WO2024095637A1 - Composition durcissable par rayons actiniques et objet durci - Google Patents

Composition durcissable par rayons actiniques et objet durci Download PDF

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WO2024095637A1
WO2024095637A1 PCT/JP2023/034725 JP2023034725W WO2024095637A1 WO 2024095637 A1 WO2024095637 A1 WO 2024095637A1 JP 2023034725 W JP2023034725 W JP 2023034725W WO 2024095637 A1 WO2024095637 A1 WO 2024095637A1
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meth
acrylate
monofunctional monomer
acrylamide
curable composition
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PCT/JP2023/034725
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English (en)
Japanese (ja)
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俊貴 児島
和哉 前田
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三洋化成工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G

Definitions

  • the present invention relates to an active energy ray-curable composition and a cured product.
  • the object of the present invention is to provide an active energy ray-curable composition that gives a cured product that is highly flexible and stretchable.
  • the present invention provides an active energy ray-curable composition containing a monofunctional monomer (A), a polyfunctional (meth)acrylate (C) having a number average molecular weight of 500 to 40,000, and a photopolymerization initiator (D), wherein the monofunctional monomer (A) contains a monofunctional monomer (A1) having a homopolymer glass transition temperature of less than 25° C. and a monofunctional monomer (A2) having a homopolymer glass transition temperature of 25° C.
  • the content of the monofunctional monomer (A) is 10 to 75% by weight
  • the content of the polyfunctional (meth)acrylate (C) is 25 to 90% by weight
  • the content of the photopolymerization initiator (D) is 0.1 to 20% by weight, based on the total weight of the monofunctional monomer (A) and the polyfunctional (meth)acrylate (C), and the molecular weight between crosslinking points is 1,000 to 25,000; and a cured product obtained by curing the active energy ray-curable composition.
  • the active energy ray-curable composition of the present invention has the effect of producing a cured product that is highly flexible and stretchable.
  • the active energy ray-curable composition of the present invention is an active energy ray-curable composition that contains a monofunctional monomer (A), a polyfunctional (meth)acrylate (C) having a number average molecular weight of 500 to 40,000, and a photopolymerization initiator (D).
  • A monofunctional monomer
  • C polyfunctional (meth)acrylate
  • D photopolymerization initiator
  • (meth)acrylate means “methacrylate or acrylate”
  • (meth)acrylic means “methacrylic or acrylic”
  • (meth)acryloyl means “methacryloyl or acryloyl”.
  • the essential components of the active energy ray-curable composition of the present invention the monofunctional monomer (A), the polyfunctional (meth)acrylate (C) having a number average molecular weight of 500 to 40,000, and the photopolymerization initiator (D), are described below in order.
  • the monofunctional monomer (A) contains a monofunctional monomer (A1) whose homopolymer has a glass transition temperature of less than 25°C and a monofunctional monomer (A2) whose homopolymer has a glass transition temperature of 25°C or higher.
  • the chemical structure of the monofunctional monomer (A1) having a homopolymer glass transition temperature of less than 25°C is not particularly limited as long as the homopolymer has a glass transition temperature of less than 25°C.
  • the glass transition temperature of a homopolymer refers to the temperature at which the loss tangent (tan ⁇ ) is maximum when the dynamic viscoelasticity of the polymer obtained by homopolymerizing the monofunctional monomer using the method described below is measured using the method described below.
  • the laminate of (2) is irradiated with 1000 mJ/cm2 at an illuminance of 1500 mW/cm2 (UV- A ) using an ultraviolet irradiation device (e.g., VPS/I600 manufactured by Fusion UV Systems Japan, lamp: D bulb) in an environment of 25 ° C.
  • the laminate of (2) is then turned over and irradiated from the other side with 1000 mJ/ cm2 to cure the composition.
  • the hardened sample of (3) is cut into a test piece having a length of 40 mm, a width of 5 mm, and a thickness of 1 mm.
  • ⁇ Dynamic viscoelasticity measurement method> Using this test piece, the dynamic viscoelasticity is measured under the following conditions using a dynamic viscoelasticity measuring device (eg, Rheogel-E4000, manufactured by UBM). Measurement mode: temperature dependence, measurement temperature range: -80°C to 200°C, frequency: 10 Hz, heating rate: 4°C/min, distortion waveform: sine wave, measurement jig: tensile.
  • the temperature at which the ratio (tan ⁇ ) of the loss modulus E" to the storage modulus E' in the obtained spectrum is maximum is defined as the glass transition temperature (Tg).
  • the monofunctional monomer (A1) having a homopolymer glass transition temperature of less than 25°C is preferably at least one selected from the group consisting of monofunctional (meth)acrylates (E) having a linear or branched alkyl group with 10 to 22 carbon atoms, monofunctional urethane (meth)acrylates (F) and other monofunctional (meth)acrylates (G).
  • Examples of monofunctional (meth)acrylates (E) having a straight-chain or branched alkyl group having 10 to 22 carbon atoms include decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, and behenyl (meth)acrylate.
  • These (meth)acrylates can be easily produced by direct esterification or transesterification of (meth)acrylic acid or methyl (meth)acrylate with natural or synthetic alcohol.
  • the alkyl group will be straight-chained and have an even carbon number. If a synthetic alcohol is used, for example, Dobanol (manufactured by Mitsubishi Chemical Corporation), the alkyl group will be a mixture of straight-chain and branched, and the number of carbon atoms will be a mixture of odd and even. If Diadol (manufactured by Mitsubishi Chemical Corporation) is used, the alkyl group will be a mixture of straight-chain and branched, and the number of carbon atoms will be only odd. In the present invention, these monofunctional (meth)acrylates (E) having a linear or branched alkyl group having 10 to 22 carbon atoms may be used alone or in combination of two or more kinds.
