WO2016063624A1 - 活性エネルギー線硬化性樹脂組成物、その製造方法、塗料、塗膜、及び積層フィルム - Google Patents

活性エネルギー線硬化性樹脂組成物、その製造方法、塗料、塗膜、及び積層フィルム Download PDF

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WO2016063624A1
WO2016063624A1 PCT/JP2015/074198 JP2015074198W WO2016063624A1 WO 2016063624 A1 WO2016063624 A1 WO 2016063624A1 JP 2015074198 W JP2015074198 W JP 2015074198W WO 2016063624 A1 WO2016063624 A1 WO 2016063624A1
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meth
acrylate
active energy
energy ray
curable resin
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PCT/JP2015/074198
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English (en)
French (fr)
Japanese (ja)
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加藤　直樹
伊藤　正広
英樹 渡邊
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Dic株式会社
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Priority to JP2016500424A priority Critical patent/JP6032382B2/ja
Priority to KR1020177008321A priority patent/KR102350778B1/ko
Priority to CN201580057729.5A priority patent/CN107075049B/zh
Publication of WO2016063624A1 publication Critical patent/WO2016063624A1/ja

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    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • 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
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic

Definitions

  • the present invention is a composition that suppresses the generation of gel in the dispersion step and is excellent in storage stability, and further has an active energy ray curable resin composition having good appearance and transparency of the cured coating film,
  • the present invention relates to a coating material containing the resin composition, a coating film comprising the coating material, and a laminated film having the coating layer.
  • Inorganic fine particle dispersed active energy ray-curable resin composition obtained by dispersing inorganic fine particles in the resin composition exhibits various performances such as increasing the hardness of the coating film, adjusting the refractive index, and imparting conductivity. It is attracting attention as a new material that can be used.
  • a coating film made of a resin composition in which inorganic fine particles are dispersed has a drawback that it is inferior in transparency as compared with a coating film made of an organic single resin composition. In order to obtain a resin composition having both hardness and transparency of the coating film, it is necessary to more stably disperse the inorganic fine particles pulverized to a smaller particle diameter in the resin.
  • dispersion by a wet ball mill can be considered as a method of pulverizing inorganic fine particles to a smaller particle size and performing stable dispersion in a resin.
  • a resin component having a polymerizable group such as an acryloyl group
  • they are polymerized to cause thickening or gelation. There was a fear.
  • the inorganic fine particle dispersion type resin composition obtained by such a method has a low non-volatile fraction, a concentration step may be required, but the concentration of the dispersion is stable because the aggregation of inorganic fine particles is likely to occur. The operation was difficult and the operation was complicated.
  • Problems to be solved by the present invention include a method for producing an active energy ray-curable resin composition that can prevent the occurrence of thickening and gelation, and can stably pulverize and disperse inorganic fine particles with good productivity. And an active energy ray-curable resin composition in which the resulting coating film has both high transparency and appearance (smoothness), and a coating film using the composition, a coating film, and a laminated film formed by forming the coating film Is to provide.
  • the present inventors have added an antioxidant in addition to the polyfunctional acrylate monomer or oligomer serving as a dispersion medium, thereby increasing the viscosity or gel due to polymerization of the acryloyl group.
  • the inorganic fine particles can be pulverized and stably dispersed in the resin, resulting in excellent storage stability over time, a high non-volatile fraction, and a cured coating film having high transparency and smoothness.
  • the inventors have found that a fine particle dispersion type active energy ray-curable resin composition can be easily and efficiently produced, and have completed the present invention.
  • the present invention comprises an active energy ray-curable resin composition comprising an active energy ray-curable resin (A), an antioxidant (C), and inorganic fine particles (D), and the production thereof.
  • a method is provided.
  • the present invention further provides a coating film containing the composition, a coating film obtained by curing the coating composition, and a laminated film including a layer comprising the coating film.
  • the manufacturing method of the active energy ray-curable resin composition which can perform the grinding
  • the active energy ray-curable resin (A) used in the present invention is a dispersion medium for inorganic fine particles (D), has a relatively high molecular weight, and is polyfunctional, which reduces curling of the resulting coating film. From the viewpoint that a coating film having high hardness and excellent curl resistance can be obtained.
  • the active energy ray-curable resin (A) preferably has a weight average molecular weight (Mw) in the range of 3,000 to 100,000.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) is 3,000 or more, the curing shrinkage of the resulting coating film is reduced, and the curl resistance is improved.
  • a weight average molecular weight (Mw) is 100,000 or less, a viscosity is appropriate and manufacture of a composition becomes easy.
  • the range of 5,000 to 80,000 is more preferable, and the range of 6,000 to 50,000 is most preferable in that the coating film has little curing shrinkage and excellent leveling properties.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured under the following conditions using a gel permeation chromatograph (GPC).
  • Measuring device HLC-8220 manufactured by Tosoh Corporation Column: Tosoh Corporation guard column H XL -H + Tosoh Corporation TSKgel G5000H XL + Tosoh Corporation TSKgel G4000H XL + Tosoh Corporation TSKgel G3000H XL + Tosoh Corporation TSKgel G2000H XL Detector: RI (differential refractometer) Data processing: Tosoh Corporation SC-8010 Measurement conditions: Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard; Polystyrene sample; 0.4% by mass tetrahydrofuran solution in terms of resin solids filtered through microfilter (100 ⁇ l)
  • the active energy ray-curable resin (A) has a (meth) acryloyl group in the molecular structure, and the (meth) acryloyl equivalent is preferably in the range of 100 g / eq to 600 g / eq.
  • the (meth) acryloyl group means an acryloyl group or a methacryloyl group
  • the (meth) acryl equivalent means the solid content weight (g / eq) of the resin (A) per mole of the (meth) acryloyl group. ).
  • the (meth) acryloyl equivalent of the resin (A) is 100 g / eq or more, the cross-linking density of the obtained coating film is appropriate, and curling of the coating film due to curing shrinkage can be suppressed. Moreover, when the (meth) acryloyl equivalent of resin (A) is 600 g / eq or less, it becomes easy to raise the hardness of the coating film obtained.
  • those having a (meth) acryloyl equivalent in the range of 150 g / eq to 500 g / eq are more preferable in terms of excellent balance between curl resistance and hardness of the coating film, and 170 g / eq Those in the range of ⁇ 450 g / eq are particularly preferred.
  • the active energy ray-curable resin (A) includes, for example, a poly (meth) acrylate (E) having a urethane structure, a poly (meth) acrylate (F) of an acrylic polymer, and a poly (meth) acrylate (G) of an epoxy compound. ) And the like.
  • the poly (meth) acrylate (E) having a urethane structure is, for example, a polyol compound (e1) and a polyisocyanate compound (e2) with respect to a hydroxyl group of the polyol compound (e1), an isocyanate group of the polyisocyanate (e2).
  • Examples thereof include poly (meth) acrylate (E2) having a urethane structure obtained by reacting (e2) with hydroxyl group-containing (meth) acrylate (e3).
  • the polyol compound (e1) used as the raw material for the poly (meth) acrylate (E1) having the urethane structure is, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1 , 3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1, Aliphatic diols such as 5-pentanediol, 3-methyl 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol;
  • Aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol;
  • Ether diols such as polyoxyethylene glycol and polyoxypropylene glycol
  • Alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A;
  • Ring-opening polymerization of the aliphatic diol or aliphatic polyol with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether.
  • Modified polyether diol or polyol obtained by:
  • Aliphatic diols or polyols, and aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid; (anhydrous) aromatics such as phthalic acid, terephthalic acid, isophthalic acid, and orthophthalic acid Dicarboxylic acids; Alicyclic dicarboxylic acids such as hexahydrophthalic acid and 1,4-cyclohexanedicarboxylic acid; Aliphatic unsaturations such as tetrahydrophthalic acid, (anhydrous) maleic acid, fumaric acid, citraconic acid, itaconic acid, and glutaconic acid Dicarboxylic acids; various tricarboxylic acids such as 1,2,5-hexanetricarboxylic acid, trimellitic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,
  • the polyisocyanate compound (e2) used as a raw material for the poly (meth) acrylates (E1) and (E2) having a urethane structure is composed of various diisocyanate monomers, adduct-type polyisocyanate compounds having urethane bond sites in the molecule, molecules Examples thereof include a nurate polyisocyanate compound having an isocyanurate ring structure.
  • diisocyanate monomer examples include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene.
  • Aliphatic diisocyanates such as range isocyanate;
  • Cycloaliphatic diisocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate;
  • 1,5-naphthylene diisocyanate 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate
  • aromatic diisocyanates such as 1,4-phenylene diisocyanate and tolylene diisocyanate.
  • the adduct type polyisocyanate compound having a urethane bond site in the molecule can be obtained, for example, by reacting a diisocyanate monomer with a polyol compound.
  • a diisocyanate monomer used in the reaction include the various diisocyanate monomers described above, and these may be used alone or in combination of two or more.
  • the polyol compound used in the reaction include various polyol compounds exemplified as the polyol compound (e1).
  • the nurate type polyisocyanate compound having an isocyanurate ring structure in the molecule is obtained, for example, by reacting a diisocyanate monomer with a monoalcohol and / or a diol.
