute or more and less than 3 minutes. ⁇ : Tack disappears in 3 minutes or more and less than 10 minutes. ⁇ : Tack does not disappear even after 10 minutes or more.
  • the hardening nail cosmetic of the example simultaneously contained (meth)acrylamide (A) and a polymerizable compound (B).
  • A methacrylamide
  • B polymerizable compound
  • the curable nail cosmetic of the present disclosure can be suitably used as a base gel gel nail that is applied directly to the nail.
  • the obtained cured film has good surface hardness and surface gloss, and can be suitably used as a top coat gel nail.
  • the curable composition of the comparative example had low curability, and the surface hardness and surface gloss of the cured film were low.
  • Examples 68 to 72 and Comparative Examples 25 and 26 (preparation and evaluation of hardenable dental materials)
  • the curable composition obtained in Table 1, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photopolymerization initiator (C) and other components were weighed at the mass ratio shown in Table 11, By mixing at 35° C. for 1 hour, hardenable dental materials of Examples and Comparative Examples were prepared. The solubility or dispersibility (when an insoluble inorganic filler was blended) of the obtained hardenable dental material was visually observed.
  • a cured dental material was prepared using the curable dental material by the method described below, and the curability of the curable dental material and the surface smoothness, hardness, and adhesive strength of the obtained cured dental material were evaluated. Table 11 shows these evaluation results.
  • a dental light irradiator (Tokuso Power Light, manufactured by Tokuyama Dental Co., Ltd., light output density 700 mW/cm 2 , light intensity on the irradiation surface 640 to 650 mW/cm 2 , light source is a halogen lamp, irradiation
  • a polypropylene film (diameter: 8 mm) was placed in close contact with the polypropylene film and irradiated for 30 seconds, the polypropylene film was peeled off, and the cured product was touched with hands to check for stickiness and the presence of uncured components, and the curability was evaluated according to the following criteria.
  • ⁇ No stickiness at all (completely cured). ⁇ : Slight stickiness, but no finger marks remain on the surface (almost completely cured, no need to wipe off uncured components). ⁇ : Sticky and finger marks remain on the surface (incompletely cured, uncured components need to be wiped off). ⁇ : So sticky that fingers stick to the surface (many uncured components remain, making it unusable as a cured film).
  • the surface smoothness of Cured Dental Materials was visually observed to determine whether the hardenable dental materials were smooth or smooth.
  • the surface smoothness was evaluated according to the following criteria. ⁇ : The surface is smooth and glossy. ⁇ : The surface is almost smooth, and slightly cloudy or slight unevenness is observed. ⁇ : The entire surface is cloudy, and some unevenness and granules are observed. ⁇ : The entire surface is cloudy and covered with particles.
  • Knoop hardness is 200KHN or more (equivalent to permanent tooth enamel).
  • Knoop hardness is 70 KHN or more and less than 200 KHN (equivalent to dentin).
  • Knoop hardness is less than 70 KHN.
  • Measurement could not be performed because it was not cured.
  • bonding strength (dentin bonding strength) of cured dental materials
  • a bovine lower forehead anterior tooth was polished with #1000 water-resistant abrasive paper under water injection, a flat dentin surface for bonding was carved out, and compressed air was blown for 10 seconds. After drying, tape with holes of 3 mm in diameter was attached to set the surface to be adhered. Thereafter, an adhesive test piece was prepared by a known method (see the method described in JP-A No. 2010-208964). The adhesive test pieces were immersed in water at 37°C for 24 hours, and then the tensile adhesive strength was measured using an Instron universal testing machine (crosshead speed 2 mm/min). The adhesive strength between the texture and dentin was used.
  • the tensile adhesive strength value is the average value of five test pieces.
  • ⁇ Bond strength between enamel and dentin is both 20 MPa or more.
  • ⁇ The adhesive strength between enamel and dentin is 20 Mpa or more for only one of them.