  • these monofunctional (meth)acrylates (E) having a linear or branched alkyl group having 10 to 22 carbon atoms may be used alone or in combination of two or more kinds.
  • lauryl (meth)acrylate, isodecyl (meth)acrylate, and isostearyl (meth)acrylate are preferred from the viewpoints of the elongation rate of the cured product, the strength of the cured product, and the adhesion to the substrate.
  • the monofunctional urethane (meth)acrylate (F) in the present invention means a monomer having one (meth)acryloyl group and at least one urethane group in the molecule. From the viewpoint of viscosity, a monomer having one (meth)acryloyl group and one urethane group is preferred.
  • Examples of the monofunctional urethane (meth)acrylate (F) include a reaction product of a monofunctional (meth)acrylate having a hydroxyl group (a) and an organic monoisocyanate compound (b).
  • Examples of the monofunctional (meth)acrylate (a) having a hydroxyl group include hydroxyalkyl (meth)acrylates (2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 1,4-cyclohexanedimethanol monoacrylate).
  • the hydroxyl group-containing monofunctional (meth)acrylate (a) may be used alone or in combination of two or more kinds.
  • Examples of the organic monoisocyanate compound (b) include an aliphatic monoisocyanate compound (b1), an alicyclic monoisocyanate compound (b2), and an aromatic monoisocyanate compound (b3).
  • Examples of the aliphatic monoisocyanate compound (b1) include methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, hexyl isocyanate, octyl isocyanate, lauryl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, and octadecyl isocyanate.
  • Examples of the alicyclic monoisocyanate compound (b2) include cyclohexyl isocyanate.
  • Examples of the aromatic monoisocyanate compound (b3) include phenyl isocyanate and tolylene isocyanate.
  • the organic monoisocyanate compound (b) may be used alone or in combination of two or more kinds.
  • organic monoisocyanate compounds (b) from the viewpoint of the elongation rate and viscosity of the cured product, the aliphatic monoisocyanate compound (b1) and the alicyclic monoisocyanate compound (b2) are preferred, the aliphatic monoisocyanate compound (b1) is more preferred, and methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, and hexyl isocyanate are particularly preferred.
  • the monofunctional urethane (meth)acrylate (F) a reaction product obtained by subjecting a monofunctional (meth)acrylate having a hydroxyl group (a) and an organic monoisocyanate compound (b) to a urethane reaction by a known method can be used.
  • products available on the market may be used, and examples of commercially available products include Viscoat #216 (2-[(butylamino)carbonyl]oxyethyl acrylate: manufactured by Osaka Organic Chemical Industry Co., Ltd.), Etermer EM2080 (manufactured by Choko Materials Co., Ltd.), and Genomer 1122 (manufactured by RAHN).
  • Other monofunctional (meth)acrylates (G) include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-ethylhexyl diglycol (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, 2,2,2-tetrafluoroethyl (meth)acrylate, 1H,1H,2H,2H-perf
  • the acrylates include fluorodecyl (meth)acrylate, 4-butylphenyl (meth)acrylate,
  • the chemical structure of the monofunctional monomer (A2) having a homopolymer glass transition temperature of 25°C or higher is not particularly limited as long as the homopolymer glass transition temperature is 25°C or higher.
  • Examples of the monofunctional monomer (A2) having a homopolymer glass transition temperature of 25°C or higher include (meth)acrylates (H) having an alicyclic skeleton, monofunctional monomers (I) having a nitrogen atom in the molecule, and other monofunctional (meth)acrylates (J), and from the viewpoint of curability, monofunctional monomers (I) having a nitrogen atom in the molecule are preferred.
  • Examples of the (meth)acrylate (H) having an alicyclic skeleton include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 1-ethylcyclohexyl (meth)acrylate, and adamantyl (meth)acrylate.
  • these (meth)acrylates (H) having an alicyclic skeleton may be used alone or in combination of two or more kinds.
  • (meth)acrylates (H) having an alicyclic skeleton isobornyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, and 1-ethylcyclohexyl (meth)acrylate are preferred from the viewpoint of the elongation rate and strength of the cured product.
  • Examples of the monofunctional monomer (I) having a nitrogen atom in the molecule include N-substituted vinyl monomers and N-substituted (meth)acrylamides, with N-substituted (meth)acrylamides being preferred from the viewpoint of curability.
  • Examples of N-substituted vinyl monomers include N-vinylpyrrolidone, N-vinylcarbazole, N-vinylcaprolactam, N-vinylimidazole, and vinylmethyloxazolidinone.
  • the N-substituted (meth)acrylamide means a (meth)acrylamide in which one or two hydrogen atoms of the amino group are substituted with a substituent such as a hydrocarbon group.
  • N-substituted (meth)acrylamide examples include linear amides (I1) having an N-(meth)acryloyl group, cyclic amides (I2) having an N-(meth)acryloyl group, and diacetone acrylamide.
  • chain amides (I1) having an N-(meth)acryloyl group examples include N-alkyl(meth)acrylamides (I11), N,N-dialkyl(meth)acrylamides (I12), N-hydroxyalkyl(meth)acrylamides (I13), N-alkoxyalkyl(meth)acrylamides (I14), and N-alkyl-N-alkoxy(meth)acrylamides (I15).
  • N-alkyl(meth)acrylamides (I11) include N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-dodecyl(meth)acrylamide, and N-octadecyl(meth)acrylamide.