  • a diisocyanate monomer used in the reaction include the various diisocyanate monomers described above, and these may be used alone or in combination of two or more.
  • Monoalcohols used in the reaction include hexanol, 2-ethylhexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n- Heptadecanol, n-octadecanol, n-nonadecanol, eicosanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol 2-octyldodecanol, 2-decyltetradecanol and the like, and examples of the diol include various diols exemplified as the polyol compound (e1). These monoalcohol
  • the hydroxyl group-containing (meth) acrylate compound (e3) used as a raw material for the poly (meth) acrylates (E1) and (E2) having a urethane structure is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta) ) Acrylates, hydroxy mono (meth) acrylates such as 4-hydroxybutyl (meth) acrylate, 2-hydroxy3-phenoxypropyl (meth) acrylate; hydroxy such as glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate Di (meth) acrylate; hydroxytri (meth) acrylate such as pentaerythritol tri (meth) acrylate; hydroxype such as dipentaerythritol penta (meth) acrylate and sorbitol penta (meth) acrylate Such data (meth) acrylate. These may be used alone or in
  • the poly (meth) acrylates (E1) and (E2) having the urethane structure may be used alone or in combination of two or more.
  • the production of the poly (meth) acrylates (E1) and (E2) having the urethane structure is, for example, a urethanization catalyst such as tin (II) octoate and zinc (II) octoate in a temperature range of 20 to 120 ° C. Can be used as appropriate.
  • the reaction may be performed under solvent-free conditions, or a solvent that is inactive with respect to a hydroxyl group or an isocyanate group, such as toluene, xylene, methyl ethyl ketone, or methyl isobutyl ketone.
  • the poly (meth) acrylate (F) of the acrylic polymer is obtained by adding a monomer (f2) having a (meth) acryloyl group and a carboxyl group to a (meth) acrylic polymer (f1) having an epoxy group.
  • a monomer (f4) having a (meth) acryloyl group and an epoxy group is added to a poly (meth) acrylate (f1) of an acrylic polymer obtained by reaction and a (meth) acrylic polymer (f3) having a carboxyl group.
  • poly (meth) acrylate (F3) of an acrylic polymer obtained by addition reaction is a monomer (f6) having a (meth) acryloyl group and one isocyanate group in the poly (meth) acrylate (f2) of an acrylic polymer obtained by reaction, and a (meth) acrylic polymer (f5) having a hydroxyl group.
  • poly (meth) acrylate (F3) of an acrylic polymer obtained by addition reaction isocyanate
  • the (meth) acrylic polymer (f1) having an epoxy group used as a raw material for the poly (meth) acrylate (F1) of the acrylic polymer is, for example, a polymerizable monomer having a (meth) acryloyl group and an epoxy group. It can be obtained by a homopolymerization reaction of (H) or a copolymerization reaction with another polymerizable monomer (I).
  • the polymerizable monomer (H) having a (meth) acryloyl group and an epoxy group used as a raw material for the (meth) acrylic polymer (f1) having an epoxy group is, for example, glycidyl (meth) acrylate, ⁇ - Glycidyl ethyl (meth) acrylate, glycidyl ⁇ -n-propyl (meth) acrylate, ⁇ -n-butyl glycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid -4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxypentyl, ⁇ -ethyl (meth) acrylic acid-6,7-epoxypentyl, ⁇ -methylglycidyl (meth) acrylate, (meth) acrylic Acid-3,4-epoxycyclohexyl, lactone-modified (
  • glycidyl (meth) acrylate, ⁇ -ethyl is preferable in that the (meth) acryloyl group equivalent of the poly (meth) acrylate (F1) of the acrylic polymer can be easily adjusted to the above-described preferable range.
  • Particularly preferred are glycidyl (meth) acrylate and glycidyl ⁇ -n-propyl (meth) acrylate.
  • polymerizable monomers (I) used as a raw material for the (meth) acrylic polymer (f1) having the epoxy group are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) Propyl acrylate, (meth) acrylic acid-n-butyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid hexyl, (meth) acrylic acid hepsyl, (meth) acrylic acid octyl, (meth) acrylic acid Nonyl, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, docosyl (meth) acrylate (Meth) acrylic acid esters having an alkyl group having 1 to
  • (Meth) acrylic acid esters having an alicyclic alkyl group such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate ;
  • Unsaturated dicarboxylic acid esters such as dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, methyl ethyl fumarate, methyl butyl fumarate, methyl ethyl itaconate;
  • Styrene derivatives such as styrene, ⁇ -methylstyrene, chlorostyrene;
  • Diene compounds such as butadiene, isoprene, piperylene, dimethylbutadiene;
  • Vinyl halides such as vinyl chloride and vinyl bromide and vinylidene halides
  • Unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone;
  • Vinyl esters such as vinyl acetate and vinyl butyrate
  • Vinyl ethers such as methyl vinyl ether and butyl vinyl ether
  • Vinyl cyanides such as acrylonitrile, methacrylonitrile, vinylidene cyanide
  • N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
  • Fluorine-containing ⁇ -olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene;
  • (Per) fluoroalkyl / perfluorovinyl ether having 1 to 18 carbon atoms in the (per) fluoroalkyl group such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether;
  • Silyl group-containing (meth) acrylates such as ⁇ -methacryloxypropyltrimethoxysilane
  • These may be used alone or in combination of two or more. Among these, it becomes easy to adjust the (meth) acryloyl group equivalent of the poly (meth) acrylate (G1) of the acrylic polymer to the above-mentioned preferable range, and the obtained coating film is not too brittle.
  • (Meth) acrylic acid esters having an alkyl group having 1 to 22 carbon atoms and (meth) acrylic acid esters having an alicyclic alkyl group are preferred, and having an alkyl group having 1 to 22 carbon atoms (meth) Acrylic acid esters are more preferred. Particularly preferred are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth) acrylate.
  • the (meth) acrylic polymer (f1) having an epoxy group may be a homopolymer of a polymerizable monomer (H) having a (meth) acryloyl group and an epoxy group, or other polymerization.
  • a copolymer with the polymerizable monomer (I) may be used.
  • the epoxy equivalent of the (meth) acrylic polymer (f1) having an epoxy group may be adjusted so that the acryloyl equivalent of the poly (meth) acrylate (F1) of the resulting acrylic polymer is in the range of 100 to 600 g / eq. In terms of ease, it is in the range of 80 to 500 g / eq, preferably in the range of 120 to 470 g / eq, and particularly preferably in the range of 150 to 400 g / eq.
  • the (meth) acrylic polymer (f1) having an epoxy group can be produced by, for example, addition polymerization in the temperature range of 80 ° C. to 150 ° C. in the presence of a polymerization initiator, a random copolymer, A block copolymer, a graft copolymer, etc. are mentioned.
  • a polymerization initiator a random copolymer
  • a block copolymer a graft copolymer, etc.
  • a bulk polymerization method a solution polymerization method, a suspension polymerization method, an emulsion polymerization method and the like can be used.
  • the reaction and the subsequent reaction of the (meth) acrylic polymer (f1) with the polymerizable monomer (f2) having a (meth) acryloyl group and a carboxyl group are continuously performed.
  • the solution polymerization method is preferable in that it is possible.
  • the solvent used when the (meth) acrylic polymer (f1) having an epoxy group is produced by a solution polymerization method has a boiling point of 80 ° C. or higher in consideration of the reaction temperature.
  • Ether solvents such as n-butyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane;
  • Alcoholic solvents such as isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, diacetone alcohol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 3-methyl-3-methoxybutanol;
  • hydrocarbon solvents such as toluene, xylene, Solvesso 100, Solvesso 150, Swazol 1800, Swazol 310, Isopar E, Isopar G, Exxon Naphtha No. 5, Exxon Naphtha No. 6 and the like. These may be used alone or in combination of two or more.
  • ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoint of excellent solubility of the obtained (meth) acrylic polymer (f1) having an epoxy group.
  • Examples of the catalyst used in the production of the (meth) acrylic polymer (f1) having an epoxy group include 2,2′-azobisisobutyronitrile and 2,2′-azobis- (2,4-dimethylvalero). Nitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile) and the like; benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, t-butylperoxyethylhexanoate 1,1'-bis- (t-butylperoxy) cyclohexane, t-amylperoxy-2-ethylhexanoate, organic peroxides such as t-hexylperoxy-2-ethylhexanoate, hydrogen peroxide, etc. Is mentioned.
  • the peroxide When a peroxide is used as the catalyst, the peroxide may be used together with a reducing agent to form a redox type initiator.
  • the monomer (f2) having a (meth) acryloyl group and a carboxyl group used as a raw material for the poly (meth) acrylate (F1) of the acrylic polymer is, for example, (meth) acrylic acid; ⁇ -carboxyethyl (meth) Acrylic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and unsaturated carboxylic acids having ester bonds such as modified lactones thereof; maleic acid; succinic anhydride And carboxyl group-containing polyfunctional (meth) acrylate obtained by reacting an anhydride such as maleic anhydride with a hydroxyl group-containing polyfunctional (meth) acrylate monomer such as pentaerythritol triacrylate.
