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WO2019124048A1 - Résine (méth)acrylate uréthane, composition de résine durcissable, objet durci, et film stratifié - Google Patents

Résine (méth)acrylate uréthane, composition de résine durcissable, objet durci, et film stratifié Download PDF

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Publication number
WO2019124048A1
WO2019124048A1 PCT/JP2018/044510 JP2018044510W WO2019124048A1 WO 2019124048 A1 WO2019124048 A1 WO 2019124048A1 JP 2018044510 W JP2018044510 W JP 2018044510W WO 2019124048 A1 WO2019124048 A1 WO 2019124048A1
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WIPO (PCT)
Prior art keywords
meth
acrylate
dipentaerythritol
urethane
mass
Prior art date
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Ceased
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PCT/JP2018/044510
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English (en)
Japanese (ja)
Inventor
直人 井上
伊藤　正広
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DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to JP2019560932A priority Critical patent/JP7234938B2/ja
Publication of WO2019124048A1 publication Critical patent/WO2019124048A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C08F290/08—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 side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings

Definitions

  • the present invention relates to a urethane (meth) acrylate resin which is excellent in abrasion resistance, flexibility, curl resistance and impact resistance in a cured coating film, a curable resin composition containing the same, a cured product and a laminated film.
  • Plastic films manufactured using polyethylene terephthalate resin (PET), acrylic resin, polycarbonate resin, acetylated cellulose resin, etc. are industrial applications such as a polarizing plate protective film incorporated in the inside of a flat panel display and a surface protective film of a touch panel Are often used.
  • PET polyethylene terephthalate resin
  • acrylic resin acrylic resin
  • polycarbonate resin polycarbonate resin
  • acetylated cellulose resin etc.
  • the surface of these plastic films is easily damaged by themselves, and the processability is low, so that there is a lack of performance such as cracking and cracking easily.
  • a coat layer made of an active energy ray curable resin or the like is provided on the surface. To compensate for these performances.
  • a coating agent for reinforcing a plastic film for example, a resin composition containing a urethane acrylate obtained by reacting dipentaerythritol polyacrylate having a hydroxyl value of 80 to 120 mg KOH / g and hexamethylene diisocyanate is known.
  • the resin composition is high in surface hardness of a cured product and excellent in abrasion resistance, but is easily curled and is not sufficiently tough or flexible of a coating film, so it is easily cracked by an external impact. there were.
  • the problem to be solved by the present invention is urethane (meth) acrylate resin capable of forming a cured coating film excellent in abrasion resistance, flexibility, curl resistance and impact resistance, and a curable resin composition containing the same.
  • An object, a cured product and a laminated film are provided.
  • the present inventor uses a urethane (meth) acrylate resin containing an isocyanate compound and dipentaerythritol (meth) acrylate having a specific hydroxyl value as essential reaction raw materials.
  • a urethane (meth) acrylate resin containing an isocyanate compound and dipentaerythritol (meth) acrylate having a specific hydroxyl value as essential reaction raw materials.
  • the present invention is a urethane (meth) acrylate resin comprising an isocyanate compound (A) and dipentaerythritol (meth) acrylate (B) as essential reaction raw materials, wherein the dipentaerythritol (meth) acrylate (
  • the present invention relates to a urethane (meth) acrylate resin characterized in that the hydroxyl value of B) is in the range of more than 120 mg KOH / g to 150 mg KOH / g, a curable resin composition containing the same, a cured product and a laminated film.
  • the urethane (meth) acrylate resin of the present invention can form a cured coating film excellent in scratch resistance, curl resistance, flexibility, and impact resistance, so it should be suitably used as a coating agent for protecting various substrate surfaces.
  • the laminated film having the cured coating film is excellent in abrasion resistance and curl resistance, and is highly flexible so that it is not easily cracked when it is bent or wound, and further, there is a drop on the film. Even in the case of impact resistance that is hard to break.
  • the urethane (meth) acrylate resin of the present invention uses the isocyanate compound (A) and dipentaerythritol (meth) acrylate (B) as essential reaction raw materials.
  • isocyanate compound (A) examples include aliphatic isocyanate compounds and isocyanate compounds having an aromatic ring or an alicyclic structure in the molecule.
  • aliphatic isocyanate compound examples include aliphatic diisocyanate compounds such as butane diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. It can be mentioned. Further, isocyanurate modified products, biuret modified products, allophanate modified products and the like which are modified products of these isocyanate compounds can also be used. These aliphatic isocyanate compounds can be used alone or in combination of two or more.
  • the isocyanate compound having an aromatic ring or an alicyclic structure in the molecule is, for example, an isocyanate compound (A1) represented by any of the following structural formulas (A1-1) to (A1-3);
  • R 1 is each independently an alkyl group having 1 to 4 carbon atoms, and j is an integer of 0 or 1 to 4.
  • R 2 is independently a hydrogen atom or 1 to 4 carbon atoms. Any of the alkyl groups)
  • Isocyanate compound (A2) represented by the following structural formula (A2-1) or (A2-2);
  • R 3 is each independently an alkyl group having 1 to 4 carbon atoms, or a structural portion represented in the parenthesis) And any of the bonding points linked via a methylene group marked with an asterisk (*), k is 0, 1 or 2 and n is an integer of 0 or 1 to 8.)