  • N,N-dialkyl(meth)acrylamide (I12) includes N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-dibutyl(meth)acrylamide, N,N-diisobutyl(meth)acrylamide, N,N-di-tert-butyl(meth)acrylamide, N,N-diheptyl(meth)acrylamide, N,N-dioctyl(meth)acrylamide, N,N-di-tert-octyl(meth)acrylamide, N,N-didodecyl(meth)acrylamide, and N,N-dioctadecyl(meth)acrylamide.
  • the two alkyl groups in N,N-dialkyl(meth)acrylamide (I12) may be the same or different, and the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 8, and particularly preferably 1 to 4, from the viewpoint of curability.
  • N-hydroxyalkyl(meth)acrylamide (I13) includes N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, and N-(3-hydroxypropyl)(meth)acrylamide. From the viewpoint of curability, the number of carbon atoms in the alkyl group of N-hydroxyalkyl(meth)acrylamide (I13) is preferably 1 to 20, more preferably 1 to 8, and particularly preferably 1 to 4.
  • N-alkoxyalkyl(meth)acrylamide (I14) includes N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-propoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide, N-methoxypropyl(meth)acrylamide, N-ethoxypropyl(meth)acrylamide, N-methoxybutyl(meth)acrylamide, and N-ethoxybutyl(meth)acrylamide.
  • the number of carbon atoms in the alkoxyalkyl group of N-alkoxyalkyl(meth)acrylamide (I14) is preferably 2 to 20, more preferably 2 to 8, and particularly preferably 2 to 6.
  • the number of carbon atoms in the alkyl group of the alkoxyalkyl group is preferably 1 to 4, more preferably 1 to 3, and particularly preferably 1 to 2.
  • N-alkyl-N-alkoxy(meth)acrylamide (I15) includes N-methyl-N-methoxy(meth)acrylamide, N-methyl-N-ethoxy(meth)acrylamide, N-methyl-N-propoxy(meth)acrylamide, N-methyl-N-butoxy(meth)acrylamide, N-ethyl-N-methoxy(meth)acrylamide, N-ethyl-N-ethoxy(meth)acrylamide, N-ethyl-N-butoxy(meth)acrylamide, N-propyl-N-methoxy(meth)acrylamide, N-propyl-N-ethoxy(meth)acrylamide, N-butyl-N-methoxy(meth)acrylamide, and N-butyl-N-ethoxy(meth)acrylamide.
  • Examples of the cyclic amide (I2) having an N-(meth)acryloyl group include N-(meth)acryloylmorpholine, N-(meth)acryloylthiomorpholine, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, and N-(meth)acryloylpiperidine.
  • the number of carbon atoms in the cyclic amide having an N-(meth)acryloyl group is preferably 7 to 20, more preferably 7 to 18, and particularly preferably 7 to 16.
  • these N-substituted (meth)acrylamides may be used alone or in combination of two or more.
  • N-substituted (meth)acrylamides from the viewpoints of viscosity, curability, and elongation of the cured product, preferred are N,N-dialkyl(meth)acrylamides (I12), N-alkoxyalkyl(meth)acrylamides (I14), and cyclic amides having an N-(meth)acryloyl group (I2), more preferred are N,N-dialkyl(meth)acrylamides (I12) and cyclic amides having an N-(meth)acryloyl group (I2), and particularly preferred are N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and N-(meth)acryloylmorpholine.
  • Other monofunctional (meth)acrylates (J) include cyclic trimethylolpropane formal (meth)acrylate, 2-phenoxyethyl acrylate, etc.
  • a bifunctional (meth)acrylate having a number average molecular weight of 500 to 40,000 is preferred, and examples of such a bifunctional (meth)acrylate include the bifunctional (meth)acrylate (K) represented by the general formula (1) and other bifunctional (meth)acrylates (L).
  • the bifunctional (meth)acrylate (K) represented by the general formula (1) is as follows. CH 2 ⁇ CXCO-O-(R—O) n -COCX ⁇ CH 2 (1) [In the general formula (1), n is an integer of 2 to 15, R is an alkylene group having 2 to 6 carbon atoms (when there are multiple R in one molecule, each R is independently an alkylene group having 2 to 6 carbon atoms), and each X is independently a hydrogen atom or a methyl group.]
  • R represents an alkylene group having 2 to 6 carbon atoms, and specific examples thereof include an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,2-butylene group, a 1,3-butylene group, and a 1,4-butylene group. From the viewpoint of hardness of the cured product, R preferably has 2 to 3 carbon atoms, and more preferably is an ethylene group or a 1,2-propylene group. n is an integer of 2 or more and 15 or less, and is preferably an integer of 7 or more and 15 or less from the viewpoint of low outgassing properties and bending resistance.
  • n means the number of repeats of the alkyleneoxy group. The same applies hereinafter.
  • These difunctional (meth)acrylates (K) can be used alone or in combination of two or more.
  • Other bifunctional (meth)acrylates (L) include di(meth)acrylates (L1) of 4-25 moles of alkylene oxide (alkylene group has 2-4 carbon atoms) adducts of dihydric phenol compounds, diesters of (meth)acrylic acid and 1-15 moles of alkylene oxide (alkylene group has 2-4 carbon atoms) adducts of dihydric alcohols having 2-30 carbon atoms, diesters of diglycidyl ether and (meth)acrylic acid, and di(meth)acrylates of ethylene oxide adducts of fluorene, silicone diacrylates (L2), urethane diacrylates (L3), etc.
  • Di(meth)acrylates (L1) of 4 to 25 moles of alkylene oxide (alkylene group carbon number 2 to 4) adducts of dihydric phenol compounds include di(meth)acrylates of alkylene oxide adducts of dihydric phenol compounds [monocyclic phenols (catechol, resorcinol, hydroquinone, etc.), condensed polycyclic phenols (dihydroxynaphthalene, etc.), bisphenol compounds (bisphenol A, bisphenol F, bisphenol S, etc.)], such as di(meth)acrylates of ethylene oxide (hereinafter, ethylene oxide may be abbreviated as EO) adducts of catechol, di(meth)acrylates of propylene oxide (hereinafter, 1,2- or 1,3-propylene oxide may be abbreviated as PO) adducts of dihydroxynaphthalene, and di(meth)acrylates of EO adducts of bisphenol A.