  • anhydride such as maleic anhydride
  • the (meth) acryloyl group equivalent of the poly (meth) acrylate (F1) of the acrylic polymer can be easily adjusted to the above-mentioned preferable range.
  • (Meth) acrylate and 2-acryloyloxyethyl succinic acid are preferred, and (meth) acrylic acid is particularly preferred.
  • the poly (meth) acrylate (E1) of the acrylic polymer reacts the (meth) acrylic polymer (f1) having the epoxy group with the monomer (f2) having a (meth) acryloyl group and a carboxyl group.
  • the reaction is performed, for example, by polymerizing a (meth) acrylic polymer (f1) having an epoxy group by a solution polymerization method, and adding a monomer (f2) having a (meth) acryloyl group and a carboxyl group to the reaction system.
  • a method such as appropriately using a catalyst such as triphenylphosphine in a temperature range of 80 to 150 ° C.
  • the acryloyl equivalent of the poly (meth) acrylate (F1) of the acrylic polymer is preferably in the range of 100 to 600 g / eq. This is because the (meth) acrylic polymer (f1) having an epoxy group and (meth) )
  • the acryloyl group and the carboxyl group can be adjusted by the reaction ratio with the monomer (e2).
  • the carboxyl group in the monomer (f2) having a (meth) acryloyl group and a carboxyl group is 0.4 to 0.4 mol per 1 mol of the epoxy group in the (meth) acrylic polymer (f1) having an epoxy group.
  • the poly (meth) acrylate (F1) of the acrylic polymer thus obtained has a hydroxyl group generated by a reaction between a carboxyl group and an epoxy group in the molecule.
  • a monomer having one isocyanate group and (meth) acryloyl group in the hydroxyl group (J) The poly (meth) acrylate (F1 ′) of an acrylic polymer obtained by addition reaction of (A)) can also be used as the compound (A) of the present invention.
  • Examples of the monomer (J) having one isocyanate group and (meth) acryloyl group include a compound represented by the following general formula 1, and a single monomer having one isocyanate group and one (meth) acryloyl group.
  • Monomer, monomer having one isocyanate group and two (meth) acryloyl groups, monomer having one isocyanate group and three (meth) acryloyl groups, one isocyanate group and four (meth) acryloyl groups A monomer having a group, a monomer having one isocyanate group and five (meth) acryloyl groups, and the like.
  • R 1 is a hydrogen atom or a methyl group.
  • R 2 is an alkylene group having 2 to 4 carbon atoms.
  • n represents an integer of 1 to 5.
  • these (meth) acryloyl group and monomer (J) having one isocyanate group include 2-acryloyloxyethyl isocyanate (trade name: “Karenz AOI” manufactured by Showa Denko KK) ), 2-methacryloyloxyethyl isocyanate (trade name: “Karenz MOI” manufactured by Showa Denko KK), 1,1-bis (acryloyloxymethyl) ethyl isocyanate (product name: “Karenz BEI” manufactured by Showa Denko KK), etc. ).
  • Other examples include compounds obtained by adding a hydroxyl group-containing (meth) acrylate compound to one isocyanate group of a diisocyanate compound.
  • Examples of the diisocyanate compound used in the reaction include various diisocyanate monomers exemplified as the polyisocyanate compound (e1).
  • Examples of the hydroxyl group-containing (meth) acrylate compound used in the reaction include various hydroxyl group-containing (meth) acrylate compounds exemplified as the hydroxyl group-containing (meth) acrylate compound (e3). These may be used alone or in combination of two or more. Among these, 2-hydroxyethyl (meth) acrylate is easy in that the (meth) acryloyl group equivalent of the poly (meth) acrylate (F1 ′) of the resulting acrylic polymer can be easily adjusted to the above-mentioned preferable range.
  • Hydroxy mono (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy3-phenoxypropyl (meth) acrylate, and the like, and 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate is particularly preferred.
  • the reaction between the poly (meth) acrylate (F1) of the acrylic polymer and the monomer (J) having one isocyanate group and (meth) acryloyl group is, for example, poly (meth) acrylate (F1) of the acrylic polymer.
  • the monomer (I) having a (meth) acryloyl group and one isocyanate group is added dropwise thereto, and the mixture is heated to 50 to 120 ° C.
  • the poly (meth) acrylates (F1) and (F1 ′) of the acrylic polymer contain more hydroxyl groups in the molecule and interact with the inorganic particles (D) due to the interaction between the hydroxyl groups and the inorganic particles (D). Since the dispersibility is enhanced, poly (meth) acrylate (F1) of the acrylic polymer is preferable.
  • the (meth) acrylic polymer (f3) having a carboxyl group used as a raw material for the poly (meth) acrylate (F2) of the acrylic polymer is, for example, a polymerizable monomer having a (meth) acryloyl group and a carboxyl group. It can be obtained by a homopolymerization reaction of (K) or a copolymerization reaction with another polymerizable monomer (L).
  • the polymerizable monomer (K) having a (meth) acryloyl group and a carboxyl group used as a raw material of the (meth) acrylic polymer (f3) having the carboxyl group is, for example, the (meth) acryloyl group and the carboxyl group.
  • the various monomers illustrated as a monomer (f2) which has these are mentioned, These may each be used independently and may use 2 or more types together.
  • the other polymerizable monomer (L) used as a raw material for the (meth) acrylic polymer (f3) having a carboxyl group is, for example, various monomers exemplified as the other polymerizable monomer (I). And may be used singly or in combination of two or more.
  • the (meth) acrylic polymer (f3) having a carboxyl group may be a homopolymer of a polymerizable monomer (K) having a (meth) acryloyl group and a carboxyl group, or another polymerizable monomer.
  • a copolymer with (L) may be used.
  • the mass ratio of both when copolymerizing [polymerizable monomer having (meth) acryloyl group and carboxyl group] Body (K)]: [other polymerizable monomer (L)] is preferably in the range of 25 to 100 parts by mass: 75 to 0 parts by mass, and in the range of 40 to 100 parts by mass: 60 to 0 parts by mass. Is more preferable.
  • the (meth) acrylic polymer (f3) having a carboxyl group can be produced, for example, under the same conditions as the production of the (meth) acrylic polymer (f1) having an epoxy group.
  • the monomer (f4) having a (meth) acryloyl group and an epoxy group used as a raw material for the poly (meth) acrylate (F2) of the acrylic polymer is, for example, polymerizable having the (meth) acryloyl group and the epoxy group.
  • the various monomers illustrated as a monomer (G) are mentioned, These may each be used independently and may use 2 or more types together.
  • the poly (meth) acrylate (F2) of the acrylic polymer reacts the (meth) acrylic polymer (f3) having the carboxyl group with the monomer (f4) having a (meth) acryloyl group and an epoxy group.
  • the reaction is performed, for example, by polymerizing a (meth) acrylic polymer (f1) having an epoxy group by a solution polymerization method, and adding a monomer (f2) having a (meth) acryloyl group and a carboxyl group to the reaction system.
  • a catalyst such as triphenylphosphine as appropriate under a temperature condition of 80 to 150 ° C.
  • the (meth) acryloyl equivalent of the poly (meth) acrylate (F2) of the acrylic polymer is preferably in the range of 100 to 600 g / eq. This is because the (meth) acrylic polymer (f3) having a carboxyl group And the (meth) acryloyl group and the epoxy group can be adjusted by the reaction ratio of the monomer (f4). Usually, the epoxy group in the monomer (f4) having a (meth) acryloyl group and an epoxy group is 0.4 per mol of the carboxyl group in the (meth) acrylic polymer (f3) having a carboxyl group. By reacting in a range of ⁇ 1.1 mol, the acryloyl equivalent of the resulting acrylic (meth) acrylate (F2) can be adjusted to the above preferred range.
  • the poly (meth) acrylate (F2) of the acrylic polymer thus obtained has a hydroxyl group generated by a reaction between a carboxyl group and an epoxy group in the molecule.
  • the monomer (J) having the one isocyanate group and (meth) acryloyl group is added to the hydroxyl group as necessary.
  • An acrylic polymer poly (meth) acrylate (F2 ′) obtained by addition reaction may be used. The reaction can be carried out under the same conditions as the reaction between the poly (meth) acrylate (F1) of the acrylic polymer and the monomer (J) having one isocyanate group and (meth) acryloyl group.
  • the (meth) acrylic polymer (f5) having a hydroxyl group used as a raw material for the poly (meth) acrylate (F3) of the acrylic polymer is, for example, a polymerizable monomer (M) having a (meth) acryloyl group and a hydroxyl group. ) Or a copolymerization reaction with another polymerizable monomer (N).
  • the (meth) acryloyl group and the polymerizable monomer (M) having a hydroxyl group used as a raw material for the (meth) acrylic polymer (f5) having a hydroxyl group are, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, and the like. These may be used alone or in combination of two or more.
  • 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate are preferable in that the obtained (meth) acrylic polymer (f5) has a high hydroxyl value.
  • the hydroxyl value of the (meth) acrylic polymer (f5) is high and leaving the hydroxyl group in the poly (meth) acrylate (F3) of the finally obtained acrylic polymer, inorganic fine particles (D) The dispersibility with respect to can be improved.
  • the other polymerizable monomer (N) used as a raw material of the (meth) acrylic polymer (f5) having a hydroxyl group is, for example, various single quantities exemplified as the other polymerizable monomer (I). Body, and these may be used alone or in combination of two or more.
