WO2013164941A1 - Curable resin composition - Google Patents

Curable resin composition Download PDF

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Publication number
WO2013164941A1
WO2013164941A1 PCT/JP2013/060855 JP2013060855W WO2013164941A1 WO 2013164941 A1 WO2013164941 A1 WO 2013164941A1 JP 2013060855 W JP2013060855 W JP 2013060855W WO 2013164941 A1 WO2013164941 A1 WO 2013164941A1
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metal oxide
mass
meth
curable resin
present
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PCT/JP2013/060855
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French (fr)
Japanese (ja)
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丈章 齋木
依慶 米山
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横浜ゴム株式会社
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Publication of WO2013164941A1 publication Critical patent/WO2013164941A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/44Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present invention relates to a curable resin composition.
  • Patent Document 1 a curable resin composition for the purpose of forming a high-hardness film has been proposed (for example, Patent Document 1).
  • an object of this invention is to provide the curable resin composition used as the film which has high hardness.
  • the present inventor applied ultrasonic waves to a composition containing silica having a primary average particle diameter of 20 nm (for example, for hard coat) to aggregate about 2 to 5 silica. First, it was found that the hardness of the hard coat obtained was improved, and further research was conducted on this.
  • the (b) metal oxide contains secondary aggregates, the secondary aggregate has a particle size of 150 nm or less, and the amount of secondary aggregates having a particle size of 100 nm or more is in the (b) metal oxide.
  • the present invention was completed by finding that the curable resin composition of 1% by mass or more has a high hardness.
  • the present invention provides the following 1 to 5.
  • (d) an organic solvent The (b) metal oxide contains secondary aggregates, the secondary aggregate has a particle size of 150 nm or less, and the amount of secondary aggregates having a particle size of 100 nm or more is in the (b) metal oxide.
  • Curable resin composition which is 1 mass% or more. 2.
  • a laminate comprising a substrate and a resin layer obtained by using the curable resin composition according to any one of 1 to 4 on the substrate.
  • the curable resin composition of the present invention becomes a film having high hardness.
  • the laminate of the present invention has a high hardness resin layer.
  • FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention.
  • the curable resin composition of the present invention (the composition of the present invention) (A) 10 to 90% by mass of an ethylenic compound having 3 or more ethylenically unsaturated groups in the molecule; (B) 5 to 75% by mass of a metal oxide, (C) contains 0.1 to 10% by weight of a photopolymerization initiator, and (d) an organic solvent,
  • the (b) metal oxide contains secondary aggregates, the secondary aggregate has a particle size of 150 nm or less, and the amount of secondary aggregates having a particle size of 100 nm or more is in the (b) metal oxide.
  • the curable resin composition is 1% by mass or more.
  • (A) The ethylenic compound will be described below.
  • an ethylenic compound contained in the composition of the present invention [this may hereinafter be referred to as component (a) or (a).
  • the description of the components contained in the composition of the present invention in this way is the same for (b) to (d). ]
  • the ethylenically unsaturated group is not particularly limited as long as it has —C ⁇ C—.
  • the ethylenically unsaturated group has, for example, a hydrogen atom; a hydrocarbon group that can have a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom; a carbonyl group; a carbonyloxy group be able to.
  • (meth) acryloyl means one or both of acryloyl and methacryloyl.
  • the ethylenic compound can have 3 to 14 ethylenically unsaturated groups in one molecule.
  • the ethylenic compound may have one or more hydroxy groups in one molecule.
  • the ethylenic compound may have no hydroxy group in one molecule.
  • the hydrocarbon group which may have hetero atoms, such as an oxygen atom, a nitrogen atom, and a sulfur atom, is mentioned, for example.
  • Examples of (a) ethylenic compounds include (meth) acrylic acid esters of polyhydric alcohols and urethane (meth) acrylates.
  • (A) These dendrimer types may be sufficient as an ethylenic compound.
  • polyhydric alcohol (meth) acrylic acid esters include trifunctional groups such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol tri (meth) acrylate; pentaerythritol tetra Tetrafunctional system such as (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate; dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythri
  • the urethane (meth) acrylate that can be used as the component (a) for example, a (meth) acrylic acid ester of a polyhydric alcohol (in this case, the (meth) acrylic acid ester of a polyhydric alcohol is, for example, at least one And a reaction product of a polyisocyanate compound.
  • the (meth) acrylic acid ester of polyhydric alcohol used when producing urethane (meth) acrylate include the same as described above.
  • Examples of the polyisocyanate compound used in producing urethane (meth) acrylate include tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and tolidine diisocyanate.
  • Aromatic polyisocyanates such as 1,5-naphthalene diisocyanate and triphenylmethane triisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis (Isocyanate methyl) Cyclohexane, (including linear and / or cycloaliphatic systems.) Aliphatic polyisocyanates such as dicyclohexylmethane diisocyanate; these isocyanurate, biuret body, adduct thereof.
  • the number of ethylenically unsaturated groups contained in one molecule of urethane (meth) acrylate is more preferably 3-15.
  • a compound having 3 to 6 ethylenically unsaturated groups in one molecule such as dipentaerythritol hexa (meth) acrylate from the viewpoint of higher hardness and excellent optical properties;
  • a compound having 7 to 14 ethylenically unsaturated groups in the molecule may be a dendrimer type); urethane (meth) acrylate is preferred.
  • a component can be used individually or in combination of 2 types or more, respectively.
  • the amount of the compound having 7 to 14 ethylenically unsaturated groups is based on 100 parts by mass of the compound having 3 to 6 ethylenically unsaturated groups in one molecule from the viewpoint of higher hardness and excellent optical properties.
  • the amount is preferably 10 to 50 parts by mass, and more preferably 15 to 35 parts by mass.
  • the ester has 3 to 14 ethylenically unsaturated groups in one molecule and does not have a hydroxy group (for example, all hydroxy groups of a polyhydric alcohol are (meth) acrylic ester). It is more preferable to have 3 to 6 ethylenically unsaturated groups in one molecule and no hydroxy group.
  • the amount ratio of the (meth) acrylic acid ester of the polyhydric alcohol and the urethane (meth) acrylate is 20 to 150 masses of urethane (meth) acrylate with respect to 100 mass parts of the (meth) acrylic acid ester of the polyhydric alcohol. Part is preferable, and 40 to 120 parts by mass is more preferable.
  • the component (a) is not particularly limited for its production. For example, a conventionally well-known thing is mentioned. (A) can be used individually or in combination of 2 or more types.
  • the metal oxide (b) contained in the composition of the present invention is such that the metal oxide contains a secondary aggregate, and the secondary aggregate has a particle size of 150 nm or less and a secondary particle size of 100 nm or more. The amount of the aggregate is 1% by mass or more in the metal oxide.
  • the metal oxide is a metal oxide. Specific examples include silica, aluminum oxide (alumina), titanium oxide (titania), zinc oxide, tin oxide, and cerium oxide.
  • the metal oxide is preferably silica from the viewpoint of higher hardness, excellent dispersibility in a resin or solvent, and excellent optical properties.
  • Silica is not particularly limited as long as it has a silanol group. Silica includes untreated ones, surface treated ones and the like. Examples of silica include colloidal silica.
  • the metal oxide further has an ethylenically unsaturated group from the viewpoints of higher hardness, excellent reactivity with the resin, and excellent optical characteristics.
  • an ethylenically unsaturated group which a metal oxide can have further the thing similar to the ethylenically unsaturated group which (a) has is mentioned, for example.
  • transducing an ethylenically unsaturated group further into a metal oxide it is also called a (meth) acryloyloxy group [(meth) acryl group, for example.
  • a silane coupling agent having The silane coupling agent having a (meth) acryloyloxy group is not particularly limited as long as it is a compound having at least a (meth) acryloyloxy group and a hydrolyzable silyl group.
  • the (meth) acryloyloxy group and the hydrolyzable silyl group can be bonded via, for example, an organic group.
  • the organic group include a hydrocarbon group that may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof.
  • Examples of the silane coupling agent having a (meth) acryloyloxy group include 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, and 3- (meth) acryloyloxypropylmethyl.
  • (Meth) acryloyloxyalkyl dialkoxy silanes such as diethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane, and (meth) acryloyloxyalkyltrialkoxysilanes.
  • 3- (meth) acryloyloxypropyltrimethoxysilane is preferred from the viewpoints of excellent optical properties, excellent initial adhesion and wear resistance, and higher hardness.
  • the metal oxide having an ethylenically unsaturated group can be obtained, for example, by reacting a silane coupling agent having a (meth) acryloyloxy group with silica (for example, untreated silica).
  • the metal oxide (b) is preferably hydrophobized from the viewpoint of higher hardness and excellent optical properties.
  • Hydrophobizing agents used for hydrophobizing metal oxides include, for example, trimethylsilane, chlorotrimethylsilane (generally trimethylsilyl group-containing compounds), 3- (meth) acryloyloxypropyltrimethoxysilane And silane coupling agents having a (meth) acryloyloxy group as mentioned above. Of these, 3- (meth) acryloyloxypropyltrimethoxysilane is preferred from the viewpoints of excellent optical properties, excellent initial adhesion and wear resistance, excellent reactivity, and higher hardness.
  • the hydrophobized metal oxide can be obtained, for example, by reacting a hydrophobizing agent with silica (for example, untreated silica).
  • the metal oxide contains secondary aggregates.
  • the composition of the present invention has high hardness and excellent optical properties because the (b) metal oxide contains secondary aggregates.
  • the particle diameter of the secondary aggregate contained in the metal oxide is 150 nm or less.
  • the particle diameter means (b) the distribution of metal oxide.
  • the particle size of the secondary aggregate contained in the metal oxide is preferably 5 to 150 nm from the viewpoint of higher hardness and excellent optical characteristics.
  • a metal oxide contains 1 mass% or more of secondary aggregates having a particle diameter of 100 nm or more in the total amount of (b) metal oxide. From the viewpoint that (b) the metal oxide has higher hardness and excellent optical properties, it is preferable that the secondary aggregate having a particle diameter of 100 nm or more is contained in 1 to 10% by mass in the total amount of (b) metal oxide. It is more preferably ⁇ 7% by mass, and further preferably 3 ⁇ 5% by mass. Further, secondary aggregates having a particle size of 100 to 150 nm are preferably contained in 1 to 10% by mass of the total amount of (b) metal oxide, more preferably 3 to 7% by mass, and more preferably 3 to 5% by mass. Is more preferable. (B) It is mentioned as one of the aspects with preferable that a metal oxide does not contain primary particles with a particle diameter of 100 nm or more.
  • the metal oxide may further contain primary particles.
  • metal oxide containing the metal oxide of particle diameter less than 100 nm includes primary particles and / or secondary aggregates of the metal oxide.
  • the primary particles of the metal oxide include, for example, a raw material metal oxide used in producing the composition of the present invention, and primary particles dispersed from the secondary aggregate formed in producing the composition of the present invention. Is mentioned.
  • the metal oxide preferably contains primary particles and secondary aggregates at a particle diameter of less than 100 nm.
  • the particle diameter of the primary particles at a particle diameter of less than 100 nm is preferably 30 nm or less from the viewpoint of higher hardness and excellent optical properties.
  • the particle diameter of the secondary aggregate when the particle diameter is less than 100 nm is preferably 70 nm or less, more preferably 5 to 70 nm from the viewpoint of higher hardness and excellent optical characteristics.
  • the metal oxide preferably contains 99% by mass or less of the metal oxide having a particle diameter of less than 100 nm in the total amount of (b) the metal oxide. 99% by mass is more preferable, 93 to 97% by mass is further preferable, and 95 to 97% by mass is particularly preferable.