  • silicone diacrylate (L2) examples include EBECRYL350 and EBECRYL1360.
  • Urethane diacrylate (L3) is a urethane (meth)acrylate containing polyol (m), polyisocyanate (n), and active hydrogen group-containing (meth)acrylate (c) as constituent raw materials.
  • Polyols (m) include linear aliphatic polyols (m1) having 1 to 20 carbon atoms, alicyclic polyols (m2) having 6 to 20 carbon atoms, and aromatic polyols (m3) having 6 to 20 carbon atoms, as well as their alkylene oxide adducts [ethylene oxide (EO), 1,2- or 1,3-propylene oxide (PO), and 1,2-, 1,3-, 1,4- or 2,3-butylene oxide, etc.].
  • EO ethylene oxide
  • PO 1,2- or 1,3-propylene oxide
  • 2,3-butylene oxide 1,3-butylene oxide
  • linear aliphatic polyol (m1) examples include linear aliphatic diols having 1 to 20 carbon atoms (ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, etc.), branched aliphatic diols (1,2-propanediol, 1,2-, 1,3- or 2,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, etc.), and linear alipha
  • Examples of alicyclic polyols (m2) having 6 to 20 carbon atoms include 1,2-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, 1,4-bis(hydroxymethyl)cyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane, and 1,3,5-cyclohexanetriol.
  • aromatic polyols (m3) having 6 to 20 carbon atoms include resorcinol, hydroquinone, naphthalene diol, and bisphenols (such as bisphenol A, bisphenol F, and bisphenol S).
  • the number of moles of alkylene oxide added is preferably 1 to 50 moles, more preferably 4 to 30 moles, from the viewpoint of the elongation of the cured product.
  • polys (m) from the viewpoint of elongation of the cured product, preferred are alkylene oxide adducts of the above-mentioned chain aliphatic polyols (m1), more preferred are 1,4-butylene oxide adducts of the aliphatic polyols (m1), and particularly preferred is poly-1,4-butylene oxide (polytetramethylene glycol).
  • the polyol (m) may be used alone or in combination of two or more kinds.
  • polyisocyanates (n) examples include linear aliphatic polyisocyanates (n1) having 4 to 20 carbon atoms, alicyclic polyisocyanates (n2) having 6 to 22 carbon atoms, and aromatic polyisocyanates (n3) having 8 to 22 carbon atoms.
  • chain aliphatic polyisocyanates (n1) having 4 to 20 carbon atoms examples include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.
  • alicyclic polyisocyanates (n2) having 6 to 22 carbon atoms include cyclohexane-1,3-diylbismethylene diisocyanate, isophorone diisocyanate (IPDI), 2,4- or 2,6-methylcyclohexane diisocyanate (hydrogenated TDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI; hereafter sometimes referred to as MDIH), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexylene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, and dimer acid diisocyanate.
  • IPDI isophorone diisocyanate
  • TDI 2,4- or 2,6-methylcyclohexane diisocyanate
  • MDIH di
  • Aromatic polyisocyanates (n3) having 8 to 22 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'- or 2,4'-diphenylmethane diisocyanate (MDI), m- or p-isocyanatophenylsulfonyl isocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, m- or p-xylylene diisocyanate (XDI), and ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diis
  • polyisocyanates (n) from the viewpoint of elongation and light resistance of the cured product, preferred are alicyclic polyisocyanates (n2) having 6 to 22 carbon atoms and aromatic polyisocyanates (n3) having 8 to 22 carbon atoms, more preferred are alicyclic polyisocyanates having 6 to 20 carbon atoms and aromatic polyisocyanates having 8 to 20 carbon atoms, particularly preferred are cyclohexane-1,3-diylbismethylene diisocyanate, IPDI, XDI, TMXDI, MDI and TDI, and most preferred is IPDI.
  • the polyisocyanate (n) may be used alone or in combination of two or more kinds.
  • Examples of the active hydrogen group-containing (meth)acrylate (c) include hydroxyl group-containing (meth)acrylate (c1), amino group-containing (meth)acrylate (c2), and carboxyl group-containing (meth)acrylate (c3), etc. Among these, preferred is the hydroxyl group-containing (meth)acrylate.
  • Examples of the hydroxyl group-containing (meth)acrylate (c1) include hydroxyalkyl (meth)acrylate (c11) and polyalkylene glycol mono(meth)acrylate (c12).
  • Hydroxyalkyl (meth)acrylates (c11) preferably include hydroxyalkyl (meth)acrylates having 4 to 20 carbon atoms, and specific examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate.
  • polyalkylene glycol mono(meth)acrylates (c12) examples include polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate.
  • amino group-containing (meth)acrylates (c2) include monoalkyl (carbon number 1-4) aminoalkyl (carbon number 2-6) (meth)acrylates ⁇ aminoethyl, aminopropyl, methylaminoethyl, ethylaminoethyl, butylaminoethyl, or methylaminopropyl (meth)acrylate ⁇ and dialkyl (carbon number 1-4) aminoalkyl (carbon number 2-6) (meth)acrylates ⁇ dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, etc. ⁇ .
  • carboxyl group-containing (meth)acrylates (c3) examples include 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl phthalate, and 2-(meth)acryloyloxyethyl hexahydrophthalate.