  • Alicyclic diisocyanate compounds such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, etc .; aromatic diisocyanate compounds such as diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate;
  • polymethylene polyphenyl polyisocyanate etc. which have a repeating structure represented by following Structural formula (1) are mentioned. Further, isocyanurate modified products, biuret modified products, allophanate modified products and the like which are modified products of these isocyanate compounds can also be used. These isocyanate compounds having an aromatic ring or an alicyclic structure in their molecule can be used alone or in combination of two or more.
  • R 4 is each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
  • R 5 is each independently an alkyl group having 1 to 4 carbon atoms, or a structural formula (1 And m is an integer of 0 or 1 to 3, and l is an integer of 1 or more. )
  • the dipentaerythritol (meth) acrylate (B) is obtained by (meth) acrylated a part of hydroxyl groups of dipentaerythritol, as long as it has a hydroxyl group capable of reacting with the isocyanate compound (A), It may be a single compound or a mixture of a plurality of compounds.
  • dipentaerythritol (meth) acrylate (B) dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol Erythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate can be used alone respectively.
  • dipentaerythritol mono (meth) acrylate dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta
  • One or more meta) acrylates may be contained and used as a mixture, and, if necessary, dipentaerythritol hexa (meth) acrylate may also be contained.
  • dipentaerythritol (meth) acrylate (B) can form a urethane (meth) acrylate resin capable of forming a cured coating film excellent in scratch resistance, flexibility, curl resistance, and impact resistance
  • the dipentaerythritol (meth) acrylate (B) contains the dipentaerythritol tetra (meth) acrylate (b1), the dipentaerythritol (meth) of the dipentaerythritol tetra (meth) acrylate (b1)
  • the content of the acrylate (B) is 10 to 50 because a urethane (meth) acrylate resin capable of forming a cured coating film excellent in scratch resistance, flexibility, curl resistance, and impact resistance can be obtained.
  • the range of mass% is preferable, the range of 12 to 45 mass% is more preferable, and the range of 15 to 40 mass% is particularly preferable.
  • the dipentaerythritol (meth) acrylate (B) contains the dipentaerythritol tetra (meth) acrylate (b1) and the dipentaerythritol penta (meth) acrylate (b2), scratch resistance, flexibility, Since a urethane (meth) acrylate resin capable of forming a cured coating film excellent in curl resistance and impact resistance can be obtained, the dipentaerythritol tetra (meth) acrylate (b1) and the dipentaerythritol penta (meth) are obtained.
  • the ratio of the content of acrylate (b2) [(b1) / (b2)] is preferably in the range of 20/80 to 80/20, and more preferably in the range of 30/70 to 60/40.
  • the dipentaerythritol (meth) acrylate (B) contains the dipentaerythritol hexa (meth) acrylate (b3), a cured coating excellent in scratch resistance, flexibility, curl resistance, and impact resistance Since a urethane (meth) acrylate resin capable of forming a film can be obtained, the content of the dipentaerythritol (hexa) acrylate (b3) in the dipentaerythritol (meth) acrylate (B) is 1 to 60 mass. The range of% is preferable, and the range of 5 to 50% by mass is more preferable.
  • the content of each component in the dipentaerythritol (meth) acrylate (B) and the ratio of the content of each component are calculated from the area ratio of the liquid chromatography chart measured under the following conditions. Value.
  • Device "LCMS-2010 EV” manufactured by Shimadzu Corporation
  • Data processing "LCMS Solution” manufactured by Shimadzu Corporation Column: Tosoh Corp.
  • ODS-100V (2.0 mm ID ⁇ 150 mm, 3 ⁇ m) 40 ° C.
  • Eluent water / acetonitrile, 0.4 mL / min Detector: PDA, MS Sample Preparation: 1.
  • the hydroxyl value of the dipentaerythritol (meth) acrylate (B) is a urethane (meth) acrylate resin capable of forming a cured coating film excellent in scratch resistance, flexibility, curl resistance, and impact resistance. Since it is obtained, it is more than 120 mg KOH / g and not more than 150 mg KOH / g, the range of 122 to 145 mg KOH / g is preferable, and the range of 122 to 140 mg KOH / g is more preferable.
  • the hydroxyl value of the dipentaerythritol (meth) acrylate (B) is an actual value measured according to JIS K 0070 (1992) neutralization titration method, or each component calculated from the area ratio of a liquid chromatography chart. Is a calculated value calculated from the composition ratio of
  • Examples of the method for producing the dipentaerythritol (meth) acrylate (B) include a method in which dipentaerythritol and acrylic acid are subjected to an esterification reaction.
  • a high molecular weight component (b ') or the like such as an addition reaction product of dipentaerythritol (meth) acrylates (B) may be generated as a by-product.
  • b ′) may be used after purification and removal, or as a raw material of the urethane (meth) acrylate resin as it is a crude product of dipentaerythritol (meth) acrylate (B) containing the high molecular weight component (b ′) good.