  • the metal oxide has higher hardness and excellent optical properties
  • the metal oxide contains a metal oxide having a particle diameter of 30 nm or less in a total amount of (b) 60 to 90% by mass or less. 70 to 85% by mass is more preferable.
  • the metal oxide may not contain a secondary aggregate having a particle diameter of more than 150 nm, or may contain a secondary aggregate having a particle diameter of more than 150 nm.
  • the amount of the secondary aggregate having a particle diameter exceeding 150 nm is preferably 0 to 10% by mass in the total amount of the metal oxide (b) from the viewpoint of higher hardness and excellent optical properties. More preferably, it is ⁇ 5% by mass.
  • a metal oxide having a primary average particle diameter of 35 nm or less is used as a starting metal oxide used in producing a metal oxide, which has higher hardness and excellent optical characteristics. It is preferable from the viewpoint.
  • the primary average particle diameter of the raw material metal oxide is more preferably 30 nm or less, and further preferably 20 nm or less.
  • the raw metal oxide does not include those having a particle diameter of 100 nm or more.
  • the raw material metal oxide includes the same components as the metal oxide (b).
  • the metal oxide has an ethylenically unsaturated group
  • a surface-treated one such as when the metal oxide is hydrophobized
  • these can be produced by applying a surface treatment agent such as a silane coupling agent having a (meth) acryloyloxy group or a hydrophobic treatment agent.
  • An organic solvent can be used in the production, and examples of the organic solvent (b) used in producing the metal oxide include the same as the organic solvent (d) described later.
  • the amount of the organic solvent used in producing the metal oxide can be added to the amount of (d) the organic solvent described later, and the amount can be used in the present invention.
  • a metal oxide can be used individually or in combination of 2 types or more, respectively.
  • the photopolymerization initiator will be described below.
  • the photopolymerization initiator (c) contained in the composition of the present invention is not particularly limited as long as the monomer can be polymerized by light.
  • Examples of the photopolymerization initiator (c) include acetophenone compounds, benzoin ether compounds, benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, phosphine oxide compounds, and the like.
  • benzoin benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone Methylphenylglyoxylate, ethylphenylglyoxylate, 4,4'-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1, Carbonyl compounds such as 2-diphenylethane-1-one and 1-hydroxycyclohexyl phenyl ketone; Sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; Azobis Sobuchironitoriru, azo compounds such as azobis
  • 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1- are preferable in terms of light stability, high efficiency of photocleavage, surface curability, compatibility with resins, low volatility, and low odor.
  • Phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one is preferred.
  • (C) can be used alone or in combination of two or more.
  • the organic solvent will be described below.
  • the organic solvent (d) contained in the composition of the present invention include ketones such as methyl ethyl ketone (MEK) and methyl isobutyketone (MIBK); propylene glycol monomethyl ether (PGME), and isopropyl alcohol (IPA). Such alcohols.
  • the organic solvent (d) can be at least one selected from the group consisting of these. Of these, MEK and MIBK are preferred from the viewpoint of excellent drying properties and paintability.
  • the composition of the present invention comprises 10 to 10% of (a) in the total amount of the composition (in the present invention, this can be the sum of (a), (b), (c) and (d), the same shall apply hereinafter).
  • the amount of (a) is preferably 15 to 60% by mass, more preferably 20 to 50% by mass.
  • the composition of the present invention contains 5 to 75% by weight of (b) in the total amount of the composition, and the amount of (b) is 10 to 75% by mass from the viewpoint of higher hardness and excellent optical properties. It is preferably 15 to 30% by mass.
  • the composition of the present invention contains (c) in an amount of 0.1 to 10% by weight in the total amount of the composition, and from the viewpoint of higher hardness and excellent optical properties, the amount of (c) is 1 to 8% by weight. It is preferably 1 to 6% by mass.
  • the amount of (d) the organic solvent can be 5 to 60% by mass based on the total amount of the composition.
  • composition of the present invention is, for example, an ethylenic compound other than (a), a metal oxide other than (b), an anti-aging agent, an antistatic agent, a flame retardant, and adhesiveness, as long as the object of the present invention is not impaired. It may further contain additives such as an imparting agent, a dispersing agent, an antioxidant, an antifoaming agent, a leveling agent, a matting agent, a light stabilizer, a dye and a pigment.
  • additives such as an imparting agent, a dispersing agent, an antioxidant, an antifoaming agent, a leveling agent, a matting agent, a light stabilizer, a dye and a pigment.
  • a method for producing the composition of the present invention for example, (a), a raw metal oxide having a primary average particle diameter of 10 to 35 nm, (c), (d), and an additive that can be used as necessary.
  • ultrasonic waves are applied to a mixture of at least (a) and a raw metal oxide having a primary average particle diameter of 10 to 35 nm from the viewpoint of higher hardness, excellent reactivity with a resin, and excellent optical characteristics. Is preferably irradiated.
  • a component other than (a) or the raw metal oxide is mixed with the raw metal oxide to obtain a mixture.
  • a component other than (a) or the raw metal oxide is mixed with the raw metal oxide to obtain a mixture.
  • the metal oxide secondary aggregate has a particle size larger than that of the raw metal oxide, and the particle size distribution of the metal oxide spreads in a direction in which the particle size increases more than the particle size distribution of the raw metal oxide.
  • the raw material metal oxide appropriately aggregates the primary particles to make it (b) a metal oxide, and has a primary average particle diameter from the viewpoint of higher hardness and excellent optical properties. Is preferably 10 to 35 nm, more preferably 10 to 30 nm, and even more preferably 10 to 20 nm.
  • the raw material metal oxide can appropriately aggregate the primary particles to form (b) a metal oxide, and does not contain secondary aggregates from the viewpoint of higher hardness and excellent optical properties. It is mentioned as one of the preferable aspects.
  • the starting metal oxide can be the same as (b) except that the primary particle diameter is 10 to 35 nm and does not contain secondary aggregates.
  • the amount of raw material metal oxide used can be the same as in (b).
  • the frequency can be obtained by appropriately agglomerating the raw metal oxide to form (b) a metal oxide, from the viewpoint of higher hardness and excellent optical characteristics. 20 to 200 kHz is preferable, and 40 to 100 kHz is preferable.
  • the output is preferably 50 W or more, and preferably 50 to 100 W.
  • the ultrasonic irradiation time is preferably 1 to 120 minutes, and preferably 5 to 30 minutes, for the same reason as the frequency.
  • the apparatus used for irradiating ultrasonic waves is not particularly limited. For example, a conventionally well-known thing is mentioned.
  • the composition of the present invention can be used as, for example, a plastic surface protective agent, a hard coat agent, an ultraviolet curable coating material, a primer composition, and the like.
  • the substrate to which the composition of the present invention can be applied is not particularly limited. Examples thereof include plastic, rubber, glass, metal, ceramic, and polyethylene terephthalate (PET) film.
  • PET polyethylene terephthalate
  • the plastic to which the composition of the present invention can be applied may be either a thermosetting resin or a thermoplastic resin.
  • plastics include poor adhesion such as polymethyl methacrylate resin (PMMA resin), polycarbonate resin, polystyrene resin, acrylonitrile / styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, polyamide resin. Resin.
  • the method for applying the composition of the present invention to the substrate is not particularly limited, and for example, a known coating method such as brush coating, flow coating, dip coating, spray coating, spin coating or the like can be employed.
  • Examples of the curing method of the composition of the present invention include a curing method using ultraviolet rays.
  • the irradiation amount of the ultraviolet light used for curing the composition of the present invention is 500 to 3,000 mJ / cm 2 from the viewpoint of fast curability and workability. Is preferred.
  • the apparatus used for irradiating ultraviolet rays is not particularly limited. For example, a conventionally well-known thing is mentioned. Heating may be used in combination for curing.
  • the composition of the present invention has high hardness and excellent optical properties (transparency).
  • the pencil hardness is preferably 6H or more, and more preferably 7H or more.
  • the laminate of the present invention will be described below.
  • the laminated body of this invention is a laminated body which has a base material and the resin layer obtained using the curable resin composition of this invention on the said base material.
  • the base material and curable resin composition used in the laminate of the present invention are the same as described above.
  • the laminate of the present invention is not particularly limited for its production. For example, it can be obtained by applying the composition of the present invention to a substrate and curing it.
  • FIG. 1 is a cross-sectional view schematically showing a cross section of an example of a laminate of the present invention.
  • the laminate 100 includes a resin layer 102 and a base material 104.
  • the thickness of the resin layer and the substrate is not particularly limited. Since the laminate of the present invention has a resin layer having high hardness and excellent optical properties, it is excellent in transparency. The effects described above are exhibited particularly when the laminate of the present invention has a resin layer on its surface.
  • composition Of the components shown in the following table (units of the amount of each component are parts by mass), the component (a) and the raw metal oxide [containing part of (d)] are mixed in advance to form a mixture. Using a 100W ultrasonic cleaner (three-frequency ultrasonic cleaner MODEL VS-100III, manufactured by ASONE Co., Ltd.), ultrasonic waves were irradiated under the conditions shown in the table, and the mixture after irradiation was subjected to (a) component and raw metal oxidation Components other than the product [(c) and (d) shown in the same table] were added and mixed to produce a composition.
  • a 100W ultrasonic cleaner three-frequency ultrasonic cleaner MODEL VS-100III, manufactured by ASONE Co., Ltd.
  • the upper numerical value of each raw metal oxide is the net amount of the raw metal oxide after being treated with the silane coupling agent or not being treated with the silane coupling agent.
  • the numerical value in the lower parenthesis of the oxide is the amount of the organic solvent used as part of (d).
  • the composition (coating material) obtained as described above was used as a base material [PMMA (polymethyl methacrylate) -PC (polycarbonate) -PMMA (three-layer structure), thickness: 0.65 mm, manufactured by Sumitomo Chemical Co., Ltd.
  • the film thickness is about 25 ⁇ m using a spray gun, dried in an oven at 70 ° C.
  • ethylenic compound 1 DPHA (dipentaerythritol hexaacrylate), manufactured by Sartomer, Inc.
  • ethylenic compound 2 dendrimer type acrylate compound. It has 14 or more functional acryloyloxy groups.
  • Product name Viscoat V # 1000 manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • Ethylene compound 3 urethane acrylate obtained by reacting dipentaerythritol pentaacrylate (DPPA) with hexamethylene diisocyanate (HDI). It has 10 acryloyloxy groups per molecule.
  • Raw metal oxide 1 Trade name MEK-Ac-2101 (acrylic-treated colloidal silica, manufactured by Nissan Chemical Industries, average primary particle size: 10-20 nm) 30 parts by mass (of acrylic-treated colloidal silica Net amount), 3-acryloyloxypropyltrimethoxysilane (5 parts by mass, trade name KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent having a (meth) acryloyloxy group, and methyl ethyl ketone as an organic solvent (70 parts by mass) was reacted under stirring at 80 ° C.
  • MEK-Ac-2101 acrylic-treated colloidal silica, manufactured by Nissan Chemical Industries, average primary particle size: 10-20 nm
  • 3-acryloyloxypropyltrimethoxysilane 5 parts by mass, trade name KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.
  • silane coupling agent having a (meth) acryloyl
  • the obtained raw metal oxide 1 contains 33.3% by mass of silica treated with the present silane coupling agent, and 66.7% by mass of methyl ethyl ketone as an organic solvent.
  • the above-described ultrasonic irradiation causes the primary oxide among the metal oxides having a particle diameter of 10 to 30 nm in the mixture after ultrasonic irradiation. It is considered that about 50% by mass of the amount of the metal oxide having a particle diameter of 10 to 30 nm is contained in the form dispersed in the particles.