  • hydroxyl group-containing (meth)acrylates (c) from the viewpoints of reactivity in the urethane reaction and elongation of the cured product, preferred are hydroxyl group-containing (meth)acrylates (c1), more preferred are hydroxyl group-containing monofunctional (meth)acrylates, particularly preferred are hydroxyalkyl (meth)acrylates (c11), and most preferred is 2-hydroxyethyl (meth)acrylate.
  • the active hydrogen group-containing (meth)acrylate (c) may be used alone or in combination of two or more kinds.
  • the urethane diacrylate (L3) may be used alone or in combination of two or more kinds.
  • the molar ratio of the isocyanate groups in the polyisocyanate (n) to the active hydrogen groups in the polyol (m) and active hydrogen group-containing (meth)acrylate (c) [isocyanate groups in (n)/total of active hydrogen groups in (m) and active hydrogen groups in (c)] is not particularly limited, but is preferably 1/0.5 to 1/10, more preferably 1/0.7 to 1/5, and particularly preferably 1/1 to 1/2, from the viewpoint of storage stability.
  • the urethane diacrylate (L3) in the present invention can be produced by reacting a polyol (m), a polyisocyanate (n) and an active hydrogen group-containing (meth)acrylate (c) by a known method.
  • a polyol (m) and a polyisocyanate (n) it is preferable to produce the urethane prepolymer having two or more isocyanate groups by subjecting a polyol (m) and a polyisocyanate (n) to a polyaddition reaction, and then subjecting the urethane prepolymer to an addition reaction with an active hydrogen group-containing (meth)acrylate (c).
  • a urethanization catalyst may be used.
  • the urethanization catalyst include metal compounds (organobismuth compounds, organotin compounds, organotitanium compounds, etc.) and quaternary ammonium salts.
  • the polyfunctional (meth)acrylate (C) having a number average molecular weight of 500 to 40,000 may be a trifunctional or higher functional (meth)acrylate, such as urethane tetraacrylate.
  • the photopolymerization initiator (D) is not limited as long as it generates radicals, ions, and the like when irradiated with active energy rays, thereby initiating a polymerization reaction of the monomers.
  • a photopolymerization initiator that generates radicals when irradiated with active energy rays can be preferably used.
  • Preferred examples of the photopolymerization initiator (D) include acylphosphine oxide compounds (D1), ⁇ -hydroxyalkylphenone compounds (D2), ⁇ -aminoalkylphenone compounds (D3), ketal compounds (D4), benzoylformate compounds (D5), thioxanthone compounds (D6), benzophenone compounds (D7), and oxime ester compounds (D8).
  • Examples of the acylphosphine oxide compound (D1) include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and ethyl 2,4,6-trimethylbenzoylphenylphosphinate.
  • ⁇ -Hydroxyalkylphenone compounds (D2) include 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one.
  • Examples of ⁇ -aminoalkylphenone compounds (D3) include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-butan-1-one, and 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-butan-1-one.
  • ketal compounds (D4) include benzyl dimethyl ketal.
  • benzoyl formate compounds (D5) examples include methyl benzoyl formate, etc.
  • Thioxanthone compounds (D6) include 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone.
  • benzophenone compounds (D7) include benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-bismethylaminobenzophenone.
  • Examples of the oxime ester compound (D8) include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) and 1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxime).
  • these photopolymerization initiators (D) may be used alone or in combination of two or more.
  • the acylphosphine oxide compounds (D1) and ⁇ -hydroxyalkylphenone compounds (D2) are preferred from the viewpoints of curability and transmittance of the cured product, with the acylphosphine oxide compounds (D1) being more preferred, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide being particularly preferred.
  • the content of monofunctional monomer (A) in the present invention is 10 to 75% by weight based on the total weight of monofunctional monomer (A) and polyfunctional (meth)acrylate (C). If the content of monofunctional monomer (A) is less than 10% by weight, the elongation of the cured product will be insufficient, and if it exceeds 75% by weight, the elasticity of the cured product will be insufficient.
  • the content of the monofunctional monomer (A1) having a homopolymer glass transition temperature of less than 25° C. is preferably 5 to 30% by weight, more preferably 5 to 25% by weight, based on the total content of the monofunctional monomer (A) and the polyfunctional (meth)acrylate (C), from the viewpoints of curability and flexibility.
  • the content of the monofunctional monomer (A2) having a homopolymer glass transition temperature of 25° C. or higher is preferably 5 to 70% by weight based on the total weight of the monofunctional monomer (A) and the polyfunctional (meth)acrylate (C) from the viewpoints of curability and flexibility.
  • the content of the polyfunctional (meth)acrylate (C) in the present invention is 25 to 90% by weight based on the total weight of the monofunctional monomer (A) and the polyfunctional (meth)acrylate (C). If the content of the polyfunctional (meth)acrylate (C) is less than 25% by weight, the elasticity of the cured product is insufficient, and if it exceeds 90% by weight, the elongation percentage is insufficient.
  • the content of the photopolymerization initiator (D) in the present invention is 0.1 to 20% by weight, preferably 2 to 20% by weight, more preferably 2 to 18% by weight, and even more preferably 5 to 15% by weight, based on the total weight of the monofunctional monomer (A) and the polyfunctional (meth)acrylate (C). If the content of the photopolymerization initiator (D) is less than 0.1% by weight, the curability will be insufficient, and if it exceeds 20% by weight, the transmittance of the cured product will be insufficient.
  • the molecular weight between crosslinking points in the present invention is 1000 to 25000.
  • the molecular weight between crosslinking points is expressed as [Mc] (g/mol), and from the viewpoint of flexibility and restorability, it is preferably 1200 to 20000 g/mol, more preferably 1300 to 15000.