  • the content of the high molecular weight component (b ') in the crude product of the dipentaerythritol (meth) acrylate (B) is preferably in the range of 1 to 20% by mass.
  • the said urethane (meth) acrylate resin makes the said isocyanate compound (A) and the said dipentaerythritol (meth) acrylate (B) an essential reaction raw material, as needed, other monohydroxy (meta) may be used. Acrylate compounds, other polyol compounds, etc. can also be used.
  • Examples of the other monohydroxy (meth) acrylate compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, tri Aliphatic (meth) acrylate compounds such as methylolpropane di (meth) acrylate and pentaerythritol tri (meth) acrylate; 4-hydroxyphenyl acrylate; ⁇ -hydroxyphenethyl acrylate; 4-hydroxyphenethyl acrylate; 1- acrylic acid Aromatic ring-containing (meth) acrylate compounds such as phenyl-2-hydroxyethyl, 3-hydroxy-4-acetylphenyl acrylate and 2-hydroxy-3-phenoxypropyl acrylate; the above (meth) Polyether-modified (meth) obtained by ring-opening polymerization of a acrylate compound with various cyclic ether compounds such as ethylene oxide
  • hydroxy (meth) acrylate compounds can be used alone or in combination of two or more.
  • an urethane (meth) acrylate resin capable of forming a cured coating film excellent in scratch resistance, flexibility, curl resistance, and impact resistance can be obtained, aliphatic (meth) acrylate compounds or the compounds thereof Polyether modified products and lactone modified products are preferred.
  • the dipentaerythritol (meth) acrylate (B) and monohydroxy (meth) acrylate compounds It is preferable that the ratio of the said dipentaerythritol (meth) acrylate (B) with respect to the total mass of and becomes 70 mass% or more, and it is more preferable that it becomes 90 mass% or more.
  • Examples of the other polyol compound include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, and the like.
  • polyol compounds can be used alone or in combination of two or more.
  • these other polyol compounds when these other polyol compounds are used, the effects of the present invention are sufficiently exhibited. Therefore, the dipentaerythritol with respect to the total mass of the dipentaerythritol (meth) acrylate (B) and the other polyol compound is sufficient.
  • the proportion of erythritol (meth) acrylate (B) is preferably 70% by mass or more, and more preferably 90% by mass or more.
  • the method for producing the urethane (meth) acrylate resin is, for example, an isocyanate group which the isocyanate (A) has, the isocyanate compound (A) and the dipentaerythritol (meth) acrylate (B);
  • the molar ratio [(NCO) / (OH)] to the hydroxyl group of erythritol (meth) acrylate (B) is in the range of 1 / 1.05 to 1/2, and the temperature range of 20 to 120 ° C.
  • the method of performing using a urethanization catalyst is mentioned.
  • the (meth) acryloyl group equivalent of the urethane (meth) acrylate resin is in the range of 100 to 500 g / eq because it can form a cured coating film excellent in scratch resistance, flexibility, curl resistance, and impact resistance. Preferably, the range of 100 to 250 g / eq is more preferable.
  • the (meth) acryloyl group equivalent of urethane (meth) acrylate resin in this invention is a value calculated as a theoretical value from the reaction raw material.
  • the weight average molecular weight (Mw) of the urethane (meth) acrylate resin is 1,500 to 100, because a cured coating film excellent in scratch resistance, flexibility, curl resistance, and impact resistance can be formed.
  • the range of 000 is preferable, and the range of 3,000 to 5,000 is more preferable.
  • the weight average molecular weight (Mw) of the said urethane (meth) acrylate resin shows the value measured by gel permeation chromatography (GPC) method.
  • the curable resin composition of the present invention contains the urethane (meth) acrylate resin and a photopolymerization initiator.
  • photopolymerization initiator examples include benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4,4'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone , Various benzophenones such as Michler's ketone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;
  • Xanthones such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, thioxanthones; various acyloethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether;
  • ⁇ -diketones such as benzyl and diacetyl; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; various benzoic acids such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate;
  • 1-hydroxycyclohexyl phenyl ketone which is active against light of a wider range of wavelengths and can improve the curing property of the cured coating film of the curable resin composition
  • Hydroxy-2-methyl-1-phenylpropan-1-one 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-Dimethoxy-1,2-diphenylethan-1-one, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide, 2-methyl-1 -[4- (Methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-di Chiruamino -1- (4-morpholinophenyl) - it is prefer
  • the addition amount of the photopolymerization initiator is an amount that can sufficiently exhibit the function as a photopolymerization initiator, and a range in which precipitation of crystals and deterioration of coating film properties do not occur is preferable, and specifically, The range of 0.05 to 20 parts by mass is preferable with respect to 100 parts by mass of the urethane (meth) acrylate resin, and the range of 0.1 to 10 parts by mass is more preferable.
  • the said curable resin composition can improve the curability of the cured coating film of the said curable resin composition, it can also contain a photosensitizer.