  • Raw material metal oxide 2 A silane coupling agent was treated in the same manner as raw material metal oxide 1 except that Al 2 O 3 particles (CIK Nanotech, average primary particle size: 10-31 nm) were used. A raw material metal oxide 2 was produced. Although details are unknown, when the raw material metal oxide 2 is used, the above-described ultrasonic irradiation causes a primary oxide among the metal oxides having a particle diameter of 10 to 30 nm in the mixture after ultrasonic irradiation. It is considered that about 50% by mass of the amount of the metal oxide having a particle diameter of 10 to 30 nm is contained in the form dispersed in the particles.
  • Raw material metal oxide 3 Trade name MEK-ST (No surface treatment, colloidal silica manufactured by Nissan Chemical Industries, average primary particle size: 10-20 nm) Although details are unknown, raw material metal oxide 3
  • 10-30 nm particles of metal oxide having a particle diameter of 10-30 nm are dispersed to primary particles. It is considered that about 50 mass% of the amount of the metal oxide having a diameter is contained.
  • C-1 Photopolymerization initiator 1: Irgacure 184 (manufactured by BASF), 1-hydroxy-cyclohexyl-phenyl-ketone (d-1)
  • Comparative Examples 1 to 3 not containing secondary aggregates of 100 nm or more had a low pass rate of the pencil hardness test.
  • Comparative Example 2 since the ultrasonic treatment is not sufficient, it is considered that secondary aggregates of 100 nm or more are not generated.
  • Comparative Example 3 it is considered that the secondary aggregates were dispersed because the ultrasonic treatment was too strong.
  • Comparative Example 4 In Comparative Example 4 containing no metal oxide, the pass rate of the pencil hardness test was poor.
  • Comparative Example 5 in which the amount of the metal oxide was less than 5% by mass and no secondary aggregate of 100 nm or more was included, the pass rate of the pencil hardness test was low.
  • Examples 1 to 6 the hardness of the resulting coating was high.
  • Examples 1 to 6 are excellent in transparency and optical characteristics.
  • the composition of the present invention can form a film with high hardness, and is excellent in transparency and optical characteristics.
  • the laminated body of this invention has a resin film which is excellent in the optical characteristic of high hardness, its hardness is high and it is excellent in transparency.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The purpose of the present invention is to provide a curable resin composition which forms a coating film that has high hardness. The present invention provides: a curable resin composition which contains (a) 10-90% by mass of an ethylenic compound having three or more ethylenically unsaturated groups in each molecule, (b) 5-75% by mass of a metal oxide, (c) 0.1-10% by mass of a photopolymerization initiator and (d) an organic solvent, and wherein the metal oxide contains secondary aggregates that have particle diameters of 150 nm or less and the amount of the secondary aggregates having particle diameters of 100 nm or more is 1% by mass or more of the metal oxide (b); and a laminate which uses the curable resin composition.

Description

硬化性樹脂組成物Curable resin composition
 本発明は硬化性樹脂組成物に関する。 The present invention relates to a curable resin composition.
 従来、高い硬度の被膜を形成することを目的とする硬化性樹脂組成物が提案されている(例えば特許文献1)。 Conventionally, a curable resin composition for the purpose of forming a high-hardness film has been proposed (for example, Patent Document 1).
特開2009-292916号公報JP 2009-292916 A
 しかし、本願発明者はシリカ等の金属酸化物を含有する硬化性樹脂組成物は得られる被膜の硬度について改善の余地があることを見出した。
 そこで、本発明は高い硬度を有する被膜となる硬化性樹脂組成物を提供することを目的とする。
However, the present inventor has found that the curable resin composition containing a metal oxide such as silica has room for improvement in the hardness of the resulting film.
Then, an object of this invention is to provide the curable resin composition used as the film which has high hardness.
 本発明者は、上記課題を解決すべく鋭意研究した結果、一次平均粒子径20nmのシリカを配合した組成物(例えばハードコート用)に超音波を当ててシリカを2~5個程度で凝集させることにより、得られるハードコートの硬度が向上することをまず初めに見出し、これについて更に研究を進めて、
(a)分子内にエチレン性不飽和基を3個以上有するエチレン性化合物10~90質量%、
(b)金属酸化物5~75質量%、
(c)光重合開始剤0.1~10質量%、及び
(d)有機溶剤を含有し、
 前記(b)金属酸化物は二次凝集体を含み、前記二次凝集体の粒子径は150nm以下であり、粒子径100nm以上の二次凝集体の量が前記(b)金属酸化物中の1質量%以上である、硬化性樹脂組成物が高い硬度を有する被膜となることを見出し、本発明を完成させた。
As a result of diligent research to solve the above problems, the present inventor applied ultrasonic waves to a composition containing silica having a primary average particle diameter of 20 nm (for example, for hard coat) to aggregate about 2 to 5 silica. First, it was found that the hardness of the hard coat obtained was improved, and further research was conducted on this.
(A) 10 to 90% by mass of an ethylenic compound having 3 or more ethylenically unsaturated groups in the molecule;
(B) 5 to 75% by mass of a metal oxide,
(C) contains 0.1 to 10% by weight of a photopolymerization initiator, and (d) an organic solvent,
The (b) metal oxide contains secondary aggregates, the secondary aggregate has a particle size of 150 nm or less, and the amount of secondary aggregates having a particle size of 100 nm or more is in the (b) metal oxide. The present invention was completed by finding that the curable resin composition of 1% by mass or more has a high hardness.
 すなわち、本発明は、下記1~5を提供する。
 1.(a)分子内にエチレン性不飽和基を3個以上有するエチレン性化合物10~90質量%、
(b)金属酸化物5~75質量%、
(c)光重合開始剤0.1~10質量%、及び
(d)有機溶剤を含有し、
 前記(b)金属酸化物は二次凝集体を含み、前記二次凝集体の粒子径は150nm以下であり、粒子径100nm以上の二次凝集体の量が前記(b)金属酸化物中の1質量%以上である、硬化性樹脂組成物。
 2. 前記(b)金属酸化物が更にエチレン性不飽和基を有する上記1に記載の硬化性樹脂組成物。
 3. 前記(b)金属酸化物が疎水化処理されたものを含む上記1又は2に記載の硬化性樹脂組成物。
 4. 前記(b)金属酸化物が更に一次粒子を含む上記1~3のいずれかに記載の硬化性樹脂組成物。
 5. 基材と、前記基材の上に上記1~4のいずれかに記載の硬化性樹脂組成物を用いて得られる樹脂層とを有する積層体。
That is, the present invention provides the following 1 to 5.
1. (A) 10 to 90% by mass of an ethylenic compound having 3 or more ethylenically unsaturated groups in the molecule;
(B) 5 to 75% by mass of a metal oxide,
(C) contains 0.1 to 10% by weight of a photopolymerization initiator, and (d) an organic solvent,
The (b) metal oxide contains secondary aggregates, the secondary aggregate has a particle size of 150 nm or less, and the amount of secondary aggregates having a particle size of 100 nm or more is in the (b) metal oxide. Curable resin composition which is 1 mass% or more.
2. 2. The curable resin composition according to 1 above, wherein the (b) metal oxide further has an ethylenically unsaturated group.
3. The curable resin composition according to 1 or 2 above, wherein the metal oxide (b) is subjected to a hydrophobic treatment.
4). 4. The curable resin composition as described in any one of 1 to 3 above, wherein (b) the metal oxide further contains primary particles.
5. A laminate comprising a substrate and a resin layer obtained by using the curable resin composition according to any one of 1 to 4 on the substrate.
 本発明の硬化性樹脂組成物は高い硬度を有する被膜となる。
 本発明の積層体は高い硬度の樹脂層を有する。
The curable resin composition of the present invention becomes a film having high hardness.
The laminate of the present invention has a high hardness resin layer.
図1は本発明の積層体の一例を模式的に表す断面図である。FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention.
 本発明について以下詳細に説明する。
 本発明の硬化性樹脂組成物(本発明の組成物)は、
(a)分子内にエチレン性不飽和基を3個以上有するエチレン性化合物10~90質量%、
(b)金属酸化物5~75質量%、
(c)光重合開始剤0.1~10質量%、及び
(d)有機溶剤を含有し、
 前記(b)金属酸化物は二次凝集体を含み、前記二次凝集体の粒子径は150nm以下であり、粒子径100nm以上の二次凝集体の量が前記(b)金属酸化物中の1質量%以上である、硬化性樹脂組成物である。
The present invention will be described in detail below.
The curable resin composition of the present invention (the composition of the present invention)
(A) 10 to 90% by mass of an ethylenic compound having 3 or more ethylenically unsaturated groups in the molecule;
(B) 5 to 75% by mass of a metal oxide,
(C) contains 0.1 to 10% by weight of a photopolymerization initiator, and (d) an organic solvent,
The (b) metal oxide contains secondary aggregates, the secondary aggregate has a particle size of 150 nm or less, and the amount of secondary aggregates having a particle size of 100 nm or more is in the (b) metal oxide. The curable resin composition is 1% by mass or more.
 (a)エチレン性化合物について以下に説明する。本発明の組成物に含有される(a)エチレン性化合物[これを以下(a)成分又は(a)ということがある。本発明の組成物に含有される成分をこのように表記することは(b)~(d)についても同様である。]は、1分子内にエチレン性不飽和基を3個以上有する化合物である。
 エチレン性不飽和基は-C=C-を有するものであれば特に制限されない。エチレン性不飽和基は-C=C-の他に、例えば、水素原子;酸素原子、窒素原子、硫黄原子のようなヘテロ原子を有することができる炭化水素基;カルボニル基;カルボニルオキシ基を有することができる。エチレン性不飽和基としては、例えば、ビニル基、(メタ)アクリロイル基[CH2=CR-CO-(Rは水素原子又はメチル基)]、(メタ)アクリロイルオキシ基[CH2=CR-CO-O-(Rは水素原子又はメチル基)]、ビニル芳香族炭化水素基、CH(-COOR1)=CH-CO-O-(R1は炭化水素基である。)、CH3COO―CH=CH―が挙げられる。本発明において(メタ)アクリロイルはアクリロイル及びメタクリロイルのうちの一方又は両方であることを意味する。
 (a)エチレン性化合物は、1分子内にエチレン性不飽和基を3~14個有することができる。(a)エチレン性化合物は、1分子内にヒドロキシ基を1つ以上有してもよい。また(a)エチレン性化合物は、1分子内にヒドロキシ基を有さないものとすることができる。
 (a)成分が有するエチレン性不飽和基以外の構造としては、例えば、酸素原子、窒素原子、硫黄原子のようなヘテロ原子を有してもよい炭化水素基が挙げられる。
(A) The ethylenic compound will be described below. (A) an ethylenic compound contained in the composition of the present invention [this may hereinafter be referred to as component (a) or (a). The description of the components contained in the composition of the present invention in this way is the same for (b) to (d). ] Is a compound having 3 or more ethylenically unsaturated groups in one molecule.
The ethylenically unsaturated group is not particularly limited as long as it has —C═C—. In addition to —C═C—, the ethylenically unsaturated group has, for example, a hydrogen atom; a hydrocarbon group that can have a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom; a carbonyl group; a carbonyloxy group be able to. Examples of the ethylenically unsaturated group include a vinyl group, a (meth) acryloyl group [CH 2 ═CR—CO— (R is a hydrogen atom or a methyl group)], a (meth) acryloyloxy group [CH 2 ═CR—CO —O— (R is a hydrogen atom or a methyl group)], a vinyl aromatic hydrocarbon group, CH (—COOR 1 ) ═CH—CO—O— (R 1 is a hydrocarbon group), CH 3 COO— CH = CH-. In the present invention, (meth) acryloyl means one or both of acryloyl and methacryloyl.