  • the active energy ray-curable composition of the present invention may contain another monomer (M) other than the monofunctional monomer (A) and the polyfunctional (meth)acrylate (C) having a number average molecular weight of 500 to 40,000, within a range that does not impair the effects of the present invention.
  • the other monomer (M) include difunctional or higher functional (meth)acrylates other than the polyfunctional (meth)acrylate (C) [for example, difunctional (meth)acrylates (N) (excluding those corresponding to the polyfunctional (meth)acrylate (C)), trifunctional or higher functional (meth)acrylates (O), and (meth)acrylates having a phosphate group (P), etc.].
  • the storage stability of the active energy ray-curable composition may become insufficient, and therefore it is preferable not to use such a monomer.
  • Examples of the bifunctional (meth)acrylate (N) include polyalkylene glycol (alkylene group having 2 to 4 carbon atoms) di(meth)acrylate (N1), di(meth)acrylate (N2) of an alkylene oxide (alkylene group having 2 to 4 carbon atoms) adduct of a dihydric phenol compound, diester of an alkylene oxide (alkylene group having 2 to 4 carbon atoms) adduct of a polyhydric (preferably dihydric to octahydric) alcohol having 2 to 30 carbon atoms and (meth)acrylic acid, diester of a diglycidyl ether and (meth)acrylic acid, and di(meth)acrylate of an ethylene oxide adduct of fluorene, cyclohexanemethanol di(meth)acrylate, ethoxylated cyclohexanemethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and 1,
  • these bifunctional (meth)acrylates (N) may be used alone or in combination of two or more.
  • trifunctional or higher (meth)acrylates (O) include trifunctional (meth)acrylate monomers and tetrafunctional or higher (meth)acrylate monomers.
  • trifunctional (meth)acrylate monomers include trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane modified with an alkylene oxide having 3 to 4 carbon atoms, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane tri((meth)acryloyloxypropyl)ether, sorbitol tri(meth)acrylate, tri(meth)acrylate of an adduct of pentaerythritol with 1 to 30 moles of an alkylene oxide having 3 to 4 carbon atoms, and ethoxylated glycerin tri(meth)acrylate.
  • tetrafunctional or higher (meth)acrylate monomers include pentaerythritol tetra(meth)acrylate, sorbitol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol propionate tetra(meth)acrylate, tetra(meth)acrylate of an adduct of pentaerythritol with 1 to 11 moles of an alkylene oxide having 3 to 4 carbon atoms, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(me
  • the (meth)acrylate (P) having a phosphate group is not limited as long as it is a phosphate ester having a (meth)acryloyl group, and examples thereof include those having 1 to 3 functional groups in the (meth)acryloyl group.
  • (meth)acrylates (P) having a phosphate group from the viewpoint of metal adhesion, preferred are (meth)acrylates having a phosphate group with a functionality of 1 to 2 (meth)acryloyl groups, and more preferred are 2-(meth)acryloyloxyethyl acid phosphate, bis ⁇ 2-(meth)acryloyloxyethyl ⁇ acid phosphate, and a reaction product of a 6-hexanolide addition polymer of 2-hydroxyethyl methacrylate and phosphoric anhydride.
  • the content of the other monomer (M) is preferably 0 to 20% by weight, more preferably 0 to 10% by weight, based on the total weight of the monofunctional monomer (A) and the polyfunctional (meth)acrylate (C).
  • the total content of the polyfunctional (meth)acrylate (C) and the difunctional or higher (meth)acrylate other than the polyfunctional (meth)acrylate (C) is preferably 50% by weight or less based on the total weight of the monofunctional monomer (A) and the polyfunctional (meth)acrylate (C) from the viewpoint of elongation.
  • the active energy ray-curable composition of the present invention may contain various additives as necessary within the range that does not impair the effects of the present invention.
  • the additives include leveling agents, charge adjusters, light stabilizers, ultraviolet absorbers, surface treatment agents, antioxidants, antiaging agents, crosslinking accelerators, plasticizers, preservatives, pH adjusters, antifoaming agents, and moisturizing agents.
  • the method for producing the active energy ray-curable composition of the present invention is not particularly limited.
  • the active energy ray-curable composition can be produced by stirring and mixing the above-mentioned components in a suitable container such as a glass beaker, a can, or a plastic cup with a stirring rod, a spatula, or the like, or by uniformly mixing the components with a known mixing device (a method using a mechanical stirrer, a magnetic stirrer, or the like, a mixing device equipped with a paddle-shaped stirring spring, a dissolver, a ball mill, a planetary mixer, or the like).
  • a known mixing device a method using a mechanical stirrer, a magnetic stirrer, or the like, a mixing device equipped with a paddle-shaped stirring spring, a dissolver, a ball mill, a planetary mixer, or the like.
  • the active energy ray-curable composition of the present invention is preferably in a liquid state at room temperature, and its viscosity can be measured using an E-type viscosity measuring device [such as "VISCOMETER TV-25L” manufactured by Toki Sangyo Co., Ltd.] and a B-type viscosity measuring device.
  • E-type viscosity measuring device such as "VISCOMETER TV-25L” manufactured by Toki Sangyo Co., Ltd.
  • the active energy ray-curable composition is applied to a substrate by a known method, and then cured by irradiating the composition with active energy rays.
  • the active energy rays in the present invention include ultraviolet rays and electron beams.
  • the active energy rays used for curing the active energy ray-curable composition of the present invention can be adjusted by selecting a photopolymerization initiator.
  • the composition can be photocured by irradiation with active energy rays having a wavelength of 200 to 700 nm, and it is preferable that the composition is cured by irradiation with light (ultraviolet light) having a wavelength of 200 to 400 nm.