  • the photosensitizer examples include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, and sulfur such as sodium diethyl dithiophosphate and s-benzyl isothiuronium-p-toluenesulfonate. A compound etc. are mentioned.
  • the curable resin composition of the present invention may further comprise, in addition to the urethane (meth) acrylate resin, other photocurable compounds (R), organic solvents, ultraviolet absorbers, antioxidants, silicone additives, fluorine It may contain a system additive, a silane coupling agent, a phosphoric acid ester compound, an organic bead, an inorganic fine particle, an inorganic filler, a rheology control agent, a defoamer, an antifogging agent, a colorant and the like.
  • R photocurable compounds
  • Examples of the other photocurable compound (R) include various (meth) acrylate monomers, and other urethane (meth) acrylate resins other than the urethane (meth) acrylate resin, and epoxy (meth) acrylate resin And dendrimer type (meth) acrylate resins, (meth) acryloyl group-containing acrylic resins, and the like.
  • the (meth) acrylate monomer is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate ) Acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloyl morpholine, N-vinyl pyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth)
  • urethane (meth) acrylate resin for example, urethane (meth) acrylate resin using isocyanate compounds other than the said isocyanate compound (A), and hydroxy (meta) other than dipentaerythritol (meth) acrylate (B) Urethane (meth) acrylate resin using an acrylate compound is mentioned.
  • Examples of the epoxy (meth) acrylate resin include those obtained by reacting various epoxy resins such as bisphenol-type epoxy resin and novolac-type epoxy resin with (meth) acrylic acid or a derivative thereof to (meth) acrylate .
  • the dendrimer type (meth) acrylate resin is a resin having a regular multi-branched structure and having a (meth) acryloyl group at the end of each branched chain. It is called a star polymer. Examples of such compounds include, but are not limited to, those represented by the following structural formulas (2-1) to (2-8), but the present invention is not limited thereto, and a multi-branched structure having regularity may be used. Any resin may be used as long as it is a resin having a (meth) acryloyl group at the end of each branched chain.
  • R 3 is a hydrogen atom or a methyl group
  • R 4 is a hydrocarbon group having 1 to 4 carbon atoms.
  • R 3 is a hydrogen atom or a methyl group
  • R 4 is a hydrocarbon group having 1 to 4 carbon atoms.
  • a dendrimer type (meth) acrylate resin for example, “Biscoat # 1000” manufactured by Osaka Organic Chemical Co., Ltd. [weight-average molecular weight (Mw) 1,500 to 2,000, average (meth) acryloyl per molecule] Radical number 14], “Biscoat 1020” [Weight average molecular weight (Mw) 1,000 to 3,000], “SIRIUS 501” [Weight average molecular weight (Mw) 15,000 to 23,000], manufactured by MIWON "SP-1106 [Weight average molecular weight (Mw) 1,630, average (meth) acryloyl group number 18 per molecule], "CN 2301", “CN 2302” (average number (meth) acryloyl group number 16 per one molecule), manufactured by SARTOMER, " CN 2303 “[average (meth) acryloyl group number 6 per one molecule],” CN 2304 " Average (meth) acryloyl group number 18 per molecule], "E
  • the weight average molecular weight (Mw) of the dendrimer type (meth) acrylate resin is preferably in the range of 1,000 to 30,000.
  • the average number of (meth) acryloyl groups per molecule is preferably in the range of 5 to 30.
  • the (meth) acryloyl group-containing acrylic resin can be obtained, for example, by polymerizing a (meth) acrylate monomer ( ⁇ ) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group or a glycidyl group as an essential component
  • a (meth) acrylate monomer ( ⁇ ) having a reactive functional group capable of reacting with these functional groups to an acrylic resin intermediate may be mentioned.
  • Examples of the (meth) acrylate monomer ( ⁇ ) having a reactive functional group include, for example, hydroxyl group-containing (meth) acrylate monomers such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; (meth) acrylic acid Carboxyl group-containing (meth) acrylate monomers; isocyanate group-containing (meth) acrylate monomers such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, etc .; glycidyl (meth) Examples thereof include glycidyl group-containing (meth) acrylate monomers such as acrylate and 4-hydroxybutyl acrylate glycidyl ether. These (meth) acrylate monomers ( ⁇ ) may be used alone or in combination of two or more.
  • the acrylic resin intermediate may be one obtained by copolymerizing other polymerizable unsaturated group-containing compounds, if necessary, in addition to the (meth) acrylate monomer ( ⁇ ).
  • the other polymerizable unsaturated group-containing compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate ) Acrylic acid alkyl esters; Cyclocyclic (meth) acrylates such as cyclohexyl (meth) acrylate, isoboronyl (meth) acrylate, dicyclopentanyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl Aromatic ring-containing (meth) acrylates such as acrylates; silyl group-containing (meth) acrylates such
  • the reaction ratio of both makes curability
  • the ratio of the (meth) acrylate monomer ( ⁇ ) to the total of both is preferably in the range of 20 to 70% by mass, and more preferably in the range of 30 to 60% by mass.
  • the said acrylic resin intermediate can be manufactured by the method similar to a common acrylic resin.