(A) The ethylenic compound can have 3 to 14 ethylenically unsaturated groups in one molecule. (A) The ethylenic compound may have one or more hydroxy groups in one molecule. In addition, (a) the ethylenic compound may have no hydroxy group in one molecule.
(A) As a structure other than the ethylenically unsaturated group which component has, the hydrocarbon group which may have hetero atoms, such as an oxygen atom, a nitrogen atom, and a sulfur atom, is mentioned, for example.
 (a)エチレン性化合物としては例えば、多価アルコールの(メタ)アクリル酸エステル、ウレタン(メタ)アクリレートが挙げられる。(a)エチレン性化合物はこれらのデンドリマータイプであってもよい。
 多価アルコールの(メタ)アクリル酸エステルとしては、例えば、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールトリ(メタ)アクリレートのような3官能系;ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、トリペンタエリスリトールテトラ(メタ)アクリレートのような4官能系;ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリペンタエリスリトールペンタ(メタ)アクリレート、トリペンタエリスリトールヘキサ(メタ)アクリレート、トリペンタエリスリトールヘプタ(メタ)アクリレート、トリペンタエリスリトールオクタ(メタ)アクリレートのような5官能以上の系が挙げられる。
Examples of (a) ethylenic compounds include (meth) acrylic acid esters of polyhydric alcohols and urethane (meth) acrylates. (A) These dendrimer types may be sufficient as an ethylenic compound.
Examples of polyhydric alcohol (meth) acrylic acid esters include trifunctional groups such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol tri (meth) acrylate; pentaerythritol tetra Tetrafunctional system such as (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate; dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol Penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol o Data (meth) 5 or higher functional systems such as acrylate.
 (a)成分として使用することができるウレタン(メタ)アクリレートとしては、例えば、多価アルコールの(メタ)アクリル酸エステル(この場合、多価アルコールの(メタ)アクリル酸エステルは例えば、少なくとも1つのヒドロキシ基を有する。)とポリイソシアネート化合物との反応物が挙げられる。
 ウレタン(メタ)アクリレートを製造する際に使用される多価アルコールの(メタ)アクリル酸エステルとしては例えば上記と同様のものが挙げられる。
 ウレタン(メタ)アクリレートを製造する際に使用される、ポリイソシアネート化合物としては、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、フェニレンジイソシアネート、ポリメチレンポリフェニレンポリイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、トリジンジイソシアネート、1,5-ナフタレンジイソシアネート、トリフェニルメタントリイソシアネートのような芳香族系ポリイソシアネート;ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、ノルボルナンジイソシアネート、トランスシクロヘキサン-1,4-ジイソシアネート、イソホロンジイソシアネート、ビス(イソシアネートメチル)シクロヘキサン、ジシクロヘキシルメタンジイソシアネートのような脂肪族系ポリイソシアネート(鎖状及び/又は脂環式系を含む。);これらのイソシアヌレート体、ビューレット体、アダクト体が挙げられる。
 ウレタン(メタ)アクリレート1分子が有するエチレン性不飽和基の数は3~15個であるのがより好ましい。
As the urethane (meth) acrylate that can be used as the component (a), for example, a (meth) acrylic acid ester of a polyhydric alcohol (in this case, the (meth) acrylic acid ester of a polyhydric alcohol is, for example, at least one And a reaction product of a polyisocyanate compound.
Examples of the (meth) acrylic acid ester of polyhydric alcohol used when producing urethane (meth) acrylate include the same as described above.
Examples of the polyisocyanate compound used in producing urethane (meth) acrylate include tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and tolidine diisocyanate. Aromatic polyisocyanates such as 1,5-naphthalene diisocyanate and triphenylmethane triisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis (Isocyanate methyl) Cyclohexane, (including linear and / or cycloaliphatic systems.) Aliphatic polyisocyanates such as dicyclohexylmethane diisocyanate; these isocyanurate, biuret body, adduct thereof.
The number of ethylenically unsaturated groups contained in one molecule of urethane (meth) acrylate is more preferably 3-15.
 (a)成分はなかでも、硬度がより高く、光学特性に優れるという観点から、ジペンタエリスリトールヘキサ(メタ)アクリレートのような1分子内にエチレン性不飽和基を3~6個有する化合物;1分子内にエチレン性不飽和基を7~14個有する化合物(デンドリマータイプであってもよい。);ウレタン(メタ)アクリレートが好ましい。
 (a)成分はそれぞれ単独でまたは2種以上を組み合わせて使用することができる。
 (a)成分として、1分子内にエチレン性不飽和基を3~6個有する化合物と1分子内にエチレン性不飽和基を7~14個有する化合物とを併用する場合、1分子内にエチレン性不飽和基を7~14個有する化合物の量は、硬度がより高く、光学特性に優れるという観点から、1分子内にエチレン性不飽和基を3~6個有する化合物100質量部に対して、10~50質量部であるのが好ましく、15~35質量部であるのがより好ましい。
 (a)成分として、多価アルコールの(メタ)アクリル酸エステルとウレタン(メタ)アクリレートとを併用する場合、硬度がより高く、光学特性に優れるという観点から、多価アルコールの(メタ)アクリル酸エステルは、1分子内にエチレン性不飽和基を3~14個有すること、ヒドロキシ基を有さないこと(例えば多価アルコールのすべてのヒドロキシ基が(メタ)アクリル酸エステル化されている。)が好ましく、1分子内にエチレン性不飽和基を3~6個有し、かつ、ヒドロキシ基を有さないのがより好ましい。多価アルコールの(メタ)アクリル酸エステルとウレタン(メタ)アクリレートとの量比は、多価アルコールの(メタ)アクリル酸エステル100質量部に対して、ウレタン(メタ)アクリレートが、20~150質量部であるのが好ましく、40~120質量部であるのがより好ましい。
 (a)成分はその製造について特に制限されない。例えば従来公知のものが挙げられる。(a)はそれぞれ単独でまたは2種以上を組み合わせて使用することができる。
Among the components (a), a compound having 3 to 6 ethylenically unsaturated groups in one molecule such as dipentaerythritol hexa (meth) acrylate from the viewpoint of higher hardness and excellent optical properties; A compound having 7 to 14 ethylenically unsaturated groups in the molecule (may be a dendrimer type); urethane (meth) acrylate is preferred.
(A) A component can be used individually or in combination of 2 types or more, respectively.
(A) When a compound having 3 to 6 ethylenically unsaturated groups in one molecule and a compound having 7 to 14 ethylenically unsaturated groups in one molecule are used in combination as components (a), The amount of the compound having 7 to 14 ethylenically unsaturated groups is based on 100 parts by mass of the compound having 3 to 6 ethylenically unsaturated groups in one molecule from the viewpoint of higher hardness and excellent optical properties. The amount is preferably 10 to 50 parts by mass, and more preferably 15 to 35 parts by mass.
(A) When (meth) acrylic acid ester of polyhydric alcohol and urethane (meth) acrylate are used together as component (a), (meth) acrylic acid of polyhydric alcohol from the viewpoint of higher hardness and excellent optical properties The ester has 3 to 14 ethylenically unsaturated groups in one molecule and does not have a hydroxy group (for example, all hydroxy groups of a polyhydric alcohol are (meth) acrylic ester). It is more preferable to have 3 to 6 ethylenically unsaturated groups in one molecule and no hydroxy group. The amount ratio of the (meth) acrylic acid ester of the polyhydric alcohol and the urethane (meth) acrylate is 20 to 150 masses of urethane (meth) acrylate with respect to 100 mass parts of the (meth) acrylic acid ester of the polyhydric alcohol. Part is preferable, and 40 to 120 parts by mass is more preferable.
The component (a) is not particularly limited for its production. For example, a conventionally well-known thing is mentioned. (A) can be used individually or in combination of 2 or more types.
 (b)金属酸化物について以下に説明する。本発明の組成物に含有される(b)金属酸化物は、前記金属酸化物は二次凝集体を含み、前記二次凝集体の粒子径は150nm以下であり、粒子径100nm以上の二次凝集体の量が前記金属酸化物中の1質量%以上である。
 (b)金属酸化物は金属の酸化物である。具体的には例えば、シリカ、酸化アルミニウム(アルミナ)、酸化チタン(チタニア)、酸化亜鉛、酸化錫、酸化セリウムなどが挙げられる。(b)金属酸化物は、硬度がより高く、樹脂や溶剤への分散性に優れ、光学特性に優れるという観点から、シリカが好ましい。シリカはシラノール基を有するものであれば特に制限されない。シリカは無処理のもの、表面処理等がなされているものを含む。シリカとしては例えば、コロイダルシリカが挙げられる。
(B) The metal oxide will be described below. The metal oxide (b) contained in the composition of the present invention is such that the metal oxide contains a secondary aggregate, and the secondary aggregate has a particle size of 150 nm or less and a secondary particle size of 100 nm or more. The amount of the aggregate is 1% by mass or more in the metal oxide.
(B) The metal oxide is a metal oxide. Specific examples include silica, aluminum oxide (alumina), titanium oxide (titania), zinc oxide, tin oxide, and cerium oxide. (B) The metal oxide is preferably silica from the viewpoint of higher hardness, excellent dispersibility in a resin or solvent, and excellent optical properties. Silica is not particularly limited as long as it has a silanol group. Silica includes untreated ones, surface treated ones and the like. Examples of silica include colloidal silica.
 (b)金属酸化物は、硬度がより高く、樹脂との反応性に優れ、光学特性に優れるという観点から、更にエチレン性不飽和基を有するのが好ましい。
(b)金属酸化物が更に有することができるエチレン性不飽和基としては例えば、(a)が有するエチレン性不飽和基と同様のものが挙げられる。(b)金属酸化物に更にエチレン性不飽和基を導入する際に使用される化合物としては例えば、(メタ)アクリロイルオキシ基[(メタ)アクリル基ともいう。]を有するシランカップリング剤が挙げられる。(メタ)アクリロイルオキシ基を有するシランカップリング剤は、(メタ)アクリロイルオキシ基及び加水分解性シリル基を少なくとも有する化合物であれば特に制限されない。(メタ)アクリロイルオキシ基と加水分解性シリル基とは例えば、有機基を介して結合することができる。有機基としては例えば、酸素原子、窒素原子、硫黄原子のようなヘテロ原子を有してもよい炭化水素基が挙げられる。炭化水素基としては、例えば、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、これらの組み合わせが挙げられる。(メタ)アクリロイルオキシ基を有するシランカップリング剤としては、例えば、3-(メタ)アクリロイルオキシプロピルメチルジメトキシシラン、3-(メタ)アクリロイルオキシプロピルトリメトキシシラン、3-(メタ)アクリロイルオキシプロピルメチルジエトキシシラン、3-(メタ)アクリロイルオキシプロピルトリエトキシシランのような、(メタ)アクリロイルオキシアルキルジアルコキシシシラン、(メタ)アクリロイルオキシアルキルトリアルコキシシシランが挙げられる。なかでも、光学特性に優れ、初期密着性、耐摩耗性に優れ、硬度がより高いという観点から、3-(メタ)アクリロイルオキシプロピルトリメトキシシランが好ましい。
 エチレン性不飽和基を有する金属酸化物は、例えば、(メタ)アクリロイルオキシ基を有するシランカップリング剤とシリカ(例えば無処理のシリカ)とを反応させることによって得ることができる。
(B) It is preferable that the metal oxide further has an ethylenically unsaturated group from the viewpoints of higher hardness, excellent reactivity with the resin, and excellent optical characteristics.