  • LED light sources that emit ultraviolet rays include high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, high-power metal halide lamps, etc. (Latest Trends in UV/EB Curing Technology, edited by RadTech Research Group, CMC Publishing, p. 138, 2006) and LEDs. Among them, LEDs consume less power and generate less ozone than other light sources, have low running costs, and are environmentally friendly.
  • an LED light source ultraviolet irradiation device for example, LED light source ultraviolet irradiation device "FJ100 150x20 365, phoseon", manufactured by TECHNOLOGY Co., Ltd.] can be used.
  • the amount of ultraviolet light irradiated when curing the active energy ray-curable composition of the present invention is preferably 10 to 10,000 mJ/cm 2 , more preferably 50 to 5,000 mJ/cm 2 , from the viewpoints of curability and flexibility of the cured product.
  • a known electron beam irradiation device can be used.
  • the irradiation dose of the electron beam is preferably 1 to 10 Mrad from the viewpoints of curability and suppression of deterioration of the cured product.
  • the material to be applied to the active energy ray-curable composition of the present invention may be appropriately selected depending on the application, etc., and organic materials such as plastics and inorganic materials such as metals and glass can be used.
  • organic materials such as plastics and inorganic materials such as metals and glass
  • metals include steel, hot-dip galvanized steel, electrolytic galvanized steel, tinplate, tin-free steel, various other plated or alloy-plated steel, stainless steel, aluminum, gold, platinum, silver, copper, etc.
  • the metals may be those that have been subjected to various surface treatments such as phosphate treatment, chromate treatment, organic phosphate treatment, organic chromate treatment, and heavy metal replacement treatment.
  • plastic materials include polyester resins (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.), acrylic resins (methyl methacrylate copolymers, etc.), triacetyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS) resin, styrene resin, polysulfone resin, polyethersulfone resin, polycarbonate resin, vinyl chloride resin, polymethacrylimide resin, and polyolefin resins (polyethylene, polypropylene, cycloolefin polymer, etc.).
  • Inorganic materials include glass and ceramics. Among these, the active energy ray-curable composition of the present invention has particularly excellent adhesion to metals.
  • the active energy ray-curable composition of the present invention can be applied to a substrate by known coating methods such as spin coating, roll coating, and spray coating, and known printing methods such as lithographic printing, carton printing, metal printing, offset printing, screen printing, and gravure printing.
  • coating methods such as spin coating, roll coating, and spray coating
  • printing methods such as lithographic printing, carton printing, metal printing, offset printing, screen printing, and gravure printing.
  • the composition of the present invention has a low viscosity at room temperature, it can also be applied to inkjet coating (inkjet printing) in which fine droplets are continuously ejected.
  • inkjet printing is capable of precise, high-speed printing using relatively simple equipment, and is therefore suitable for use in the manufacture of display components such as liquid crystal displays and organic EL displays, as well as other electronic and optical components.
  • the active energy ray curable composition of the present invention has a low viscosity, and the cured product of the active energy ray curable composition has excellent elongation and elastic modulus, making it useful as a material for various electronic and optical components, including display components.
  • it can be suitably used for bonding and sealing electronic components such as display components and image sensors, and semiconductor packages. It can also be widely used in various coatings, inks (UV printing inks and UV inkjet printing inks, etc.), paints, etc.
  • the present invention may include the following configurations.
  • An active energy ray-curable composition containing a monofunctional monomer (A), a polyfunctional (meth)acrylate (C) having a number average molecular weight of 500 to 40,000, and a photopolymerization initiator (D), wherein the monofunctional monomer (A) contains a monofunctional monomer (A1) having a homopolymer glass transition temperature of less than 25° C. and a monofunctional monomer (A2) having a homopolymer glass transition temperature of 25° C.
  • the content of the monofunctional monomer (A) is 10 to 75% by weight
  • the content of the polyfunctional (meth)acrylate (C) is 25 to 90% by weight
  • the content of the photopolymerization initiator (D) is 0.1 to 20% by weight, based on the total weight of the monofunctional monomer (A) and the polyfunctional (meth)acrylate (C), and the molecular weight between crosslinking points is 1,000 to 25,000.
  • ⁇ 3> The active energy ray-curable composition according to ⁇ 1> or ⁇ 2>, wherein the monofunctional monomer (A2) is an N-substituted (meth)acrylamide.
  • Examples 1 to 14 and Comparative Examples 1 to 5 ⁇ Preparation of active energy ray-curable composition> (Examples 1 to 14 and Comparative Examples 1 to 5)
  • the monofunctional monomer (A), the polyfunctional (meth)acrylate (C) having a number average molecular weight of 500 to 40,000, the photopolymerization initiator (D), and the other monomer (M) were charged into a glass container and stirred until uniform, thereby obtaining active energy ray-curable compositions of Examples 1 to 14 and Comparative Examples 1 to 5.
  • the raw materials used in Table 1 are as follows: (A1-1): Lauryl acrylate [product name: LA, manufactured by Osaka Organic Chemical Industry Co., Ltd.] (Tg of homopolymer: -30°C) (A1-2): Isostearyl acrylate [product name: ISTA, manufactured by Osaka Organic Chemical Industry Co., Ltd.] (Tg of homopolymer: -15°C) (A1-3): 2-[(butylamino)carbonyl]oxyethyl acrylate [product name: Viscoat #216, manufactured by Osaka Organic Chemical Industry Co., Ltd.] (Tg of homopolymer: 0° C.) (A1-4): Tetrahydrofurfuryl acrylate [product name: Viscoat #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.] (Tg of homopolymer: -12°C) (A2-1): N-acryloylmorpholine [product name: ACMO, manufactured by KJ Chemicals] (Tg of
  • the coating curability was evaluated according to the following criteria.