  • the (meth) acrylic polymer (f5) having a hydroxyl group may be a homopolymer of a polymerizable monomer (M) having a (meth) acryloyl group and a hydroxyl group, or other polymerizable monomer (N And a copolymer thereof.
  • the mass ratio of both when copolymerizing [polymerizable monomer having (meth) acryloyl group and hydroxyl group] (M)]: [Other polymerizable monomer (N)] is preferably in the range of 25 to 100 parts by mass: 75 to 0 parts by mass, and in the range of 30 to 70 parts by mass: 70 to 30 parts by mass. More preferred.
  • the (meth) acrylic polymer (f5) having a hydroxyl group can be produced, for example, under the same temperature and catalytic conditions as in the production of the (meth) acrylic polymer (f1) having an epoxy group.
  • Examples of the solvent used in the production of the (meth) acrylic polymer (f5) having a hydroxyl group include various solvents listed as the solvents used in the production of the (meth) acrylic polymer (f1) having the epoxy group. .
  • the monomer (f6) having a (meth) acryloyl group and one isocyanate group used as a raw material for the poly (meth) acrylate (F3) of the acrylic polymer is, for example, the (meth) acryloyl group and one isocyanate group.
  • the various compounds illustrated as a monomer (J) which has these are mentioned. These may be used alone or in combination of two or more. Among these, an acrylic polymer poly (meth) acrylate (F3) becomes a more multifunctional compound, and a coating film having higher hardness is obtained, so that two or more (meth) acryloyl groups are contained in one molecule. In particular, 1,1-bis (acryloyloxymethyl) ethyl isocyanate is preferable.
  • the poly (meth) acrylate (F3) of the acrylic polymer comprises the (meth) acrylic polymer (f5) having the hydroxyl group and the monomer (f6) having a (meth) acryloyl group and one isocyanate group. It can be obtained by reaction. In the reaction, for example, a (meth) acrylic polymer (f5) having a hydroxyl group is polymerized by solution polymerization, and a monomer (f6) having a (meth) acryloyl group and one isocyanate group is dropped into the reaction system. In addition, it can be carried out by appropriately using a temperature condition of 50 to 120 ° C. and a catalyst such as tin (II) octanoate as appropriate.
  • a catalyst such as tin (II) octanoate
  • the acryloyl equivalent of the poly (meth) acrylate (F3) of the acrylic polymer is preferably 100 to 600 g / eq. This is because the (meth) acrylic polymer (f5) having a hydroxyl group and the (meth) acryloyl group and It can be adjusted by the reaction ratio with the monomer (f6) having one isocyanate group. Usually, the number of moles of isocyanate groups in the monomer (f6) having a (meth) acryloyl group and one isocyanate group is 0 with respect to 1 mole of the hydroxyl group in the (meth) acrylic polymer (a5) having a hydroxyl group.
  • the acryloyl equivalent of the poly (meth) acrylate (F3) of the resulting acrylic polymer can be adjusted to the above preferred range.
  • the number of moles of isocyanate groups in the monomer (f6) having a (meth) acryloyl group and one isocyanate group is 0 with respect to 1 mole of the hydroxyl group in the (meth) acrylic polymer (a5) having a hydroxyl group.
  • the poly (meth) acrylate (F3) of the resulting acrylic polymer has a hydroxyl group in the molecular structure and can be dispersed in the inorganic fine particles (D) by reacting at a ratio in the range of 0.7 to 0.9 mol. It is preferable because it can be increased.
  • the poly (meth) acrylates (F1), (F2) and (F3) of the acrylic polymer may be used alone or in combination of two or more.
  • acrylic polymer poly (meth) acrylates (F1) and (F2) have more hydroxyl groups in the molecule, so that they are well-familiar with the metal oxide surface of the inorganic fine particles (D), and the resulting dispersion It is preferable at the point which is excellent in the storage stability of a body.
  • an acrylic polymer poly (meth) acrylate (F1) is preferable in terms of easier synthesis, and the (meth) acrylic polymer (f1) having an epoxy group obtained by using glycidyl (meth) acrylate.
  • a reaction product obtained by addition reaction of (meth) acrylic acid is more preferable.
  • the hydroxyl value of the poly (meth) acrylates (F1) and (F2) of the acrylic polymer is preferably in the range of 90 to 280 g / eq, more preferably in the range of 140 to 270 g / eq.
  • the poly (meth) acrylate (G) of the epoxy compound is, for example, a compound (g1) having an epoxy group in the molecular structure other than the (meth) acrylic polymer (f1) having the epoxy group, ) It is obtained by subjecting a monomer (g2) having an acryloyl group and a carboxyl group to an addition reaction.
  • the compound (g1) having an epoxy group in the molecular structure is, for example, propylene glycol, butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, polyethylene glycol, Various diols such as polypropylene glycol, neopentyl glycol, neopentyl glycol hydroxypivalate, bisphenol A, bisphenol F, ethoxylated bisphenol A; modified diols obtained by modifying the hydroxyl groups of the various diols with ethylene glycol or propylene glycol; Propane, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, glycerin, etc.
  • Modified triols in which the hydroxyl groups of the various triols are modified with ethylene glycol or propylene glycol; polyfunctional aromatic polyols such as phenol novolac and cresol novolac; hydroxyl groups of the polyfunctional aromatic polyols are modified with ethylene glycol or propylene glycol
  • Modified polyfunctional aromatic polyols those obtained by adding epichlorohydrin or the like to hydroxyl groups such as polyfunctional alicyclic polyols, which are hydrogenated types of the above polyfunctional aromatic polyols and modified polyfunctional polyols, or bisphenol A, Examples thereof include bisphenol type epoxy resins obtained by polymerizing diglycidyl ether such as bisphenol F and bisphenol A.
  • Examples of the monomer (g2) having the (meth) acryloyl group and carboxyl group include various compounds listed as the monomer (f2) having the (meth) acryloyl group and carboxyl group.
  • the poly (meth) acrylate (G) of the epoxy compound has in its molecular structure a hydroxyl group generated by a reaction between the epoxy group of the compound (g1) and the carboxyl group of the compound (g2).
  • Poly (meth) acrylate (G ′) can also be used as the compound (A) of the present invention.
  • (G) may be used alone or in combination of two or more.
  • the poly (meth) acrylate ( F) is preferred.
  • a cured coating film can be obtained with only the above-mentioned active energy ray-curable resin (A), but it is more excellent in curability and has a higher crosslinking density to easily obtain a high hardness coating film.
  • the (meth) acrylate (B) in combination from the viewpoint of easily adjusting the viscosity of the slurry to a range suitable for dispersion without using a large amount of organic solvent. It is more preferable to use a polyfunctional (meth) acrylate having 3 to 6 (meth) acryloyl groups in the molecular structure and having a molecular weight in the range of 100 to 600.
  • the resin (A), the acrylate (B), and the inorganic fine particles can be obtained by using the (meth) acrylate (B), which has been difficult to use as a dispersion medium, in combination with the antioxidant (C). (D) and the familiarity with remarkably improved, higher coating film performance such as hardness and transparency, and the generation of gel during the dispersion can be suppressed, the composition having excellent storage stability can get.
  • the polyfunctional (meth) acrylate (B) that can be used in the present invention includes, for example, a compound having one or two (meth) acryloyl groups in the molecular structure and a molecular weight in the range of 100 to 600 ( P1) and a compound (P2) having 3 to 6 (meth) acryloyl groups in the molecular structure and having a molecular weight in the range of more than 600 and less than 3,000.
  • the compound (P1) having one or two (meth) acryloyl groups in the molecular structure and having a molecular weight in the range of 100 to 600 includes, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, Tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acryl
  • the compound (P2) having 3 to 6 (meth) acryloyl groups in the molecular structure and having a molecular weight in the range of more than 600 and less than 3,000 has, for example, 3 or more hydroxyl groups in the molecular structure. It can be obtained by adding 3 to 6 molecules of (meth) acrylic acid chloride to a polyol compound obtained by modifying a hydroxyl group of a polyol compound with a polyalkylene glycol having a polyalkylene oxide repeating unit in the range of 11 to 20.
  • Examples of the polyol compound having three or more hydroxyl groups in the molecular structure include trimethylolmethane, trimethylolethane, trimethylolpropane, tetramethylolmethane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like.
  • Examples of the polyalkylene glycol having the polyalkylene oxide repeating unit in the range of 11 to 20 include polyethylene glycol and polypropylene glycol having the repeating unit in the range of 11 to 20.
  • the (meth) acrylate (B) may be used alone or in combination of two or more.
  • dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, or trimethylolpropane triacrylate is particularly preferable in that a coating film having higher hardness can be obtained.
  • the antioxidant (C) used as an essential component is, for example, a phenol-based antioxidant, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, an organic sulfur-based antioxidant, or phosphoric acid.
  • examples include ester-based antioxidants. These may be used alone or in combination of two or more.
  • the hindered phenol antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like are less colored and do not affect the appearance of the dispersion.
  • the phenolic antioxidant butylhydroxytoluene (BHT) and the like are particularly preferable.