(B) As an ethylenically unsaturated group which a metal oxide can have further, the thing similar to the ethylenically unsaturated group which (a) has is mentioned, for example. (B) As a compound used when introduce | transducing an ethylenically unsaturated group further into a metal oxide, it is also called a (meth) acryloyloxy group [(meth) acryl group, for example. A silane coupling agent having The silane coupling agent having a (meth) acryloyloxy group is not particularly limited as long as it is a compound having at least a (meth) acryloyloxy group and a hydrolyzable silyl group. The (meth) acryloyloxy group and the hydrolyzable silyl group can be bonded via, for example, an organic group. Examples of the organic group include a hydrocarbon group that may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. Examples of the silane coupling agent having a (meth) acryloyloxy group include 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, and 3- (meth) acryloyloxypropylmethyl. (Meth) acryloyloxyalkyl dialkoxy silanes such as diethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane, and (meth) acryloyloxyalkyltrialkoxysilanes. Of these, 3- (meth) acryloyloxypropyltrimethoxysilane is preferred from the viewpoints of excellent optical properties, excellent initial adhesion and wear resistance, and higher hardness.
The metal oxide having an ethylenically unsaturated group can be obtained, for example, by reacting a silane coupling agent having a (meth) acryloyloxy group with silica (for example, untreated silica).
 (b)金属酸化物は硬度がより高く、光学特性に優れるという観点から、疎水化処理されたものであるのが好ましい。(b)金属酸化物を疎水化処理する際に使用される疎水化処理剤としては、例えば、トリメチルシランやクロロトリメチルシラン(トリメチルシリル基含有化合物全般)、3-(メタ)アクリロイルオキシプロピルトリメトキシシランのような上記に挙げられている(メタ)アクリロイルオキシ基を有するシランカップリング剤などが挙げられる。なかでも光学特性に優れ、初期密着性、耐摩耗性に優れ、反応性に優れ、硬度がより高いという観点から、3-(メタ)アクリロイルオキシプロピルトリメトキシシランが好ましい。
 疎水化処理された金属酸化物は、例えば、疎水化処理剤とシリカ(例えば無処理のシリカ)とを反応させることによって得ることができる。
The metal oxide (b) is preferably hydrophobized from the viewpoint of higher hardness and excellent optical properties. (B) Hydrophobizing agents used for hydrophobizing metal oxides include, for example, trimethylsilane, chlorotrimethylsilane (generally trimethylsilyl group-containing compounds), 3- (meth) acryloyloxypropyltrimethoxysilane And silane coupling agents having a (meth) acryloyloxy group as mentioned above. Of these, 3- (meth) acryloyloxypropyltrimethoxysilane is preferred from the viewpoints of excellent optical properties, excellent initial adhesion and wear resistance, excellent reactivity, and higher hardness.
The hydrophobized metal oxide can be obtained, for example, by reacting a hydrophobizing agent with silica (for example, untreated silica).
 (b)金属酸化物の形状としては例えば粒子状が挙げられる。
 本発明において(b)金属酸化物は二次凝集体を含む。本発明の組成物は(b)金属酸化物が二次凝集体を含むことによって硬度が高く、光学特性に優れる。(b)金属酸化物に含まれる二次凝集体の粒子径は150nm以下である。ここで本発明において粒子径は(b)金属酸化物の分布を意味する。
 (b)金属酸化物に含まれる二次凝集体の粒子径は硬度がより高く、光学特性に優れるという観点から、5~150nmであるのが好ましい。
(B) As a shape of a metal oxide, a particulate form is mentioned, for example.
In the present invention, (b) the metal oxide contains secondary aggregates. The composition of the present invention has high hardness and excellent optical properties because the (b) metal oxide contains secondary aggregates. (B) The particle diameter of the secondary aggregate contained in the metal oxide is 150 nm or less. Here, in the present invention, the particle diameter means (b) the distribution of metal oxide.
(B) The particle size of the secondary aggregate contained in the metal oxide is preferably 5 to 150 nm from the viewpoint of higher hardness and excellent optical characteristics.
 (b)金属酸化物は粒子径100nm以上の二次凝集体を(b)金属酸化物全量中1質量%以上含む。(b)金属酸化物は硬度がより高く、光学特性に優れるという観点から、粒子径100nm以上の二次凝集体を、(b)金属酸化物全量中1~10質量%含むのが好ましく、3~7質量%であるのがより好ましく、3~5質量%であるのがさらに好ましい。
 また粒子径100~150nmの二次凝集体を、(b)金属酸化物全量中1~10質量%含むのが好ましく、3~7質量%であるのがより好ましく、3~5質量%であるのがさらに好ましい。
 (b)金属酸化物は粒子径100nm以上一次粒子を含まないのが好ましい態様の1つとして挙げられる。
(B) A metal oxide contains 1 mass% or more of secondary aggregates having a particle diameter of 100 nm or more in the total amount of (b) metal oxide. From the viewpoint that (b) the metal oxide has higher hardness and excellent optical properties, it is preferable that the secondary aggregate having a particle diameter of 100 nm or more is contained in 1 to 10% by mass in the total amount of (b) metal oxide. It is more preferably ˜7% by mass, and further preferably 3˜5% by mass.
Further, secondary aggregates having a particle size of 100 to 150 nm are preferably contained in 1 to 10% by mass of the total amount of (b) metal oxide, more preferably 3 to 7% by mass, and more preferably 3 to 5% by mass. Is more preferable.
(B) It is mentioned as one of the aspects with preferable that a metal oxide does not contain primary particles with a particle diameter of 100 nm or more.
 本発明において(b)金属酸化物は更に一次粒子を含むことができる。
 また、(b)金属酸化物は粒子径100nm未満の金属酸化物を含むのが好ましい態様の1つとして挙げられる。
 ここで、粒子径100nm未満の金属酸化物には、金属酸化物の一次粒子及び/又は二次凝集体が含まれる。金属酸化物の一次粒子としては、例えば、本発明の組成物を製造する際に使用される原料金属酸化物、本発明の組成物を製造する際に生成した二次凝集体から分散した一次粒子が挙げられる。
In the present invention, (b) the metal oxide may further contain primary particles.
Moreover, it is mentioned as one of the aspects with preferable (b) metal oxide containing the metal oxide of particle diameter less than 100 nm.
Here, the metal oxide having a particle diameter of less than 100 nm includes primary particles and / or secondary aggregates of the metal oxide. Examples of the primary particles of the metal oxide include, for example, a raw material metal oxide used in producing the composition of the present invention, and primary particles dispersed from the secondary aggregate formed in producing the composition of the present invention. Is mentioned.
 (b)金属酸化物は硬度がより高く、光学特性に優れるという観点から、粒子径100nm未満において、一次粒子及び二次凝集体を含むのが好ましい。
 粒子径100nm未満における、一次粒子の粒子径は硬度がより高く、光学特性に優れるという観点から、30nm以下であるのが好ましい。
 粒子径100nm未満における、二次凝集体の粒子径は硬度がより高く、光学特性に優れるという観点から、70nm以下であるのが好ましく、5~70nmであるのがより好ましい。
 (b)金属酸化物は硬度がより高く、光学特性に優れるという観点から、粒子径100nm未満の金属酸化物を、(b)金属酸化物全量中、99質量%以下含むのが好ましく、90~99質量%がより好ましく、93~97質量%であるのがさらに好ましく、95~97質量%であるのが特に好ましい。
(B) From the viewpoint of higher hardness and excellent optical properties, the metal oxide preferably contains primary particles and secondary aggregates at a particle diameter of less than 100 nm.
The particle diameter of the primary particles at a particle diameter of less than 100 nm is preferably 30 nm or less from the viewpoint of higher hardness and excellent optical properties.
The particle diameter of the secondary aggregate when the particle diameter is less than 100 nm is preferably 70 nm or less, more preferably 5 to 70 nm from the viewpoint of higher hardness and excellent optical characteristics.
(B) From the viewpoint of higher hardness and excellent optical properties, the metal oxide preferably contains 99% by mass or less of the metal oxide having a particle diameter of less than 100 nm in the total amount of (b) the metal oxide. 99% by mass is more preferable, 93 to 97% by mass is further preferable, and 95 to 97% by mass is particularly preferable.
 (b)金属酸化物は硬度がより高く、光学特性に優れるという観点から、粒子径30nm以下の金属酸化物を、(b)金属酸化物全量中、60~90質量%以下含むのが好ましく、70~85質量%がより好ましい。 From the viewpoint that (b) the metal oxide has higher hardness and excellent optical properties, it is preferable that the metal oxide contains a metal oxide having a particle diameter of 30 nm or less in a total amount of (b) 60 to 90% by mass or less. 70 to 85% by mass is more preferable.
 (b)金属酸化物は、150nmを超える粒子径を有する二次凝集体を含まない、又は、さらに150nmを超える粒子径を有する二次凝集体を含むものとすることができる。150nmを超える粒子径を有するの二次凝集体の量は、硬度がより高く、光学特性に優れるという観点から、(b)金属酸化物全量中の0~10質量%であるのが好ましく、0~5質量%であるのがより好ましい。 (B) The metal oxide may not contain a secondary aggregate having a particle diameter of more than 150 nm, or may contain a secondary aggregate having a particle diameter of more than 150 nm. The amount of the secondary aggregate having a particle diameter exceeding 150 nm is preferably 0 to 10% by mass in the total amount of the metal oxide (b) from the viewpoint of higher hardness and excellent optical properties. More preferably, it is ˜5% by mass.
 本発明において、(b)金属酸化物を製造する際に使用される原料金属酸化物として、一次平均粒子径が35nm以下の金属酸化物を使用するのが、硬度がより高く、光学特性に優れるという観点から好ましい。原料金属酸化物の一次平均粒子径は同様の理由から30nm以下であるのより好ましく、20nm以下のであるのが更に好ましい。原料金属酸化物は粒子径100nm以上のものを含まないのが好ましい態様の1つとして挙げられる。
 原料金属酸化物はその成分としては(b)金属酸化物と同様のものが挙げられる。(b)金属酸化物がエチレン性不飽和基を有する場合、(b)金属酸化物が疎水化処理されたものである場合など、表面処理されたものを含む場合は、原料金属酸化物に対して例えば、(メタ)アクリロイルオキシ基を有するシランカップリング剤、疎水化処理剤のような表面処理剤を適用することによってこれらを製造することができる。製造の際には有機溶剤を使用することができ、(b)金属酸化物を製造する際に使用される有機溶剤としては例えば、後述する(d)有機溶剤と同様のものが挙げられる。(b)金属酸化物を製造する際に使用される有機溶剤の量を後述する(d)有機溶剤の量に合算させて、その量を本願発明に使用することができる。
 (b)金属酸化物はそれぞれ単独で又は2種以上を組合わせて使用することができる。
In the present invention, (b) a metal oxide having a primary average particle diameter of 35 nm or less is used as a starting metal oxide used in producing a metal oxide, which has higher hardness and excellent optical characteristics. It is preferable from the viewpoint. For the same reason, the primary average particle diameter of the raw material metal oxide is more preferably 30 nm or less, and further preferably 20 nm or less. One of the preferred embodiments is that the raw metal oxide does not include those having a particle diameter of 100 nm or more.