  • it can be produced by polymerizing various monomers in the presence of a polymerization initiator in a temperature range of 60 to 150.degree.
  • the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
  • the polymerization mode for example, a random copolymer, a block copolymer, a graft copolymer and the like can be mentioned.
  • ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
  • glycol ether solvents such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether are used. Is preferred.
  • the (meth) acrylate monomer ( ⁇ ) is not particularly limited as long as it can react with the reactive functional group possessed by the (meth) acrylate monomer ( ⁇ ), but from the viewpoint of reactivity, the following combination Is preferred. That is, when the hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate monomer ( ⁇ ), it is preferable to use an isocyanate group-containing (meth) acrylate as the (meth) acrylate monomer ( ⁇ ).
  • the carboxyl group-containing (meth) acrylate is used as the (meth) acrylate monomer ( ⁇ )
  • the glycidyl group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer ( ⁇ ).
  • the isocyanate group-containing (meth) acrylate is used as the (meth) acrylate monomer ( ⁇ )
  • the carboxy group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer ( ⁇ ).
  • the reaction between the acrylic resin intermediate and the (meth) acrylate monomer ( ⁇ ) is, for example, an esterification such as triphenylphosphine in a temperature range of 60 to 150 ° C. when the reaction is an esterification reaction.
  • the method etc. which use a catalyst suitably are mentioned.
  • the reaction is a urethanation reaction, the reaction may be carried out while dropping the (meth) acrylate monomer ( ⁇ ) to the acrylic resin intermediate at a temperature range of 50 to 120 ° C., and the like.
  • the weight average molecular weight (Mw) of the (meth) acryloyl group-containing acrylic resin is preferably in the range of 5,000 to 80,000.
  • the (meth) acryloyl group equivalent is preferably in the range of 100 to 500 g / equivalent.
  • the urethane (meth) of the present invention is contained in 100 parts by mass in total of the urethane (meth) acrylate resin of the present invention and the other photocurable compounds (R).
  • the acrylate resin is preferably used in a proportion of 5 parts by mass or more, more preferably 20 parts by mass or more, and particularly preferably 80 parts by mass or more.
  • organic solvent examples include ketone solvents such as methyl ethyl ketone, acetone and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; aromatic solvents such as toluene and xylene; Alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol and propylene glycol monomethyl ether; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether And glycol ether solvents such as acetate.
  • ketone solvents such as methyl ethyl ketone, acetone and isobutyl ketone
  • organic solvents can be used alone or in combination of two or more. These organic solvents are mainly used for the purpose of adjusting the viscosity of the curable composition, but in general, it is preferable to adjust the nonvolatile content to be in the range of 10 to 80% by mass.
  • Examples of the ultraviolet absorber include 2- [4- ⁇ (2-hydroxy-3-dodecyloxypropyl) oxy ⁇ -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine, 2- [4- ⁇ (2-hydroxy-3-tridecyloxypropyl) oxy ⁇ -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, Triazine derivatives such as 3,5-triazine, 2- (2'-xanthene carboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2 And xanthene carboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone and the like. These ultraviolet absorbers can be used alone or in combination of two or more.
  • antioxidants examples include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, phosphoric acid ester-based antioxidants, and the like. These antioxidants can be used alone or in combination of two or more.
  • silicone-based additive examples include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether modified dimethylpolysiloxane copolymer, polyester modified dimethylpolysiloxane copolymer, fluorine modified Polyorganosiloxane having alkyl group or phenyl group such as dimethylpolysiloxane copolymer, amino-modified dimethylpolysiloxane copolymer, polydimethylsiloxane having polyether modified acrylic group, polydimethylsiloxane having polyester modified acrylic group, etc. It can be mentioned. These silicon-based additives can be used alone or in combination of two or more.
  • fluorine-based additive examples include “Megaface” series manufactured by DIC Corporation. These fluorine-based additives can be used alone or in combination of two or more.
  • silane coupling agent examples include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and the like.
  • Styrene based silane coupling agents such as p-styryltrimethoxysilane
  • (Meth) such as 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc.
  • Acryloxy based silane coupling agent such as 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc.
  • Ureido-based silane coupling agents such as 3-ureidopropyltriethoxysilane
  • Chloropropyl based silane coupling agents such as 3-chloropropyltrimethoxysilane
  • Mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;
  • Sulfide based silane coupling agents such as bis (triethoxysilylpropyl) tetrasulfide
  • silane coupling agents such as 3-isocyanate propyltriethoxysilane. These silane coupling agents can be used alone or in combination of two or more.
  • Examples of the phosphate ester compounds include those having a (meth) acryloyl group in the molecular structure, and examples of commercially available products include “Kayamar PM-2”, “Kayamer PM-” manufactured by Nippon Kayaku Co., Ltd.
  • organic beads examples include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacryl styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads And polyester resin beads, polyamide resin beads, polyimide resin beads, polytetrafluoroethylene resin beads, polyethylene resin beads and the like. These organic beads can be used alone or in combination of two or more. The average particle size of these organic beads is preferably in the range of 1 to 10 ⁇ m.