  • the coating curability is preferably 2 or more, and more preferably 3.
  • the film was exposed to light at an irradiation intensity of 200 mW/cm 2 under a nitrogen atmosphere using an LED light source ultraviolet irradiation device [model number "FJ100 150 ⁇ 20 385", manufactured by phoseon TECHNOLOGY Co., Ltd., irradiation wavelength 385 nm] to prepare an evaluation sample.
  • the exposure amount was 2000 mJ/cm 2 .
  • the prepared evaluation sample was kept at 25° C. for 30 minutes, and the total light transmittance (%) was measured in accordance with JIS K7136: 2000 using a total light transmittance measuring device [trade name "haze-garddual", manufactured by BYK Gardner Co., Ltd.].
  • the total light transmittance is preferably 90% or more.
  • a PET film [product name: Lumirror S, manufactured by Toray Industries, Inc.] was attached to a glass plate [product name: GLASS PLATE, manufactured by AS ONE Corporation, length 200 mm x width 200 mm x thickness 5 mm], and an active energy ray curable composition was applied using an applicator so that the film thickness after curing was 100 ⁇ m.
  • ultraviolet ray irradiation device model number "VPS/I600", manufactured by Fusion UV Systems Co., Ltd.
  • ultraviolet rays were irradiated at 2000 mJ/ cm2 under a nitrogen atmosphere to obtain a PET film covered with a cured product of the active energy ray curable composition.
  • the PET film coated with the above-mentioned cured product was punched out into a dumbbell shape No. 3 in accordance with JIS K 6251:2017, and then the PET film was peeled off to obtain a test specimen for measurement.
  • the elastic modulus is preferably 1000 MPa or less, more preferably 500 MPa or less, and even more preferably 100 MPa or less.
  • the elongation is preferably 50% or more, and more preferably 100% or more.
  • Recovery rate (%) (gauge line distance before test (20 mm))/(gauge line distance after test) ⁇ 100
  • the restoration rate is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more.
  • the average number of adhered grids is preferably 80 or more, more preferably 90 or more, and even more preferably 100.
  • the active energy ray-curable composition of the present invention is excellent in both elongation and elastic modulus, and is therefore useful as a material for various electronic components, including display components such as flexible displays, stretchable devices, and various optical components.
  • display components such as flexible displays, stretchable devices, and various optical components.
  • it can be suitably used for adhesion and sealing of display components, electronic components such as image sensors, semiconductor packages, etc.
  • coatings inks (UV printing inks, UV inkjet printing inks, screen printing inks, etc.), paints, etc.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une composition durcissable par rayons actiniques comprenant des monomères monofonctionnels (A), un (méth)acrylate polyfonctionnel (C) ayant un poids moléculaire moyen en nombre de 500 à 40 000, et un initiateur de photopolymérisation (D), les monomères monofonctionnels (A) comprenant un monomère monofonctionnel (A1), dont un homopolymère a une température de transition vitreuse inférieure à 25 °C, et un monomère monofonctionnel (A2), dont un homopolymère a une température de transition vitreuse de 25 °C ou plus. Par rapport au poids total des monomères monofonctionnels (A) et du (méth)acrylate polyfonctionnel (C), la teneur des monomères monofonctionnels (A) est de 10 à 75 % en poids, la teneur du (méth)acrylate polyfonctionnel (C) est de 25 à 90 % en poids, et la teneur de l'initiateur de photopolymérisation (D) est de 0,1 à 20 % en poids. Le poids moléculaire inter-réticulation est de 1000 à 25 000.
PCT/JP2023/034725 2022-11-04 2023-09-25 Composition durcissable par rayons actiniques et objet durci WO2024095637A1 (fr)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
JP2016204597A (ja) * 2015-04-28 2016-12-08 Ｋｊケミカルズ株式会社 Ｎ−置換（メタ）アクリルアミドを用いた重合性組成物、その重合物及びそれらからなる成形品
JP2017048288A (ja) * 2015-09-01 2017-03-09 Ｋｊケミカルズ株式会社 モデル材用活性エネルギー線硬化性樹脂組成物
JP2021146657A (ja) * 2020-03-23 2021-09-27 株式会社リコー 立体造形用組成物、高分子量体、立体造形物、及び立体造形物の製造方法
JP2022037903A (ja) * 2020-08-25 2022-03-09 三洋化成工業株式会社 活性エネルギー線硬化性組成物及び硬化物
JP2022153309A (ja) * 2021-03-29 2022-10-12 三洋化成工業株式会社 活性エネルギー線硬化性組成物及びその硬化物
JP2022164601A (ja) * 2021-04-16 2022-10-27 三洋化成工業株式会社 紫外線硬化性組成物及び硬化物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016204597A (ja) * 2015-04-28 2016-12-08 Ｋｊケミカルズ株式会社 Ｎ−置換（メタ）アクリルアミドを用いた重合性組成物、その重合物及びそれらからなる成形品
JP2017048288A (ja) * 2015-09-01 2017-03-09 Ｋｊケミカルズ株式会社 モデル材用活性エネルギー線硬化性樹脂組成物
JP2021146657A (ja) * 2020-03-23 2021-09-27 株式会社リコー 立体造形用組成物、高分子量体、立体造形物、及び立体造形物の製造方法
JP2022037903A (ja) * 2020-08-25 2022-03-09 三洋化成工業株式会社 活性エネルギー線硬化性組成物及び硬化物
JP2022153309A (ja) * 2021-03-29 2022-10-12 三洋化成工業株式会社 活性エネルギー線硬化性組成物及びその硬化物
JP2022164601A (ja) * 2021-04-16 2022-10-27 三洋化成工業株式会社 紫外線硬化性組成物及び硬化物

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