  • Bond strength between enamel and dentin is both 7 MPa or more.
  • ⁇ The adhesive strength between enamel and dentin is less than 7 MPa.
  • the hardenable dental materials of Examples simultaneously contain (meth)acrylamide (A) and a polymerizable compound (B), have excellent solubility or dispersibility, and have good hardenability. was high. Furthermore, the cured dental materials obtained in the examples had good hardness, surface smoothness, and adhesive strength. On the other hand, the hardenable dental material of the comparative example does not contain A and B at the same time, has low solubility or dispersibility, cannot sufficiently harden, and has low hardness and surface smoothness of the obtained hardened product. Adhesive strength was insufficient.
  • Examples 73 to 77 and Comparative Examples 27 and 28 (Preparation and evaluation of curable decorative coating agent)
  • the curable composition obtained in Table 1, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photopolymerization initiator (C) and other components were weighed at the mass ratio shown in Table 12, The mixture was mixed at 35° C. for 1 hour to prepare curable decorative coating agents of Examples and Comparative Examples.
  • a laminate was produced by the following decorating process, and the physical properties of the laminate were evaluated.
  • the obtained decorative coating agent was applied onto a 180 ⁇ m thick PC film (“Panlite PC-2151” manufactured by Teijin) using a bar coater (No. 6), and the film thickness after drying was 5 ⁇ m. After coating, heat at 80°C for 3 minutes, and irradiate with ultraviolet light (I-Graphics inverter conveyor device similar to the above, metal halide lamp similar to the above, ultraviolet illuminance: 700 mW/cm 2 , cumulative light amount: 1000 mJ/cm 2 ) The coating film was cured to obtain a laminate having a hard coat layer. The obtained laminate was cut out, and the surface tack resistance, surface hardness, and scratch resistance of the hard coat layer of the laminate, and the elongation and bending resistance of the laminate were evaluated by the following methods. The results are shown in Table 12.
  • the obtained laminate was cut to 50 mm in length and 15 mm in width, fixed in Tensilon universal testing machine RTA-100 (manufactured by Orientec) with a distance between chucks of 25 mm, and set at a temperature of 150°C.
  • the test piece was pulled in one direction at a speed of 250 mm/min in a heated oven while visually observing the appearance, and the length (mm) of the test piece was measured when cracking or whitening occurred in the coating layer.
  • the elongation rate was calculated by the method described below, and evaluated using the machine gun described below.
  • Elongation rate (%) (specimen length after test/25) x 100% ⁇ : Elongation rate is 200% or more ⁇ : Elongation rate is 150 or more and less than 200% ⁇ : Elongation rate is 110% or more and less than 150% ⁇ : Elongation rate is less than 110%
  • the hard coat layer of the laminate was scratched with a pencil at an angle of 45° for about 10 mm in accordance with JIS K 5600, and then the surface hardness of the laminate was scratched to the hardest level that would not cause any scratches on the surface of the laminate.
  • the surface hardness of the pencil was evaluated according to the following criteria. ⁇ : Pencil hardness was 2H or more. ⁇ : Pencil hardness was HB to H. ⁇ : Pencil hardness was 3B to B. ⁇ : Pencil hardness was 4B or less.
  • the curable decorative coating agent of the example contains a polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), and is applied to the surface of a general-purpose plastic substrate.
  • a laminate having a decorative coat layer (decorative coat film) could be easily obtained.
  • the surface of the obtained laminate (coated surface such as hard coat) had tack resistance, high hardness and scratch resistance, and the obtained laminate had good bending resistance.
  • similar decorative performance was not confirmed for the curable decorative coating agent of the comparative example.
  • the decorative coating agent of the present disclosure is suitably used in a wide variety of decorative moldings, decorative processing, and decorative printing such as decorative films, decorative sheets, and decorative coatings.