The raw material metal oxide includes the same components as the metal oxide (b). (B) When the metal oxide has an ethylenically unsaturated group, (b) When the metal oxide includes a surface-treated one, such as when the metal oxide is hydrophobized, For example, these can be produced by applying a surface treatment agent such as a silane coupling agent having a (meth) acryloyloxy group or a hydrophobic treatment agent. An organic solvent can be used in the production, and examples of the organic solvent (b) used in producing the metal oxide include the same as the organic solvent (d) described later. (B) The amount of the organic solvent used in producing the metal oxide can be added to the amount of (d) the organic solvent described later, and the amount can be used in the present invention.
(B) A metal oxide can be used individually or in combination of 2 types or more, respectively.
 (c)光重合開始剤について以下に説明する。本発明の組成物に含有される光重合開始剤(c)は光によってモノマーを重合させうるものであれば特に限定されない。光重合開始剤(c)としては、例えば、アセトフェノン系化合物、ベンゾインエーテル系化合物、ベンゾフェノン系化合物、硫黄化合物、アゾ化合物、パーオキサイド化合物、ホスフィンオキサイド系化合物等が挙げられる。具体的には、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、アセトイン、ブチロイン、トルオイン、ベンジル、ベンゾフェノン、p-メトキシベンゾフェノン、ジエトキシアセトフェノン、α,α-ジメトキシ-α-フェニルアセトフェノン、メチルフェニルグリオキシレート、エチルフェニルグリオキシレート、4,4′-ビス(ジメチルアミノベンゾフェノン)、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、1-ヒドロキシシクロヘキシルフェニルケトンなどのカルボニル化合物;テトラメチルチウラムモノスルフィド、テトラメチルチウラムジスルフィドなどの硫黄化合物;アゾビスイソブチロニトリル、アゾビス-2,4-ジメチルバレロなどのアゾ化合物;ベンゾイルパーオキサイド、ジ-t-ブチルパーオキサイドなどのパーオキサイド化合物等が挙げられる。 (C) The photopolymerization initiator will be described below. The photopolymerization initiator (c) contained in the composition of the present invention is not particularly limited as long as the monomer can be polymerized by light. Examples of the photopolymerization initiator (c) include acetophenone compounds, benzoin ether compounds, benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, phosphine oxide compounds, and the like. Specifically, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone Methylphenylglyoxylate, ethylphenylglyoxylate, 4,4'-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1, Carbonyl compounds such as 2-diphenylethane-1-one and 1-hydroxycyclohexyl phenyl ketone; Sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; Azobis Sobuchironitoriru, azo compounds such as azobis-2,4-dimethylvaleronitrile; benzoyl peroxide, peroxide compounds such as di -t- butyl peroxide and the like.
 なかでも、光安定性、光開裂の高効率性、表面硬化性、樹脂との相溶性、低揮発、低臭気という点から、1-ヒドロキシシクロヘキシルフェニルケトン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オンが好ましい。
 (c)はそれぞれ単独でまたは2種以上を組み合わせて使用することができる。
Among these, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1- are preferable in terms of light stability, high efficiency of photocleavage, surface curability, compatibility with resins, low volatility, and low odor. Phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one is preferred.
(C) can be used alone or in combination of two or more.
 (d)有機溶剤について以下に説明する。本発明の組成物に含有される(d)有機溶剤としては例えば、メチルエチルケトン(MEK)、メチルイソブチケトン(MIBK)のようなケトン類;プロピレングリコールモノメチルエーテル(PGME)、イソプロピルアルコール(IPA)のようなアルコールが挙げられる。有機溶剤(d)はこれらのうちからなる群から選ばれる少なくとも1種とすることができる。なかでも、乾燥性や塗装性に優れるという観点から、MEK、MIBKが好ましい。 (D) The organic solvent will be described below. Examples of the organic solvent (d) contained in the composition of the present invention include ketones such as methyl ethyl ketone (MEK) and methyl isobutyketone (MIBK); propylene glycol monomethyl ether (PGME), and isopropyl alcohol (IPA). Such alcohols. The organic solvent (d) can be at least one selected from the group consisting of these. Of these, MEK and MIBK are preferred from the viewpoint of excellent drying properties and paintability.
 本発明の組成物は(a)を組成物全量(本発明において、これを(a)、(b)、(c)及び(d)の合計とすることができる。以下同様)中に10~90質量%含有し、硬度がより高く、光学特性に優れるという観点から、(a)の量は15~60質量%であるのが好ましく、20~50質量%であるのがより好ましい。
 本発明の組成物は(b)を組成物全量中に5~75重量%含有し、硬度がより高く、光学特性に優れるという観点から、(b)の量は10~75質量%であるのが好ましく、15~30質量%であるのがより好ましい。
 本発明の組成物は(c)を組成物全量中に0.1~10重量%含有し、硬度がより高く、光学特性に優れるという観点から、(c)の量は1~8質量%であるのが好ましく、1~6質量%であるのがより好ましい。
 本発明の組成物は(d)有機溶剤の量を組成物全量中、5~60質量%とすることができる。
The composition of the present invention comprises 10 to 10% of (a) in the total amount of the composition (in the present invention, this can be the sum of (a), (b), (c) and (d), the same shall apply hereinafter). From the viewpoint of containing 90% by mass, higher hardness and excellent optical properties, the amount of (a) is preferably 15 to 60% by mass, more preferably 20 to 50% by mass.
The composition of the present invention contains 5 to 75% by weight of (b) in the total amount of the composition, and the amount of (b) is 10 to 75% by mass from the viewpoint of higher hardness and excellent optical properties. It is preferably 15 to 30% by mass.
The composition of the present invention contains (c) in an amount of 0.1 to 10% by weight in the total amount of the composition, and from the viewpoint of higher hardness and excellent optical properties, the amount of (c) is 1 to 8% by weight. It is preferably 1 to 6% by mass.
In the composition of the present invention, the amount of (d) the organic solvent can be 5 to 60% by mass based on the total amount of the composition.
 本発明の組成物は、本発明の目的を損なわない範囲で、例えば、(a)以外のエチレン性化合物、(b)以外の金属酸化物、老化防止剤、帯電防止剤、難燃剤、接着性付与剤、分散剤、酸化防止剤、消泡剤、レベリング剤、艶消し剤、光安定剤、染料、顔料のような添加剤を更に含有することができる。 The composition of the present invention is, for example, an ethylenic compound other than (a), a metal oxide other than (b), an anti-aging agent, an antistatic agent, a flame retardant, and adhesiveness, as long as the object of the present invention is not impaired. It may further contain additives such as an imparting agent, a dispersing agent, an antioxidant, an antifoaming agent, a leveling agent, a matting agent, a light stabilizer, a dye and a pigment.
 本発明の組成物の製造方法としては例えば、(a)、一次平均粒子径10~35nmを有する原料金属酸化物、(c)、(d)、必要に応じて使用することができる添加剤を混合した後混合物に超音波を照射する方法;(a)及び一次平均粒子径10~35nmを有する原料金属酸化物を含む混合物(混合物は(d)の一部を含んでもよい。)に超音波を照射し、その後混合物に(c)、(d)、必要に応じて使用することができる添加剤を加えて混合して組成物を製造する方法が挙げられる。
 本発明において、硬度がより高く、樹脂との反応性に優れ、かつ光学特性に優れるという観点から、少なくとも(a)と一次平均粒子径10~35nmを有する原料金属酸化物との混合物に超音波を照射するのが好ましい。
As a method for producing the composition of the present invention, for example, (a), a raw metal oxide having a primary average particle diameter of 10 to 35 nm, (c), (d), and an additive that can be used as necessary. A method of irradiating the mixture with ultrasound after mixing; (a) and a mixture containing a raw metal oxide having a primary average particle diameter of 10 to 35 nm (the mixture may include a part of (d)). And (c), (d), and a method of producing a composition by adding and mixing additives that can be used as necessary.
In the present invention, ultrasonic waves are applied to a mixture of at least (a) and a raw metal oxide having a primary average particle diameter of 10 to 35 nm from the viewpoint of higher hardness, excellent reactivity with a resin, and excellent optical characteristics. Is preferably irradiated.
 本発明の組成物を製造する方法としては、具体的には、例えば、まず、混合工程において、(a)又は原料金属酸化物以外の成分と原料金属酸化物とを混合して混合物を得る。混合後、混合物中で原料金属酸化物の少なくとも一部が凝集し、金属酸化物の二次凝集体が生じる(後述する比較例1に対応)。金属酸化物の二次凝集体はその粒子径が原料金属酸化物より大きくなり、金属酸化物の粒子径の分布は原料金属酸化物の粒子径の分布よりも粒子径が増加する方向に広がる。 As a method for producing the composition of the present invention, specifically, for example, first, in the mixing step, a component other than (a) or the raw metal oxide is mixed with the raw metal oxide to obtain a mixture. After mixing, at least a part of the raw material metal oxide aggregates in the mixture to form a secondary aggregate of metal oxide (corresponding to Comparative Example 1 described later). The metal oxide secondary aggregate has a particle size larger than that of the raw metal oxide, and the particle size distribution of the metal oxide spreads in a direction in which the particle size increases more than the particle size distribution of the raw metal oxide.
 本発明において、原料金属酸化物は、一次粒子を適度に凝集させてこれを(b)金属酸化物とすることができ、硬度がより高く、光学特性に優れるという観点から、その一次平均粒子径が10~35nmであるのが好ましく、10~30nmであるのがより好ましく、10~20nmであるのがさらに好ましい。
 原料金属酸化物は、一次粒子を適度に凝集させてこれを(b)金属酸化物とすることができ、硬度がより高く、光学特性に優れるという観点から、二次凝集物を含まないのが好ましい態様の1つとして挙げられる。
 原料金属酸化物は、一次粒子径が10~35nmであり二次凝集物を含まないこと以外は(b)と同様とすることができる。原料金属酸化物の使用量は(b)と同様とすることができる。
In the present invention, the raw material metal oxide appropriately aggregates the primary particles to make it (b) a metal oxide, and has a primary average particle diameter from the viewpoint of higher hardness and excellent optical properties. Is preferably 10 to 35 nm, more preferably 10 to 30 nm, and even more preferably 10 to 20 nm.
The raw material metal oxide can appropriately aggregate the primary particles to form (b) a metal oxide, and does not contain secondary aggregates from the viewpoint of higher hardness and excellent optical properties. It is mentioned as one of the preferable aspects.
The starting metal oxide can be the same as (b) except that the primary particle diameter is 10 to 35 nm and does not contain secondary aggregates. The amount of raw material metal oxide used can be the same as in (b).
 超音波を照射する際の条件としては、周波数が、原料金属酸化物を適度に凝集させてこれを(b)金属酸化物とすることができ、硬度がより高く、光学特性に優れるという観点から、20~200kHzであるのが好ましく、40~100kHzであるのが好ましい。出力が、周波数と同様の理由から、50W以上であるのが好ましく、50~100Wであるのが好ましい。超音波の照射時間は周波数と同様の理由から、1~120分であるのが好ましく、5~30分であるのが好ましい。
 超音波を照射ために使用される装置は特に制限されない。例えば従来公知のものが挙げられる。
As a condition when irradiating with ultrasonic waves, the frequency can be obtained by appropriately agglomerating the raw metal oxide to form (b) a metal oxide, from the viewpoint of higher hardness and excellent optical characteristics. 20 to 200 kHz is preferable, and 40 to 100 kHz is preferable. For the same reason as the frequency, the output is preferably 50 W or more, and preferably 50 to 100 W. The ultrasonic irradiation time is preferably 1 to 120 minutes, and preferably 5 to 30 minutes, for the same reason as the frequency.
The apparatus used for irradiating ultrasonic waves is not particularly limited. For example, a conventionally well-known thing is mentioned.