  • phenolic antioxidant examples include 2,6-di-t-butyl-4-ethylphenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-Butylanilino) -1,3,5-triazine, 2,2-thio-diethylenebis ⁇ 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ⁇ , N, N′-hexamethylenebis ( 3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris- (3,5-di-t-butyl -4-hydroxybenzyl) -isocyanurate, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-meth
  • hindered phenolic antioxidants examples include 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, penta Erystole tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide) 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, and the like Or you may use 2 or more types.
  • hindered amine antioxidant examples include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, tris (2,2,6,6-tetramethyl-4 -Piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 '-(1,2-ethanediyl) -Bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, N- (2,2,6,6-tetramethyl-4 -Piperid
  • Organic sulfur-based antioxidants is an antioxidant containing sulfur in the molecule.
  • sulfur-containing antioxidants include dioctadecyl 3-3'-thiodipropanoate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, 4,4 Examples include '-thiobis-3-methyl-6-tert-butylphenol and thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].
  • phosphoric acid ester antioxidant examples include tris [2,4-di- (tert) -butylphenyl] phosphine tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl)].
  • the inorganic fine particles (D) used in the present invention are not particularly limited, and examples thereof include silica, alumina, zirconia, titania, barium titanate, and antimony trioxide. These may be used alone or in combination of two or more.
  • the inorganic fine particles (D) preferably have an average primary particle diameter in the range of 5 nm to 300 nm in view of obtaining a coating film with higher hardness, and a coating film with higher transparency can be obtained. Therefore, those having an average primary particle diameter in the range of 5 nm to 150 nm are particularly preferable, and those having an average primary particle diameter in the range of 5 nm to 50 nm are most preferable.
  • silica fine particles are preferable because they are easily available and easy to handle.
  • the silica fine particles include dry silica fine particles and wet silica fine particles.
  • the dry silica fine particles are, for example, silica fine particles obtained by burning silicon tetrachloride in an oxygen or hydrogen flame.
  • the wet silica fine particles are, for example, silica fine particles obtained by neutralizing sodium silicate with a mineral acid. According to the production method of the present invention, even when any silica fine particle is used, the obtained dispersion can maintain good dispersion stability over a long period of time.
  • the composition of the present invention contains the active energy ray-curable resin (A), the antioxidant (C), and the inorganic fine particles (D) as essential components.
  • the active energy ray-curable resin (A), which is an organic component in the composition, and an acrylate (B used in combination as necessary) are obtained in that a coating film having excellent storage stability and high hardness can be obtained.
  • the inorganic fine particles (D) as the inorganic component [resin (A) + acrylate (B)] / [inorganic fine particles (D)] are in the range of 10 to 90 parts by weight / 90 to 10 parts by weight. It is preferably 30 to 90 parts by mass / 70 to 10 parts by mass.
  • the active energy ray-curable resin (A) and the polyfunctional (meth) are preferred.
  • the mass ratio [resin (A)] / [acrylate (B)] to acrylate (B) is preferably in the range of 10 to 90 parts by mass / 90 to 10 parts by mass, and 10 to 70 parts by mass / 90 to 30 parts. A range of parts by mass is particularly preferable.
  • the content of the antioxidant (C) is preferably in the range of 0.05 to 0.4 wt% of the inorganic fine particles (D).
  • composition of the present invention may contain various additives as necessary.
  • various additives include a coupling agent (O) and a dispersion aid.
  • the coupling agent (O) is used for the purpose of enhancing the dispersibility of the inorganic fine particles (D) by introducing a functional group onto the surface of the inorganic fine particles (D).
  • a functional group onto the surface of the inorganic fine particles (D).
  • vinyl silane coupling agent epoxy silane coupling agent, styrene silane coupling agent, methacryloxy silane coupling agent, acryloxy silane coupling agent, amino silane coupling agent, Ureido silane coupling agents, chloropropyl silane coupling agents, mercapto silane coupling agents, sulfide silane coupling agents, isocyanate silane coupling agents, aluminum silane coupling agents, etc.
  • vinyl silane coupling agent epoxy silane coupling agent, styrene silane coupling agent, methacryloxy silane coupling agent, acryloxy silane coupling agent, amino silane coupling agent, Ureido silane coupling agents, chloropropyl silane
  • vinyl silane coupling agents include vinyl trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy Propylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- ( Minoethyl) -3-aminopropy
  • Epoxy-based silane coupling agents include, for example, diethoxy (glycidyloxypropyl) methylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Examples thereof include methyldiethoxysilane and 3-brisidoxypropyltriethoxysilane.
  • Examples of the styrene-based silane coupling agent include p-styryltrimethoxysilane.
  • methacryloxy silane coupling agent examples include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane.
  • acryloxy silane coupling agent examples include 3-acryloxypropyltrimethoxysilane.
  • Amino-based silane coupling agents include, for example, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3- Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyl Examples include trimethoxysilane.
  • ureido silane coupling agent examples include 3-ureidopropyltriethoxysilane.
  • chloropropyl silane coupling agent examples include 3-chloropropyltrimethoxysilane.
  • mercapto-based silane coupling agents examples include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethinesilane, and the like.
  • sulfide-based silane coupling agent examples include bis (triethoxysilylpropyl) tetrasulfide.
  • Examples of the isocyanate-based silane coupling agent include 3-isocyanatopropyltriethoxysilane.
  • aluminum coupling agent examples include acetoalkoxyaluminum diisopropylate. These coupling agents may be used alone or in combination of two or more.
  • dispersion aid examples include phosphate ester compounds such as isopropyl acid phosphate and triisodecyl phosphite. These may be used alone or in combination of two or more. Among these, isopropyl acid phosphate excellent in dispersion assist performance is preferable.
  • the organic solvent (T) may be added to the composition of the present invention as necessary.
  • the viscosity of the slurry is preferably in the range of 10 to 100 mPa ⁇ s, more preferably in the range of 3 to 60 mPa ⁇ s, from the viewpoint of good separation of the slurry and the medium.
  • organic solvent examples include ketone solvents such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); cyclic ether solvents such as tetrahydrofuran (THF) and dioxolane; methyl acetate, ethyl acetate, butyl acetate, and the like.
  • Esters aromatic solvents such as toluene and xylene
  • alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether. These may be used alone or in combination of two or more.
  • ketone solvents are preferred, with methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) being particularly preferred.
  • the amount of the organic solvent (T) used is preferably adjusted so that the viscosity of the slurry is in the range of 10 to 100 mPa ⁇ s.
  • the organic solvent (T) since the (meth) acrylate (B), which is usually difficult to be used for dispersion in a wet ball mill, can be used as a raw material of the slurry, the organic solvent (T) is less than usual.
  • the amount used can be reduced. Specifically, it is preferably used in the range of 30 to 70 parts by mass in 100 parts by mass of the slurry. Above all, 30 to 30 parts by mass can be obtained in that a composition having a sufficiently high nonvolatile content and does not require a concentration step or the like can be obtained. It is preferable to use in the range of 65 parts by mass.
  • the manufacturing method of the composition of this invention is demonstrated.
  • the slurry is agitated by rotating the slurry by rotating the rotary shaft, the vessel having a medium filled therein, a rotary shaft, and a rotary shaft coaxially with the rotary shaft.
  • a wet ball mill having blades, a slurry supply port installed in the vessel, a slurry discharge port installed in the vessel, and a shaft seal device disposed in a portion where the rotary shaft passes through the vessel.
  • the shaft seal device has two mechanical seal units, and a wet ball mill having a structure in which the seal portions of the two mechanical seal units are sealed with an external seal liquid is supplied to the vessel from the supply port.
  • the inorganic fine particles (D) in the slurry are pulverized, and the inorganic fine particles (D) are dispersed in the active energy ray-curable resin (A) and (meth) acrylate (B) used in combination as necessary. It is preferable to use a method of discharging from the discharge port. At this time, it is preferable to add the antioxidant (C) in advance to the slurry from the viewpoint of suppressing the generation of gel.
  • the wet ball mill Y has a shaft seal device (u1) as shown in FIG.
  • the slurry is supplied to the vessel (p1) through the supply port (s1) in FIG.
  • the vessel (p1) is filled with a medium, and the slurry and the medium are stirred and mixed by the stirring blade (r1) rotated by the rotation drive of the rotating shaft (q1), and the inorganic fine particles (D) are pulverized.
  • the inorganic fine particles (D) are dispersed in the active energy ray-curable resins (A) and (B).
  • the inside of the rotating shaft (p1) is a cavity having an opening on the discharge port (t1) side.
  • a screen-type separator 2 is installed in the cavity as a separator, and a flow path leading to the discharge port (t1) is provided inside the separator 2.
  • the slurry in the vessel (p1) is pushed by the supply pressure of the slurry, and is conveyed from the opening of the rotary shaft (p1) to the separator 2 inside thereof.
  • the separator 2 does not pass through the medium having a large particle diameter but allows only the slurry having a small particle diameter to pass through, so that the medium stays in the vessel (p1), and only the slurry is discharged from the discharge port (t1).
  • the wet ball mill Y has a shaft seal device (u1) as shown in FIG.
  • the rotary ring 3 fixed on the shaft (q1) and the fixed ring 4 fixed on the housing 1 of the shaft seal device in FIG. 1 form a seal portion.