  • the inorganic fine particles include fine particles of silica, alumina, zirconia, titania, barium titanate, antimony trioxide and the like. These inorganic fine particles may be used alone or in combination of two or more.
  • the average particle diameter of these inorganic fine particles is preferably in the range of 95 to 250 nm, and more preferably in the range of 100 to 180 nm.
  • a dispersion aid When the inorganic fine particles are contained, a dispersion aid can be used.
  • the dispersion aid include phosphoric acid ester compounds such as isopropyl acid phosphate, triisodecyl phosphite, ethylene oxide modified phosphoric acid dimethacrylate, and the like.
  • These dispersion adjuvants can be used alone or in combination of two or more.
  • Nippon Kayaku Co., Ltd. "Kayamer PM-21", “Kayamer PM-2”, Kyoeisha Chemical Co., Ltd. "light ester P-2M” etc. are mentioned, for example. .
  • the cured product of the present invention is obtained by curing the curable resin composition.
  • Examples of the method for curing the curable composition include a method of heating and a method of irradiating active energy rays such as ultraviolet rays.
  • curing can be performed by heating in a temperature range of 60 to 200 ° C. for 0.5 to 60 minutes.
  • ionizing radiation such as an electron beam, an alpha ray, a beta ray, and a gamma ray can be used in addition to the ultraviolet ray.
  • the exposure dose of the actinic energy ray is preferably in the range of 0.05 ⁇ 5J / cm 2, more preferably in the range of 0.1 ⁇ 3J / cm 2, 0.1 ⁇ 1J / cm 2 It is particularly preferable to be in the range of The above-mentioned ultraviolet irradiation amount is based on a value measured in a wavelength range of 300 to 390 nm using a UV checker UVR-N1 (manufactured by Japan Battery Co., Ltd.).
  • the laminated film of the present invention has a layer comprising the cured product on a substrate.
  • a method for producing the laminated film of the present invention for example, a method of applying the curable resin composition to at least one surface of the substrate and then irradiating an active energy ray may be mentioned.
  • the substrate examples include metal substrates, plastic substrates, glass substrates, paper substrates, wood substrates, fibrous substrates and the like.
  • plastic substrates are preferable because they have excellent adhesion to the curable resin composition.
  • the material of the plastic base material is polyester, acrylic resin (polymethyl methacrylate etc.), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), composite resin of ABS resin and polycarbonate, polystyrene, polyurethane, epoxy resin And polyvinyl chloride, polyamide, polyolefin (polyethylene, polypropylene, polycycloolefin (COP), etc.), triacetyl cellulose (TAC), polyimide and the like.
  • plastic base examples include plastic molded articles such as mobile phones, home appliances, automobile interior and exterior materials, OA equipment and the like. Also, a film base made of plastic can be used.
  • a gravure coater for example, a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, flow coater, spin coater, dipping, screen Coating methods include printing, spraying, brushing, an applicator, a bar coater, and the like.
  • the film thickness of the coating film formed using the said active energy ray curable resin composition can be suitably adjusted according to the use to be used, Usually, it is preferable that it is the range of 0.01-50 micrometers. .
  • the laminated film of the present invention may have a functional film layer such as an antireflection film, a diffusion film, a polarizing film, etc., in addition to the substrate and the layer made of the cured product.
  • a functional film layer such as an antireflection film, a diffusion film, a polarizing film, etc.
  • the laminated film of the present invention can be used as a coating layer for protecting the substrate surface since it has a cured coating film excellent in scratch resistance, flexibility, curl resistance and impact resistance.
  • it can be suitably used for the front plate application of a liquid crystal display or an organic EL display.
  • plastic molded articles such as a mobile telephone, a household appliance case, the bumper of a motor vehicle, OA apparatus, etc. are mentioned, for example.
  • a hydroxyl value is the actual value measured according to the neutralization titration method of JISK 0070 (1992).
  • a weight average molecular weight (Mw) is the value measured on condition of the following using gel permeation chromatography (GPC).
  • Measuring device manufactured by Tosoh Corporation HLC-8220 Column; Tosoh Corp. guard column H XL- H + Tosoh Corporation TSKgel G5000HXL + Tosoh Corporation TSKgel G4000HXL + Tosoh Corporation TSKgel G3000HXL + Tosoh Corporation TSKgel G2000 HXL Detector; RI (differential refractometer) Data processing: Tosoh Corp. SC-8010 Measurement conditions: Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard; Polystyrene sample; Tetrahydrofuran solution of 0.4% by mass in terms of resin solid content filtered with a microfilter (100 ⁇ l)
  • the liquid chromatography chart was measured under the following conditions.
  • Production Example 1 Production of dipentaerythritol (meth) acrylate (B1) In a flask equipped with a thermometer, a stirrer, and a condenser, 280 parts by mass of acrylic acid, 180 parts by mass of dipentaerythritol, 15 parts by mass of sulfuric acid, 1.5 parts by mass of cupric chloride, and 300 parts by mass of toluene. The temperature was raised to 105 ° C. while stirring, and the system was allowed to react at the same temperature for 13 hours while refluxing. The produced water was 65 parts by mass. To the reaction mixture, 425 parts by mass of toluene was added and washed with 200 parts by mass of distilled water.