 本発明の組成物は、例えば、プラスチック表面保護剤、ハードコート剤、紫外線硬化型塗料、プライマー組成物等として使用できる。
 本発明の組成物を適用することができる基材は特に制限されない。例えば、プラスチック、ゴム、ガラス、金属、セラミック、ポリエチレンテレフタレート(PET)フィルムなどが挙げられる。
 本発明の組成物を適用することができるプラスチックは熱硬化性樹脂、熱可塑性樹脂のいずれであってもよい。プラスチックとしては、例えば、ポリメチルメタクリレート樹脂(PMMA樹脂)、ポリカーボネート樹脂、ポリスチレン樹脂、アクリロニトリル・スチレン共重合樹脂、ポリ塩化ビニル樹脂、アセテート樹脂、ABS樹脂、ポリエステル樹脂、ポリアミド樹脂のような難接着性樹脂が挙げられる。
The composition of the present invention can be used as, for example, a plastic surface protective agent, a hard coat agent, an ultraviolet curable coating material, a primer composition, and the like.
The substrate to which the composition of the present invention can be applied is not particularly limited. Examples thereof include plastic, rubber, glass, metal, ceramic, and polyethylene terephthalate (PET) film.
The plastic to which the composition of the present invention can be applied may be either a thermosetting resin or a thermoplastic resin. Examples of plastics include poor adhesion such as polymethyl methacrylate resin (PMMA resin), polycarbonate resin, polystyrene resin, acrylonitrile / styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, polyamide resin. Resin.
 本発明の組成物を基材に適用する方法は、特に限定されず、例えば、はけ塗り、流し塗り、浸漬塗り、スプレー塗り、スピンコート等の公知の塗布方法を採用できる。
 本発明の組成物の硬化方法としては例えば紫外線による硬化方法が挙げられる。本発明の組成物を紫外線照射によって硬化させる場合、本発明の組成物を硬化させる際に使用する紫外線の照射量としては、速硬化性、作業性の観点から、500~3,000mJ/cm2が好ましい。紫外線を照射するために使用する装置は特に制限されない。例えば、従来公知のものが挙げられる。硬化させるに際し加熱を併用してもよい。
The method for applying the composition of the present invention to the substrate is not particularly limited, and for example, a known coating method such as brush coating, flow coating, dip coating, spray coating, spin coating or the like can be employed.
Examples of the curing method of the composition of the present invention include a curing method using ultraviolet rays. When the composition of the present invention is cured by ultraviolet irradiation, the irradiation amount of the ultraviolet light used for curing the composition of the present invention is 500 to 3,000 mJ / cm 2 from the viewpoint of fast curability and workability. Is preferred. The apparatus used for irradiating ultraviolet rays is not particularly limited. For example, a conventionally well-known thing is mentioned. Heating may be used in combination for curing.
 本発明の組成物は硬度が高く光学特性(透明性)に優れる。
 本発明の組成物をPMMA樹脂上で25μmの膜厚で硬化させたとき鉛筆硬度は6H以上であるのが好ましく、7H以上であるのが好ましい。
The composition of the present invention has high hardness and excellent optical properties (transparency).
When the composition of the present invention is cured with a film thickness of 25 μm on a PMMA resin, the pencil hardness is preferably 6H or more, and more preferably 7H or more.
 本発明の積層体について以下に説明する。
 本発明の積層体は、基材と、前記基材の上に本発明の硬化性樹脂組成物を用いて得られる樹脂層とを有する積層体である。
 本発明の積層体に使用される、基材、硬化性樹脂組成物は上記と同様である。
 本発明の積層体はその製造について特に制限されない。例えば、本発明の組成物を基材に塗布し硬化させることによって得ることができる。
The laminate of the present invention will be described below.
The laminated body of this invention is a laminated body which has a base material and the resin layer obtained using the curable resin composition of this invention on the said base material.
The base material and curable resin composition used in the laminate of the present invention are the same as described above.
The laminate of the present invention is not particularly limited for its production. For example, it can be obtained by applying the composition of the present invention to a substrate and curing it.
 本発明の積層体について以下添付の図面を用いて説明する。図1は、本発明の積層体の一例の断面を模式的に示す断面図である。図1において、積層体100は、樹脂層102と基材104とを有する。樹脂層、基材の厚さは特に制限されない。
 本発明の積層体は、硬度が高く光学特性に優れる樹脂層を有するので透明性に優れる。本発明の積層体がその表面に樹脂層を有する場合特に上述の効果が発揮される。
The laminate of the present invention will be described below with reference to the accompanying drawings. FIG. 1 is a cross-sectional view schematically showing a cross section of an example of a laminate of the present invention. In FIG. 1, the laminate 100 includes a resin layer 102 and a base material 104. The thickness of the resin layer and the substrate is not particularly limited.
Since the laminate of the present invention has a resin layer having high hardness and excellent optical properties, it is excellent in transparency. The effects described above are exhibited particularly when the laminate of the present invention has a resin layer on its surface.
 以下に実施例を示して本発明を具体的に説明する。ただし本発明はこれらに限定されない。
<組成物の製造>
 下記表に示す成分(各成分の量の単位は質量部)のうちの(a)成分及び原料金属酸化物[(d)の一部を含んだ状態]を予め混ぜて混合物とし、この混合物に100W超音波洗浄器(3周波超音波洗浄器 MODEL VS-100III、アズワン株式会社製)を用いて超音波を同表に示す条件で照射し、照射後の混合物に(a)成分及び原料金属酸化物以外の成分[同表に示す、(c)及び(d)]を加えて混合して組成物を製造した。
 表中、各原料金属酸化物の上段の数値は、シランカップリング剤で処理された後の又はシランカップリング剤での処理がなされない、原料金属酸化物の正味の量であり、各原料金属酸化物の下段のかっこ内の数値は(d)の一部として使用された有機溶剤の量である。
<積層体の製造>
 まず、上記のようにして得られた組成物(塗料)を、基材[PMMA(ポリメチルメタクリレート)-PC(ポリカーボネート)-PMMA(3層構造)、厚さ:0.65mm、住友化学社製]の上に、スプレーガンを用いて膜厚:25μm程度となるように塗布し、これをオーブンで70℃の条件下で10分間乾燥させ、次いで、これに川口スプリング製作所社製のGS UV SYSTEMを用いて紫外線(UV)を照射して、組成物を硬化させ(照射強度:ピーク強度が80mW/cm2、積算光量が1000mJ/cm2)、積層体を得た。
The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these.
<Production of composition>
Of the components shown in the following table (units of the amount of each component are parts by mass), the component (a) and the raw metal oxide [containing part of (d)] are mixed in advance to form a mixture. Using a 100W ultrasonic cleaner (three-frequency ultrasonic cleaner MODEL VS-100III, manufactured by ASONE Co., Ltd.), ultrasonic waves were irradiated under the conditions shown in the table, and the mixture after irradiation was subjected to (a) component and raw metal oxidation Components other than the product [(c) and (d) shown in the same table] were added and mixed to produce a composition.
In the table, the upper numerical value of each raw metal oxide is the net amount of the raw metal oxide after being treated with the silane coupling agent or not being treated with the silane coupling agent. The numerical value in the lower parenthesis of the oxide is the amount of the organic solvent used as part of (d).
<Manufacture of laminates>
First, the composition (coating material) obtained as described above was used as a base material [PMMA (polymethyl methacrylate) -PC (polycarbonate) -PMMA (three-layer structure), thickness: 0.65 mm, manufactured by Sumitomo Chemical Co., Ltd. The film thickness is about 25 μm using a spray gun, dried in an oven at 70 ° C. for 10 minutes, and then GS UV SYSTEM manufactured by Kawaguchi Spring Co., Ltd. Was used to cure the composition (irradiation intensity: peak intensity 80 mW / cm 2 , integrated light intensity 1000 mJ / cm 2 ) to obtain a laminate.
<評価>
 上述のとおりにして得られた、組成物又は積層体を用いて以下の評価を行った。結果を表に示す。
 ((b)成分の分散)
 上記のとおり得られた超音波照射後の組成物について、ナノ粒子径分布測定装置(SALD-7100、株式会社島津製作所社製)を用いて体積平均モード、測定吸光度範囲(最大度):5.0、平均回数:128、屈折率:1.70-0.20iの条件で(b)成分の分散を測定した。
 (鉛筆硬度)
 得られた積層体(各組成物につき5サンプルの積層体)を用いて、JIS K5600-5-4:1999に準拠して(条件:積層体の斜め45°の角度、9.8Nの力、先端部直径1.8mm、先端部長さ3.0mm、7H)、塗膜の鉛筆硬度を測定した。その結果、鉛筆で引っ掻いたときの傷がない状態であるものを合格、鉛筆で引っ掻いたときの傷やへこみがある状態のものを不合格とし、合格率(%)を算出した。
 (光学特性)
 ヘイズメーター(HM-150、村上色彩技術研究所製)を用いて積層体の全光線透過率(%T)、ヘイズを、初期に測定した。サンプル数n=3の平均値として結果を示す。
 ヘイズは2.0以下であるのが好ましく、1.0以下であるのがより好ましく、0.5以下であるのが更に好ましい。
<Evaluation>
The following evaluation was performed using the composition or laminate obtained as described above. The results are shown in the table.
(Dispersion of component (b))
About the composition after ultrasonic irradiation obtained as described above, using a nanoparticle size distribution measuring device (SALD-7100, manufactured by Shimadzu Corporation), volume average mode, measured absorbance range (maximum degree): 5. The dispersion of component (b) was measured under the conditions of 0, average number of times: 128, refractive index: 1.70-0.20i.
(Pencil hardness)
Using the obtained laminate (a laminate of 5 samples for each composition) in accordance with JIS K5600-5-4: 1999 (conditions: oblique 45 ° angle of laminate, force of 9.8 N, The tip diameter was 1.8 mm, the tip length was 3.0 mm, 7H), and the pencil hardness of the coating film was measured. As a result, a sample having no scratch when scratched with a pencil was accepted, a sample having a scratch or dent when scratched with a pencil was rejected, and a pass rate (%) was calculated.
(optical properties)
Using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory), the total light transmittance (% T) and haze of the laminate were initially measured. The result is shown as an average value of the number of samples n = 3.