  • Two mechanical seal units having the arranged structure are provided, and the rotation ring 3 and the stationary ring 4 in the unit are aligned in the same direction in the two units.
  • the seal portion refers to a pair of sliding surfaces formed by the rotating ring 3 and the fixed ring 4.
  • the liquid seal space 11 is supplied with an external seal liquid (R) supplied from an external seal liquid tank 7 by a pump 8 through the external seal liquid supply port 5 and through the external seal liquid discharge port 6. By being returned to the tank 7, it is circulated and supplied. As a result, the liquid seal space 11 is filled with the external seal liquid (R) in a liquid-tight manner, and the gap 9 formed between the rotating ring 3 and the fixed ring 4 in the seal portion is formed with the external seal liquid (R). ).
  • the sealing liquid (R) lubricates and cools the sliding surfaces of the rotating ring 3 and the stationary ring 4.
  • the force P1 that the stationary ring 4 is pressed against the rotating ring 3 by the inflow pressure of the external sealing liquid (R), the force P2 that the stationary ring 4 is pressed against the rotating ring 3 by the spring 10, and the external sealing liquid (R) are set so that the force with which the stationary ring 4 is separated from the rotating ring 3 by the inflow pressure is balanced with P3.
  • the gap 9 between the stationary ring 4 and the rotating ring 3 which is the sliding surface is filled with the external sealing liquid (R) in a liquid-tight manner, and the gap 9 is filled with the active energy ray-curable resin (A) and (B) does not enter.
  • the shaft seal device such as the shaft seal device (u1) is, for example, a tandem mechanical seal.
  • examples of commercially available wet ball mill Y having the tandem mechanical seal as a shaft seal device include “LMZ” series manufactured by Ashizawa Finetech Co., Ltd.
  • the external sealing liquid (R) is a non-reactive liquid, and examples thereof include various organic solvents listed as the organic solvent (T). Among these, the same slurry as the solvent contained in the component is preferable, and therefore a ketone solvent is preferable, and methyl ethyl ketone (MEK) or methyl isobutyl ketone (MIBK) is particularly preferable.
  • MEK methyl ethyl ketone
  • MIBK methyl isobutyl ketone
  • various micro beads are used.
  • the material for the microbeads include zirconia, glass, titanium oxide, copper, and zirconia silicate. Among these, zirconia microbeads are preferred because they are the hardest and less worn.
  • the media has good separation of the media from the slurry in the screen-type separator 2 in FIG. 1, the dispersibility time is relatively short due to the high pulverization capacity of the inorganic fine particles,
  • the average particle size is preferably in the range of 10 to 1000 ⁇ m in terms of median size because the impact is not too strong and the overdispersion phenomenon of inorganic fine particles is difficult to occur.
  • the above-mentioned overdispersion phenomenon refers to a phenomenon in which a new active surface is generated due to destruction of inorganic fine particles and reaggregation occurs.
  • the overdispersion phenomenon occurs, the dispersion is gelled.
  • the filling rate of the media in the vessel (p1) in FIG. 1 is in the range of 75 to 90% by volume of the vessel internal volume in that the power required for dispersion is minimized and pulverization can be performed most efficiently. It is preferable.
  • the stirring blade (r1) has a large impact when the medium collides with the inorganic fine particles (D) and increases the dispersion efficiency. Therefore, the peripheral speed of the tip is rotated so that the peripheral speed is in the range of 5 to 20 m / sec. It is preferably driven and more preferably in the range of 8 to 20 m / sec.
  • the manufacturing method using the wet ball mill Y described above may be a batch type or a continuous type. Further, in the case of a continuous type, it may be a circulation type that is supplied again after the slurry is taken out or a non-circulation type. Among these, the circulation type as shown in FIG. 3 is preferable in that the production efficiency is high and the homogeneity of the obtained dispersion is excellent.
  • FIG. 3 is a schematic view of a circulating dispersion cycle using the wet ball mill Y.
  • the slurry extracted by the pump 13 from the stock tank 12 storing the slurry in FIG. 3 is supplied to the vessel (p1) from the supply port (s1) in FIG.
  • the slurry dispersed in the vessel (p1) is returned to the stock tank 12 through the discharge port (t1) and the valve 16 in FIG.
  • the slurry returned to the tank 12 passes through the above-described dispersion path again, and is circulated and dispersed by repeating this.
  • the particle size of the slurry is appropriately measured in the course of circulation dispersion, and the dispersion is terminated when a desired value is reached.
  • the supply flow rate of the slurry to the vessel (p1) is equal to the discharge flow rate of the slurry from the vessel (p1), and the vessel (p1
  • the residence time of the slurry in () is suitable and the dispersion efficiency is high. Therefore, the range of 30 to 100 L / hour is preferable, and the range of 50 to 80 L / hour is more preferable per liter of the vessel (p1). .
  • the pump 13 is preferably a diaphragm pump, which is a pump that does not easily generate mechanoradicals.
  • Examples of commercially available products include “TPL” series manufactured by Takumina Corporation.
  • the procedure for supplying the slurry to the vessel (p1) is as follows. After the medium in the vessel (p1) of the wet ball mill Y is filled, the valve 17 connected to the product tank and the valve 18 which is an inlet for compressed air or nitrogen shown in FIG. First, the motor 14 is operated in a state in which 19 is opened. By driving the motor 14, the shaft (q1) and the stirring blade (r1) are rotationally driven. Next, the pump 13 is operated, and the raw material slurry in the stock tank 12 is supplied from the supply port (s1) into the vessel (p1) by a certain amount.
  • the dispersion is performed as described above, and the particle size of the inorganic fine particles (D) in the slurry reaches a desired value, and the procedure for terminating the dispersion is as follows.
  • the pump 13 is stopped, and then the motor 14 is stopped to finish the pulverization. Then, after closing the valve 19, the valve 17 is opened and the pump 13 is restarted to transfer the product slurry in the stock tank 12 into the product tank 15. Next, in order to extract the product slurry remaining in the vessel (p1), the pump 13 is stopped and the valve 17 is closed. Next, the line returning to the stock tank 12 via the valve 16 is connected to the product tank 15. The empty stock tank 12 is filled with the same type of solvent as that contained in the slurry, the motor 14 is restarted, the pump 13 is restarted, and the product slurry remaining in the vessel (p1) Can be collected in the product tank 15.
  • the transfer may be stopped before the total amount of the product slurry remaining in the vessel (p 1) is transferred to the product tank 15, or the total amount of the product slurry is recovered in the product tank 15. Therefore, it may be stopped at the timing when the solvent slightly mixes in the product tank 15.
  • the wet ball mill Z has a shaft seal device (u2) as shown in FIG.
  • the slurry is supplied into the vessel (p2) through the supply port (s2) in FIG.
  • the vessel (p2) is filled with a medium, and the slurry and the medium are agitated and mixed by the agitating blade (r2) rotated by the rotation drive of the rotating shaft (q2), and the inorganic fine particles (D) are pulverized.
  • the inorganic fine particles (D) are dispersed in the active energy ray-curable resins (A) and (B).
  • an impeller-type separator 20 is provided as a separator, and the impeller-type separator 20 rotates coaxially with the shaft (q2), so that a medium having a high specific gravity is moved outward in the radial direction.
  • the slurry having a low specific gravity is attracted to the axial center portion of the separator 35 and discharged from the discharge port (t2).
  • the wet ball mill Z has a shaft seal device (u2) as shown in FIG.
  • the rotary ring 22 fixed on the shaft (q2) and the fixed ring 23 fixed to the housing 21 of the shaft seal device in FIG. 5 form a seal portion.
  • the seal portion refers to a pair of sliding surfaces formed by the rotating ring 22 and the fixed ring 23.
  • the liquid seal space 24 is supplied with an external seal liquid (R) supplied from an external seal liquid tank 27 by a pump 28 through the external seal liquid supply port 25, and through the external seal liquid discharge port 26. By being returned to the tank 27, it is circulated and supplied. As a result, the liquid seal space 24 is filled with the seal liquid (R) in a liquid-tight manner, and a gap 29 formed between the rotating ring 22 and the fixed ring 23 in the seal portion becomes an external seal liquid (R ).
  • the sealing liquid (R) lubricates and cools the sliding surfaces of the rotating ring 22 and the stationary ring 23.
  • the inflow pressure of the sealing liquid (R) and the pressure of the spring 30 are set so that the force that separates the stationary ring 23 from the rotating ring 22 by the inflow pressure of P3 ′ is balanced with P3 ′.
  • the sealing liquid (R) is liquid-tightly filled in the gap 29 between the stationary ring 22 and the rotating ring 23 which are sliding surfaces, and the active energy ray-curable resin (A) and ( B) does not enter.
  • Examples of the shaft seal device such as the shaft seal device (u2) include a double-type mechanical seal.
  • Commercially available wet ball mills Z having the double mechanical seal as a shaft seal device are, for example, “Max Nano Getter” series manufactured by Ashizawa Finetech Co., Ltd., “Ultra Apex Mill (UAM)” manufactured by Kotobuki Industries Co., Ltd. Series, “Super Apex Mill (SAM)” series and the like.