  • reaction mixture was neutralized by the addition of a 20% aqueous sodium hydroxide solution, and washed with 100 parts by mass of distilled water.
  • hydroquinone monomethyl ether was added in an amount of 500 ppm based on resin solids, toluene was distilled off to obtain dipentaerythritol (meth) acrylate (B1).
  • the hydroxyl value of this dipentaerythritol (meth) acrylate (B1) was 125 mg KOH / g (measured value).
  • dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart is 23% by mass
  • the content of dipentaerythritol pentaacrylate (b2) is 36% by mass
  • dipentaerythritol hexaacrylate The content of (b3) was 26% by mass
  • the content of the high molecular weight component (b ') was 15% by mass.
  • Production Example 2 Production of dipentaerythritol (meth) acrylate (B2) In a flask equipped with a thermometer, a stirrer, and a condenser, 250 parts by mass of acrylic acid, 180 parts by mass of dipentaerythritol, 15 parts by mass of sulfuric acid, 1.5 parts by mass of cupric chloride, and 300 parts by mass of toluene. The temperature was raised to 105 ° C. while stirring, and the system was allowed to react at the same temperature for 13 hours while refluxing. The generated water was 64 parts by mass. To the reaction mixture, 425 parts by mass of toluene was added and washed with 200 parts by mass of distilled water.
  • reaction mixture was neutralized by the addition of a 20% aqueous sodium hydroxide solution, and washed with 100 parts by mass of distilled water.
  • hydroquinone monomethyl ether was added in an amount of 500 ppm based on resin solids, toluene was distilled off to obtain dipentaerythritol (meth) acrylate (B2).
  • the hydroxyl value of this dipentaerythritol (meth) acrylate (B2) was 130 mg KOH / g.
  • dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart is 26% by mass
  • the content of dipentaerythritol pentaacrylate (b2) is 39% by mass
  • the content of (b3) was 24% by mass
  • the content of the high molecular weight component (b ') was 11% by mass.
  • reaction mixture was neutralized by the addition of a 20% aqueous sodium hydroxide solution, and washed with 100 parts by mass of distilled water.
  • hydroquinone monomethyl ether in an amount of 500 ppm based on resin solids, toluene was distilled off to obtain dipentaerythritol (meth) acrylate (B3).
  • the hydroxyl value of this dipentaerythritol (meth) acrylate (B3) was 140 mg KOH / g.
  • dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart is 28% by mass
  • the content of dipentaerythritol pentaacrylate (b2) is 42% by mass
  • dipentaerythritol hexaacrylate The content of (b3) was 22% by mass
  • the content of the high molecular weight component (b ') was 8% by mass.
  • Comparative Production Example 1 Production of dipentaerythritol (meth) acrylate (B4) In a flask equipped with a thermometer, a stirrer, and a condenser, 460 parts by mass of acrylic acid, 180 parts by mass of dipentaerythritol, 15 parts by mass of sulfuric acid, 1.5 parts by mass of cupric chloride, and 300 parts by mass of toluene. The temperature was raised to 105 ° C. while stirring, and the system was allowed to react at the same temperature for 13 hours while refluxing. The generated water was 71.8 parts by mass. To the reaction mixture, 425 parts by mass of toluene was added and washed with 200 parts by mass of distilled water.
  • reaction mixture was neutralized by the addition of a 20% aqueous sodium hydroxide solution, and washed with 100 parts by mass of distilled water.
  • hydroquinone monomethyl ether was added in an amount of 500 ppm based on resin solids, toluene was distilled off to obtain dipentaerythritol (meth) acrylate (B4).
  • the hydroxyl value of this dipentaerythritol (meth) acrylate (B4) was 43 mg KOH / g.
  • the content of dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart is 0.2% by mass
  • the content of dipentaerythritol pentaacrylate (b2) is 35.2% by mass
  • the content of pentaerythritol hexaacrylate (b3) was 62.1% by mass
  • the content of high molecular weight component (b ') was 2.5% by mass.
  • Comparative Production Example 2 Production of dipentaerythritol (meth) acrylate (B5) In a flask equipped with a thermometer, a stirrer, and a condenser, 180 parts by mass of acrylic acid, 180 parts by mass of dipentaerythritol, 15 parts by mass of sulfuric acid, 1.5 parts by mass of cupric chloride, and 300 parts by mass of toluene. The temperature was raised to 105 ° C. while stirring, and the system was allowed to react at the same temperature for 13 hours while refluxing. The produced water was 50 parts by mass. To the reaction mixture, 425 parts by mass of toluene was added and washed with 200 parts by mass of distilled water.
  • reaction mixture was neutralized by the addition of a 20% aqueous sodium hydroxide solution, and washed with 100 parts by mass of distilled water.
  • hydroquinone monomethyl ether was added in an amount of 500 ppm based on resin solids, toluene was distilled off to obtain dipentaerythritol (meth) acrylate (B5).