The haze is preferably 2.0 or less, more preferably 1.0 or less, and still more preferably 0.5 or less.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 上記表に示される各成分の詳細は以下のとおりである。
・(a-1)エチレン性化合物1:DPHA(ジペンタエリスリトールヘキサアクリレート)、サートマー社製
・(a-2)エチレン性化合物2:デンドリマータイプのアクリレート化合物。アクリロイルオキシ基を14官能以上を有する。商品名ビスコートV#1000、大阪有機化学工業社製。
・(a-3)エチレン性化合物3:ジペンタエリスリトールペンタアクリレート(DPPA)とヘキサメチレンジイソシアネート(HDI)とを反応させることで得られるウレタンアクリレート。1分子当たりアクリロイルオキシ基を10個を有する。
・原料金属酸化物1:商品名MEK-Ac-2101(アクリル処理されたコロイダルシリカ、日産化学工業社製、平均1次粒子径:10-20nm。)30質量部(アクリル処理されたコロイダルシリカの正味の量)と、(メタ)アクリロイルオキシ基を有するシランカップリング剤として3-アクリロイルオキシプロピルトリメトキシシラン(5質量部、商品名KBM-5103、信越化学工業社製)と、有機溶剤としてメチルエチルケトン(70質量部)とを80℃の条件下で撹拌して反応させた。得られた原料金属酸化物1は、今回のシランカップリング剤で処理されたシリカを33.3質量%、有機溶剤としてメチルエチルケトンを全体の66.7質量%を含有する。なお、詳細は不明であるが、原料金属酸化物1を用いた場合上記の超音波照射によって、超音波照射後の混合物中には、10~30nmの粒径の金属酸化物のうち、1次粒子にまで分散されたものが、10~30nmの粒径の金属酸化物の量の50質量%程度、含まれているものと考えられる。
・原料金属酸化物2:Al23粒子(CIKナノテック社、平均1次粒子径:10-31nm)を用いた他は原料金属酸化物1と同様にして、シランカップリング剤の処理を行ない、原料金属酸化物2を製造した。なお、詳細は不明であるが、原料金属酸化物2を用いた場合上記の超音波照射によって、超音波照射後の混合物中には、10~30nmの粒径の金属酸化物のうち、1次粒子にまで分散されたものが、10~30nmの粒径の金属酸化物の量の50質量%程度、含まれているものと考えられる。
・原料金属酸化物3:商品名MEK-ST(表面処理なし、日産化学工業社製コロイダルシリカ、平均1次粒子径:10-20nm。)なお、詳細は不明であるが、原料金属酸化物3を用いた場合上記の超音波照射によって、超音波照射後の混合物中には、10~30nmの粒径の金属酸化物のうち、1次粒子にまで分散されたものが、10~30nmの粒径の金属酸化物の量の50質量%程度、含まれているものと考えられる。
・(c-1)光重合開始剤1:イルガキュアー184(BASF社製)、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン
・(d-1)有機溶剤1:メチルイソブチルケトン(MIBK)
The detail of each component shown by the said table | surface is as follows.
(A-1) ethylenic compound 1: DPHA (dipentaerythritol hexaacrylate), manufactured by Sartomer, Inc. (a-2) ethylenic compound 2: dendrimer type acrylate compound. It has 14 or more functional acryloyloxy groups. Product name Viscoat V # 1000, manufactured by Osaka Organic Chemical Industry Co., Ltd.
(A-3) Ethylene compound 3: urethane acrylate obtained by reacting dipentaerythritol pentaacrylate (DPPA) with hexamethylene diisocyanate (HDI). It has 10 acryloyloxy groups per molecule.
Raw metal oxide 1: Trade name MEK-Ac-2101 (acrylic-treated colloidal silica, manufactured by Nissan Chemical Industries, average primary particle size: 10-20 nm) 30 parts by mass (of acrylic-treated colloidal silica Net amount), 3-acryloyloxypropyltrimethoxysilane (5 parts by mass, trade name KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent having a (meth) acryloyloxy group, and methyl ethyl ketone as an organic solvent (70 parts by mass) was reacted under stirring at 80 ° C. The obtained raw metal oxide 1 contains 33.3% by mass of silica treated with the present silane coupling agent, and 66.7% by mass of methyl ethyl ketone as an organic solvent. Although details are unknown, when the raw material metal oxide 1 is used, the above-described ultrasonic irradiation causes the primary oxide among the metal oxides having a particle diameter of 10 to 30 nm in the mixture after ultrasonic irradiation. It is considered that about 50% by mass of the amount of the metal oxide having a particle diameter of 10 to 30 nm is contained in the form dispersed in the particles.
Raw material metal oxide 2: A silane coupling agent was treated in the same manner as raw material metal oxide 1 except that Al 2 O 3 particles (CIK Nanotech, average primary particle size: 10-31 nm) were used. A raw material metal oxide 2 was produced. Although details are unknown, when the raw material metal oxide 2 is used, the above-described ultrasonic irradiation causes a primary oxide among the metal oxides having a particle diameter of 10 to 30 nm in the mixture after ultrasonic irradiation. It is considered that about 50% by mass of the amount of the metal oxide having a particle diameter of 10 to 30 nm is contained in the form dispersed in the particles.
Raw material metal oxide 3: Trade name MEK-ST (No surface treatment, colloidal silica manufactured by Nissan Chemical Industries, average primary particle size: 10-20 nm) Although details are unknown, raw material metal oxide 3 In the case of using the above-mentioned ultrasonic irradiation, in the mixture after the ultrasonic irradiation, 10-30 nm particles of metal oxide having a particle diameter of 10-30 nm are dispersed to primary particles. It is considered that about 50 mass% of the amount of the metal oxide having a diameter is contained.
(C-1) Photopolymerization initiator 1: Irgacure 184 (manufactured by BASF), 1-hydroxy-cyclohexyl-phenyl-ketone (d-1) Organic solvent 1: methyl isobutyl ketone (MIBK)
 表に示す結果から明らかなように、100nm以上の二次凝集体を含まない比較例1~3は鉛筆硬度試験の合格率が低かった。比較例2は超音波処理が十分でないため100nm以上の二次凝集体が生じないと考えられる。比較例3は超音波処理が強すぎるため二次凝集体が分散したと考えられる。(b)金属酸化物を含有しない比較例4は鉛筆硬度試験の合格率が悪かった。金属酸化物の量が5質量%未満であり、100nm以上の二次凝集体を含まない比較例5は鉛筆硬度試験の合格率が低かった。
 これに対して実施例1~6は得られる被膜の硬度が高かった。また実施例1~6は透明性に優れ光学特性に優れる。
 このように本発明の組成物は硬度の高い被膜を形成することができ、透明性に優れ光学特性に優れる。また、本発明の積層体は、高い硬度の光学特性に優れる樹脂膜を有するので硬度が高く透明性に優れる。
As is apparent from the results shown in the table, Comparative Examples 1 to 3 not containing secondary aggregates of 100 nm or more had a low pass rate of the pencil hardness test. In Comparative Example 2, since the ultrasonic treatment is not sufficient, it is considered that secondary aggregates of 100 nm or more are not generated. In Comparative Example 3, it is considered that the secondary aggregates were dispersed because the ultrasonic treatment was too strong. (B) In Comparative Example 4 containing no metal oxide, the pass rate of the pencil hardness test was poor. In Comparative Example 5 in which the amount of the metal oxide was less than 5% by mass and no secondary aggregate of 100 nm or more was included, the pass rate of the pencil hardness test was low.
On the other hand, in Examples 1 to 6, the hardness of the resulting coating was high. Examples 1 to 6 are excellent in transparency and optical characteristics.
As described above, the composition of the present invention can form a film with high hardness, and is excellent in transparency and optical characteristics. Moreover, since the laminated body of this invention has a resin film which is excellent in the optical characteristic of high hardness, its hardness is high and it is excellent in transparency.
 100  積層体
 102  樹脂層
 104  基材
DESCRIPTION OF SYMBOLS 100 Laminated body 102 Resin layer 104 Base material

Claims (5)

  1. (a)分子内にエチレン性不飽和基を3個以上有するエチレン性化合物10~90質量%、
    (b)金属酸化物5~75質量%、
    (c)光重合開始剤0.1~10質量%、及び
    (d)有機溶剤を含有し、
     前記(b)金属酸化物は二次凝集体を含み、前記二次凝集体の粒子径は150nm以下であり、粒子径100nm以上の二次凝集体の量が前記(b)金属酸化物中の1質量%以上である、硬化性樹脂組成物。
    (A) 10 to 90% by mass of an ethylenic compound having 3 or more ethylenically unsaturated groups in the molecule;
    (B) 5 to 75% by mass of a metal oxide,
    (C) contains 0.1 to 10% by weight of a photopolymerization initiator, and (d) an organic solvent,
    The (b) metal oxide contains secondary aggregates, the secondary aggregate has a particle size of 150 nm or less, and the amount of secondary aggregates having a particle size of 100 nm or more is in the (b) metal oxide. Curable resin composition which is 1 mass% or more.
  2.  前記(b)金属酸化物が更にエチレン性不飽和基を有する請求項1に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, wherein the metal oxide (b) further has an ethylenically unsaturated group.
  3.  前記(b)金属酸化物が疎水化処理されたものを含む請求項1又は2に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1 or 2, wherein the metal oxide (b) is subjected to a hydrophobic treatment.
  4.  前記(b)金属酸化物が更に一次粒子を含む請求項1~3のいずれかに記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 3, wherein the metal oxide (b) further contains primary particles.
  5.  基材と、前記基材の上に請求項1~4のいずれかに記載の硬化性樹脂組成物を用いて得られる樹脂層とを有する積層体。 A laminate having a base material and a resin layer obtained using the curable resin composition according to any one of claims 1 to 4 on the base material.
PCT/JP2013/060855 2012-05-02 2013-04-10 Curable resin composition WO2013164941A1 (en)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2016190373A1 (en) * 2015-05-28 2016-12-01 三洋化成工業株式会社 Curable resin composition and method for producing same
WO2017064970A1 (en) * 2015-10-13 2017-04-20 Dic株式会社 Active energy ray-curable resin composition, coating material, coating film, and film
JP2017132833A (en) * 2016-01-25 2017-08-03 アイカ工業株式会社 Ultraviolet-curable resin composition and hard coat film

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JPS60245610A (en) * 1984-05-18 1985-12-05 Toyobo Co Ltd Ultraviolet-curable resin composition for flat coating
JPH02173163A (en) * 1988-12-27 1990-07-04 Mitsubishi Rayon Co Ltd Abrasion resistant methacrylic resin molded article and production thereof
JP2002036452A (en) * 2000-07-21 2002-02-05 Lintec Corp Highly minute antidazzle hard coating film
JP2006348214A (en) * 2005-06-17 2006-12-28 Jsr Corp Photocurable liquid composition for photo-shaping, three-dimensional shaped article and method for producing the same
JP2009132763A (en) * 2007-11-29 2009-06-18 Toyo Ink Mfg Co Ltd Curable composition
WO2010116821A1 (en) * 2009-03-30 2010-10-14 株式会社 きもと Composition and laminate

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JPS60245610A (en) * 1984-05-18 1985-12-05 Toyobo Co Ltd Ultraviolet-curable resin composition for flat coating
JPH02173163A (en) * 1988-12-27 1990-07-04 Mitsubishi Rayon Co Ltd Abrasion resistant methacrylic resin molded article and production thereof
JP2002036452A (en) * 2000-07-21 2002-02-05 Lintec Corp Highly minute antidazzle hard coating film
JP2006348214A (en) * 2005-06-17 2006-12-28 Jsr Corp Photocurable liquid composition for photo-shaping, three-dimensional shaped article and method for producing the same
JP2009132763A (en) * 2007-11-29 2009-06-18 Toyo Ink Mfg Co Ltd Curable composition
WO2010116821A1 (en) * 2009-03-30 2010-10-14 株式会社 きもと Composition and laminate

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016190373A1 (en) * 2015-05-28 2016-12-01 三洋化成工業株式会社 Curable resin composition and method for producing same
KR20170129944A (en) * 2015-05-28 2017-11-27 산요가세이고교 가부시키가이샤 Curable resin composition and method for producing same
JPWO2016190373A1 (en) * 2015-05-28 2018-03-15 三洋化成工業株式会社 Curable resin composition and method for producing the same
WO2017064970A1 (en) * 2015-10-13 2017-04-20 Dic株式会社 Active energy ray-curable resin composition, coating material, coating film, and film
JP6187845B1 (en) * 2015-10-13 2017-08-30 Dic株式会社 Active energy ray-curable resin composition, paint, coating film, and film
CN108137726A (en) * 2015-10-13 2018-06-08 Dic株式会社 Active energy ray-curable resin composition, coating, film and film
JP2017132833A (en) * 2016-01-25 2017-08-03 アイカ工業株式会社 Ultraviolet-curable resin composition and hard coat film

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TW201404791A (en) 2014-02-01

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