  • the external sealing liquid (R) is a non-reactive liquid, and examples thereof include various organic solvents listed as the organic solvent (T). Among these, the same slurry as the solvent contained in the component is preferable, and therefore a ketone solvent is preferable, and methyl ethyl ketone (MEK) or methyl isobutyl ketone (MIBK) is particularly preferable.
  • MEK methyl ethyl ketone
  • MIBK methyl isobutyl ketone
  • micro beads are used as the medium filled in the vessel (p2) in FIG.
  • the material for the microbeads include zirconia, glass, titanium oxide, copper, and zirconia silicate.
  • zirconia microbeads are preferred because they are the hardest and less worn, and have high specific gravity and good separation from the slurry in the impeller-type separator 35.
  • the media has good separation of the media from the slurry in the screen-type separator 20 in FIG. 4, and the dispersion time is relatively short due to the high pulverization ability of the silica fine particles. Since the impact is not too strong and an excessive dispersion phenomenon of silica fine particles is difficult to occur, it is preferable that the average particle diameter is in the range of 10 to 1000 ⁇ m in terms of median diameter.
  • the filling rate of the media in the vessel (p2) in FIG. 1 is in the range of 75 to 90% by volume of the vessel internal volume in that the power required for dispersion is minimized and pulverization can be performed most efficiently. It is preferable.
  • the agitating blade (r2) rotates so that the peripheral speed of the tip is in the range of 5 to 20 m / sec because the impact when the medium collides with the inorganic fine particles (D) is large and the dispersion efficiency is increased. It is preferably driven and more preferably in the range of 8 to 20 m / sec.
  • the manufacturing method using the wet ball mill Z described above may be a batch type or a continuous type. Further, in the case of a continuous type, it may be a circulation type that is supplied again after the slurry is taken out or a non-circulation type. Among these, the circulation type as shown in FIG. 6 is preferable in that the production efficiency is high and the homogeneity of the obtained dispersion is excellent.
  • FIG. 6 is a schematic view of a circulating dispersion cycle using the wet ball mill Z.
  • the slurry extracted by the pump 32 from the stock tank 31 storing the slurry in FIG. 6 is supplied to the vessel (p2) from the supply port (s2) in FIG.
  • the slurry dispersed in the vessel (p2) is returned to the stock tank 31 through the discharge port (t2) and the valve 35 in FIG.
  • the slurry returned to the stock tank 31 passes through the dispersion path described above again, and is circulated and dispersed by repeating this.
  • the particle size of the slurry is appropriately measured in the course of circulation dispersion, and the dispersion is terminated when a desired value is reached.
  • the supply flow rate of the slurry to the vessel (p2) is equal to the discharge flow rate of the slurry from the vessel (p2), and the vessel (p2
  • the residence time of the slurry in () is suitable, and the dispersion efficiency is high. Therefore, the range of 30 to 100 L / hour is preferable, and the range of 50 to 80 L / hour is more preferable per liter of the vessel (p2). .
  • the pump 32 is preferably a diaphragm pump, which is a pump that does not easily generate mechanoradicals.
  • Examples of commercially available products include “TPL” series manufactured by Takumina Corporation.
  • the procedure for supplying the slurry to the vessel (p2) is as follows. After the medium in the vessel (p2) of the wet ball mill Y is filled, the valve 36 connected to the product tank and the valve 37, which is an inlet for compressed air or nitrogen, shown in FIG. First, the motor 33 is operated in a state in which is opened. By driving the motor 33, the shaft (q2) and the stirring blade (r2) are rotationally driven. Next, the pump 32 is operated, and the raw material slurry in the stock tank 31 is supplied from the supply port (s2) into the vessel (p2) by a certain amount.
  • the dispersion is performed as described above, and the particle size of the inorganic fine particles (D) in the slurry reaches a desired value, and the procedure for terminating the dispersion is as follows.
  • the pump 32 is stopped, and then the motor 33 is stopped to finish the pulverization. Then, after closing the valve 38, the valve 36 is opened, and the pump 32 is restarted to transfer the product slurry in the stock tank 31 into the product tank 34. Next, in order to extract the product slurry remaining in the vessel (p2), the pump 32 is stopped and the valve 36 is closed. Next, the line returning to the stock tank 31 via the valve 35 is connected to the product tank 34. The empty stock tank 31 is filled with the same type of solvent as that contained in the slurry, and the motor 33 is restarted and the pump 33 is restarted to leave the product slurry remaining in the vessel (p2). Can be collected in the product tank 34.
  • the transfer of the product slurry remaining in the vessel (p2) may be stopped before it moves to the product tank 34 so that the solvent does not enter the product tank 34, or the entire product slurry is collected in the product tank 34. Therefore, it may be stopped at the timing when the solvent is mixed into the product tank 34 slightly.
  • the wet ball mill Y having a screen type separator is preferable in that the separation ability of the medium and the slurry is high.
  • the comparison in which the median diameter is in the range of 15 to 300 ⁇ m is performed. And a method of performing this dispersion step using small particles as media.
  • a relatively large medium having a median diameter in the range of 300 to 1000 ⁇ m is used. Since such a medium has a large impact force when it collides with the inorganic fine particles (D), it is suitable for pulverizing the inorganic fine particles (D) having a large particle size. Grind to a certain particle size.
  • a relatively small medium having a median diameter in the range of 15 to 300 ⁇ m is used. Although such a medium has a small impact force when colliding with the inorganic fine particles (D), the number of particles contained in the same volume is larger than that of a medium having a large particle size, so that the inorganic fine particles (D) The number of collisions with will increase. Therefore, it is used for the purpose of pulverizing the inorganic fine particles (D) pulverized to some extent in the pre-dispersion step into finer particles.
  • the pre-dispersion step and the main dispersion step are preferably performed in two stages. If the pre-dispersion step is too long, the over-dispersion phenomenon may occur. Therefore, the pre-dispersion step is preferably performed in a range in which the slurry circulates in the vessels (p1) and (p2) for 1 to 3 cycles. .
  • composition obtained by the production method of the present invention can be used as a coating itself, or as other compounds and additives as necessary.
  • additives include, for example, ultraviolet absorbers, silicon-based additives, organic beads, fluorine-based additives, rheology control agents, defoaming agents, mold release agents, silane coupling agents, antistatic agents, antifogging agents, A coloring agent, an organic solvent, an inorganic filler, etc. are mentioned.
  • 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) -1,3 Triazine derivatives such as 1,5-triazine, 2- (2'-xanthenecarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2- And xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like.
  • silicon-based additive examples include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified dimethyl.
  • examples thereof include polyorganosiloxanes having an alkyl group and a phenyl group, such as a polysiloxane copolymer and an amino-modified dimethylpolysiloxane copolymer. These may be used alone or in combination of two or more.
  • 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, Examples thereof include polyester resin beads, polyamide resin beads, polyimide resin beads, polyfluorinated ethylene resin beads, and polyethylene resin beads.
  • a preferable value of the average particle diameter of these organic beads is in the range of 1 to 10 ⁇ m. These may be used alone or in combination of two or more.
  • fluorine-based additive examples include DIC Corporation “Mega Fuck” series. These may be used alone or in combination of two or more.
  • release agent examples include “Tegorad 2200N”, “Tegorad 2300”, “Tegorad 2100” manufactured by Evonik Degussa, “UV3500” manufactured by BYK Chemie, “Paintad 8526” manufactured by Toray Dow Corning, and “SH-29PA”. Or the like. These may be used alone or in combination of two or more.
  • silane coupling agent examples include various silane coupling agents listed as the coupling agent (O). These may be used alone or in combination of two or more.
  • antistatic agent examples include pyridinium, imidazolium, phosphonium, ammonium, or lithium salts of bis (trifluoromethanesulfonyl) imide or bis (fluorosulfonyl) imide. These may be used alone or in combination of two or more.
  • organic solvent examples include various organic solvents listed as the organic solvent (T). These may be used alone or in combination of two or more.
  • the amount of each of the various additives used is preferably in a range where the effect is sufficiently exhibited and ultraviolet curing is not inhibited. Specifically, the amount of each additive is 0.01 to 40 masses per 100 mass parts of the composition of the present invention. The range of parts is preferred.
  • the paint containing the composition of the present invention further contains a photopolymerization initiator (Q).
  • the photopolymerization initiator (Q) include benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-bisdimethylaminobenzophenone, 4,4′-bisdiethylaminobenzophenone, 4,4′- Various benzophenones such as dichlorobenzophenone, Michler's ketone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;
  • ⁇ -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;
  • photopolymerization initiators 1-hydroxycyclohexyl phenyl ketone, 2-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-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- ( One or more selected from the group of 4-morpholinophenyl) -butan-1-one
  • the amount of the photopolymerization initiator (Q) used is preferably an amount that can sufficiently function as a photopolymerization initiator and does not cause crystal precipitation or deterioration of physical properties of the coating film. Is preferably used in the range of 0.05 to 20 parts by weight, particularly preferably in the range of 0.1 to 10 parts by weight, based on 100 parts by weight of the paint.
  • the paint of the present invention may further use various photosensitizers in combination with the photopolymerization initiator (Q).
  • the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.
  • the coating material of the present invention can be used as a coating layer that protects the surface of a base material by applying it on various base materials and irradiating and curing the active energy rays.