  • the hydroxyl value of this dipentaerythritol (meth) acrylate (B5) was 160 mg KOH / g.
  • dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart is 36% by mass
  • the content of dipentaerythritol pentaacrylate (b2) is 48% by mass
  • dipentaerythritol hexaacrylate The content of (b3) was 8% by mass
  • the content of the high molecular weight component (b ') was 8% by mass.
  • Isocyanate compound (A1) in Table 1 shows hexamethylene diisocyanate.
  • Isocyanate compound (A2) in Table 1 shows pentamethylene diisocyanate.
  • Example 5 Preparation of Laminated Film (1)
  • a curable resin composition was prepared by mixing 125 parts by mass of the urethane (meth) acrylate resin (1) obtained in Example 1, 3 parts by mass of a photopolymerization initiator ("Omnirad-184" manufactured by IGM), and 72 parts by mass of methyl ethyl ketone I got Next, the obtained curable resin composition was applied on a 125 ⁇ m thick polyethylene terephthalate film (hereinafter abbreviated as “PET film”) with a bar coater and dried at 80 ° C. for 2 minutes.
  • PET film polyethylene terephthalate film
  • Example 5 Preparation of laminated films (2) to (4)
  • Example 5 except that the urethane (meth) acrylate resins (2) to (4) obtained in Examples 2 to 4 were used instead of the urethane (meth) acrylate resin (1) used in Example 5
  • Laminated films (2) to (4) were obtained in the same manner as in the above.
  • Comparative Examples 3 and 4 Preparation of Laminated Films (R1) and (R2) Example 5 except that the urethane (meth) acrylate resins (C1) and (C2) obtained in Comparative Examples 1 and 2 were used instead of the urethane (meth) acrylate resin (1) used in Example 5 Laminated films (R1) and (R2) were obtained in the same manner as in the above.
  • the weight was suspended at a position where the distance from the surface of the laminated film to the lower end of the weight was 50 mm, and after confirming that the swing or rotation had stopped, it was dropped onto the laminated film. 3. After the laminated film after the drop test was allowed to stand in the room for 1 hour, damage to the coated surface was examined. 4. The distance between the surface of the laminated film and the lower end of the weight was separated by 10 mm, and the test was continued to evaluate the maximum distance at which no cracking or peeling of the cured coating occurs.
  • Examples 5 to 8 shown in Table 2 are examples of the laminated film using the urethane (meth) acrylate resin of the present invention, the cured coating film of the urethane (meth) acrylate resin is excellent in the coating film hardness. It was also confirmed that the laminated film had excellent scratch resistance, flexibility, curl resistance and impact resistance.
  • Comparative Example 3 is an example using dipentaerythritol (meth) acrylate having a hydroxyl value of 43 mg KOH / g as a raw material of urethane (meth) acrylate resin, but the cured coating film of the urethane (meth) acrylate resin is Although excellent in coating film hardness, it was confirmed that the laminated film using the urethane (meth) acrylate resin was extremely insufficient in flexibility, curl resistance and impact resistance.
  • Comparative Example 4 is an example using dipentaerythritol (meth) acrylate having a hydroxyl value of 160 mg KOH / g as a raw material of urethane (meth) acrylate resin, but the cured coating film of the urethane (meth) acrylate resin is coated It was confirmed that the film hardness was insufficient, and that the laminated film using the urethane (meth) acrylate resin was extremely insufficient in abrasion resistance.

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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)
  • Macromonomer-Based Addition Polymer (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention fournit une résine (méth)acrylate uréthane, une composition de résine durcissable comprenant celle-ci, un objet durci et un film stratifié. Ladite résine (méth)acrylate uréthane a pour matières de départ réactives essentielles un composé isocyanate (A) et un (méth)acrylate de dipentaérythritol (B), et est caractéristique en ce que l'indice d'hydroxyle dudit (méth)acrylate de dipentaérythritol (B), se trouve dans une plage supérieure à １２０ｍｇＫＯＨ／ｇ et inférieure ou égale à １５０ｍｇＫＯＨ／ｇ. Cette résine (méth)acrylate uréthane permet de former un film de revêtement durci excellent en termes de résistance à l'abrasion, souplesse, résistance au roulage et résistance aux impacts.
PCT/JP2018/044510 2017-12-19 2018-12-04 Résine (méth)acrylate uréthane, composition de résine durcissable, objet durci, et film stratifié Ceased WO2019124048A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010146801A1 (fr) * 2009-06-17 2010-12-23 日本化薬株式会社 Composé de (méth)acrylate d'uréthanne et composition de résine le contenant
JP2011523674A (ja) * 2008-06-06 2011-08-18 サイテック サーフェース スペシャリティーズ、エス．エイ． 水性照射硬化性ポリウレタン組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011523674A (ja) * 2008-06-06 2011-08-18 サイテック サーフェース スペシャリティーズ、エス．エイ． 水性照射硬化性ポリウレタン組成物
WO2010146801A1 (fr) * 2009-06-17 2010-12-23 日本化薬株式会社 Composé de (méth)acrylate d'uréthanne et composition de résine le contenant

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