  • the absolute value of the difference between the solubility parameter (SP value) of the polyfunctional (meth)acrylamide (A) and the solubility parameter (SP value) of the polymerizable compound (B) is 3.0 (cal/cm 3 )
  • R 1 represents a hydrogen atom or a methyl group, and may be the same or different.
  • R 2 and R 3 are both divalent chain carbonized carbon atoms having 3 carbon atoms. It represents a hydrogen group, and may have a linear or branched structure, and may be the same or different.
  • R 4 represents a hydrogen atom or a chain hydrocarbon group having 1 to 2 carbon atoms.
  • n is an integer from 1 to 70
  • x1 and z1 are each independently an integer from 1 to 10
  • y1 is an integer from 1 to 40
  • m is an integer of 0 or 1.
  • the polymerizable compound (B) contains a (meth)acrylate group, (meth)acrylamide group, vinyl group, vinyl ether group, methyl vinyl ether group, allyl group, (meth)allyl ether group, maleimide group, ⁇
  • the polymerizable compound (B) contains a monofunctional polymerizable compound (b1) and/or a polyfunctional polymerizable compound (b2), and the content of (b1) with respect to the total mass of the curable composition is The curable composition according to any one of (1) to (8) above, wherein the content of (b2) is 5 to 80% by mass and 0 to 40% by mass. (10) Further contains a polymerizable polymerization initiator (C) (excluding (A) and (B)), and the content of (C) is 0.1 to 20 mass based on the total mass of the curable composition. % of the curable composition according to any one of (1) to (9) above.
  • the curable composition of the present disclosure contains a polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), where (A) is amphiphilic and contains a wide variety of ( B) can be mixed in a wide range of proportions.
  • polymerizable polymerization initiators, polymerizable compounds, non-polymerizable components, additives, etc. other than (A) and (B), and the result is a general-purpose product. Suitable for use in various special coatings, adhesives, inks, water-based inks, three-dimensional modeling inks, water-based paints, sealants, nail cosmetics, dental materials, decorative coatings, etc. be able to.

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PCT/JP2023/012610 2022-03-30 2023-03-28 非水溶性多官能（メタ）アクリルアミド含有の硬化性組成物 Ceased WO2023190562A1 (ja)

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CN202380041134.5A CN119234005A (zh) 2022-03-30 2023-03-28 含有非水溶性的多官能（甲基）丙烯酰胺的固化性组合物
KR1020247035812A KR20240169052A (ko) 2022-03-30 2023-03-28 비수용성 다관능 (메트)아크릴아미드 함유의 경화성 조성물
EP23780571.8A EP4506387A4 (en) 2022-03-30 2023-03-28 HARDENING COMPOSITION CONTAINING A WATER-INSOLUBLE MULTIFUNCTIONAL (METH)ACRYLAMIDE
US18/852,127 US20250206865A1 (en) 2022-03-30 2023-03-28 Curable composition containing water-insoluble polyfunctional (meth)acrylamide
JP2024512594A JP7679126B2 (ja) 2022-03-30 2023-03-28 非水溶性多官能（メタ）アクリルアミド含有の硬化性組成物
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JP7809861B1 (ja) * 2025-05-22 2026-02-02 第一工業製薬株式会社 フィルム塗料用組成物、硬化物およびフィルム

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JP2010208964A (ja) 2009-03-09 2010-09-24 Tokuyama Dental Corp 歯科用光硬化性材料
WO2013008626A1 (ja) * 2011-07-08 2013-01-17 富士フイルム株式会社 インク組成物及び画像形成方法
JP2013043946A (ja) * 2011-08-24 2013-03-04 Fujifilm Corp インク組成物、インクセット、及び画像形成方法
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WO2025159133A1 (ja) * 2024-01-23 2025-07-31 積水フーラー株式会社 活性エネルギー線硬化型樹脂組成物
JP7809861B1 (ja) * 2025-05-22 2026-02-02 第一工業製薬株式会社 フィルム塗料用組成物、硬化物およびフィルム

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