  • the coating material of the present invention may be directly applied to the surface protection member, or a material applied on the plastic film (R) may be used as a protective film such as a polarizing plate.
  • a material applied on the plastic film (R) may be used as a protective film such as a polarizing plate.
  • the coating film obtained by using the coating material of the present invention is characterized by high hardness and low curl
  • the coating material of the present invention is applied especially on a plastic film (R) to be used as a protective film or a film-like molded product. It is preferable to use it.
  • the plastic film (R) is, for example, polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, cyclic olefin, polyimide resin.
  • the coating amount when applying the paint of the present invention to the plastic film (R) is such that the mass after drying is in the range of 0.1 to 30 g / m 2 , preferably in the range of 1 to 20 g / m 2. It is preferable to do this.
  • the film thickness of the coating film of this invention expresses sufficient hardness as a protective layer by setting it as 3% or more with respect to the film thickness of the said plastic film (R).
  • the film thickness of the coating film is preferably in the range of 3 to 100% with respect to the film thickness of the plastic film (R), more preferably in the range of 5 to 100%.
  • a film having a range of 5 to 50% with respect to the film thickness is particularly preferred.
  • Examples of the coating method of the present invention include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.
  • Examples of the active energy rays irradiated when the paint of the present invention is cured to form a coating film include ultraviolet rays and electron beams.
  • an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp is used as a light source, and the amount of light, the arrangement of the light source, etc. are adjusted as necessary.
  • a high-pressure mercury lamp it is preferable to cure at a conveyance speed of 5 to 50 m / min with respect to one lamp having a light quantity that is usually in the range of 80 to 160 W / cm.
  • an electron beam accelerator having an accelerating voltage that is usually in the range of 10 to 300 kV at a conveyance speed of 5 to 50 m / min.
  • the base material to which the paint of the present invention is applied is suitably used not only as a plastic film (R) but also as a surface coating agent for various plastic molded products, for example, cellular phones, household appliances, automobile bumpers and the like. be able to.
  • examples of the method for forming the coating film include a coating method, a transfer method, and a sheet bonding method.
  • the coating method is a method in which the paint is spray-coated or coated as a top coat on a molded product using a printing device such as a curtain coater, roll coater, gravure coater, etc., and then cured by irradiation with active energy rays. is there.
  • a transfer material obtained by applying the above-described coating material of the present invention on a substrate sheet having releasability is adhered to the surface of the molded product, and then the substrate sheet is peeled off to top coat the surface of the molded product.
  • curing by irradiation with active energy rays, or by bonding the transfer material to the surface of the molded article, curing by irradiation with active energy rays, and then peeling the substrate sheet A method of transferring the top coat to the surface is mentioned.
  • a protective sheet having a coating film made of the paint of the present invention on a base sheet, or a protective sheet having a coating film made of the paint and a decorative layer on a base sheet is plastic molded.
  • a protective layer is formed on the surface of the molded product by bonding to the product.
  • the coating material of the present invention can be preferably used for the transfer method and the sheet adhesion method.
  • a transfer material is first prepared.
  • the transfer material can be produced, for example, by applying the paint alone or mixed with a polyisocyanate compound onto a base sheet and heating to semi-cure (B-stage) the coating film. .
  • the active energy ray-curable resin (A) is a hydroxyl group in the molecular structure such as poly (meth) acrylates (F1) and (F2) of acrylic polymer, poly (meth) acrylate (G) of epoxy resin, and the like. May be used in combination with a polyisocyanate compound for the purpose of more efficiently performing the B-staging step.
  • the above-described paint of the present invention is applied onto a base sheet.
  • the method for applying the paint include a gravure coating method, a roll coating method, a spray coating method, a lip coating method, a coating method such as a comma coating method, and a printing method such as a gravure printing method and a screen printing method.
  • the coating thickness is preferably such that the thickness of the cured coating film is 0.5 to 30 ⁇ m because the wear resistance and chemical resistance are good, and it is preferably 1 to 6 ⁇ m. It is more preferable to paint so that
  • the heating is usually 55 to 160 ° C, preferably 100 to 140 ° C.
  • the heating time is usually 30 seconds to 30 minutes, preferably 1 to 10 minutes, more preferably 1 to 5 minutes.
  • the surface protective layer of the molded product using the transfer material may be formed by, for example, bonding the B-staged resin layer of the transfer material and the molded product, and then irradiating active energy rays to cure the resin layer.
  • the B-staged resin layer of the transfer material is adhered to the surface of the molded product, and then the base sheet of the transfer material is peeled to remove the B-staged resin layer of the transfer material.
  • energy rays are cured by irradiation with active energy rays to cure the resin layer by cross-linking (transfer method), or the transfer material is sandwiched in a mold and the resin is placed in the cavity.
  • a transfer material is adhered to the surface, the substrate sheet is peeled off and transferred onto the molded product, and then the energy beam is cured by irradiation with active energy rays to crosslink and cure the resin layer. And the like (molding simultaneous transfer method).
  • the sheet bonding method is specifically a resin layer formed by bonding a base sheet of a protective layer forming sheet prepared in advance and a molded product, and then thermally curing by heating to form a B-stage.
  • a method of performing cross-linking curing (post-adhesion method), and the protective layer forming sheet is sandwiched in a molding die, and a resin is injected and filled in the cavity to obtain a resin molded product, and at the same time, the surface and the protective layer are formed.
  • a method in which a resin sheet is bonded and then thermally cured by heating to crosslink and cure the resin layer (molding simultaneous bonding method).
  • the coating film of the present invention is a coating film formed by applying and curing the coating material of the present invention on the above-described plastic film (R), or the coating material of the present invention as a surface protective agent for plastic molded products. It is a coating film formed by coating and curing, and the film of the present invention is a laminated film in which a coating film is formed on a plastic film (R).
  • a polarizing plate used for a liquid crystal display, a touch panel display, or the like is obtained by applying the paint of the present invention on a plastic film (R) and irradiating active energy rays. It is preferable to use it as a protective film for the coating because of its excellent coating film hardness.
  • the paint of the present invention is applied to a protective film of a polarizing plate used for a liquid crystal display, a touch panel display, etc., and the film is formed by irradiating and curing active energy rays, the cured coating film has a high hardness. It becomes a protective film that combines high transparency.
  • an adhesive layer may be formed on the traditional side of the coating layer to which the paint of the present invention is applied.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using a gel permeation chromatograph (GPC) under the following conditions.
  • Measuring device HLC-8220 manufactured by Tosoh Corporation Column: Tosoh Corporation guard column H XL -H + Tosoh Corporation TSKgel G5000H XL + Tosoh Corporation TSKgel G4000H XL + Tosoh Corporation TSKgel G3000H XL + Tosoh Corporation TSKgel G2000H XL Detector: RI (differential refractometer) Data processing: Tosoh Corporation SC-8010 Measurement conditions: Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard; Polystyrene sample; 0.4% by mass tetrahydrofuran solution in terms of resin solids filtered through microfilter (100 ⁇ l)
  • Synthesis Example 1 (Synthesis of acrylic acrylate A1) A reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube was charged with 500 parts by mass of methyl isobutyl ketone (hereinafter abbreviated as “MIBK”) until the system temperature reached 110 ° C. while stirring. 4.
  • MIBK methyl isobutyl ketone
  • the temperature was raised, and then 250 parts by weight of glycidyl methacrylate, 80 parts by weight of methyl methacrylate, 40 parts by weight of ethyl acrylate, and t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Emulsifier Co., Ltd.) After 5 parts by mass of the mixed solution was dropped from the dropping funnel over 2 hours, the mixture was held at 110 ° C. for 15 hours. Next, the temperature was lowered to 90 ° C., 5 parts by weight of methoquinone and 130 parts by weight of acrylic acid were added, 2.6 parts by weight of triphenylphosphine was added, the temperature was further raised to 100 ° C.
  • Example 1 Methyl isobutyl solution of acrylic acrylate A1 obtained in Synthesis Example 1 22.5 parts by mass (12.5 parts by mass of acrylic acrylate A1 in 22.5 parts by mass), dipentaerythritol hexaacrylate (hereinafter abbreviated as “DPHA”) 11.25 parts by mass, Aerosil R7200 (“Aerosil R7200” manufactured by Nippon Aerosil Co., Ltd., 22.5 parts by mass of silica fine particles having an average primary particle size of 12 nm), 44 parts by mass of MIBK, and butylhydroxytoluene (hereinafter “BHT”) 0.045 parts by mass) was blended to obtain a slurry. The slurry contains 55.25 parts by mass of MIBK in 100 parts by mass.
  • DPHA dipentaerythritol hexaacrylate
  • Aerosil R7200 Aerosil R7200 (“Aerosil R7200” manufactured by Nippon Aerosil Co.,
  • the slurry is charged into the stock tank 31 in FIG. 6 and the motor 33 is operated to rotate the rotary shaft (q2) and the stirring blade (r2).
  • the peripheral speed of the tip of the stirring blade (r2) is 12 m.
  • the power of the motor 33 was adjusted to be / sec.
  • the slurry was supplied from the slurry supply port (s2) of FIG. 4 using the pump 32 so that the flow rate of the slurry was 100 ml / min.
  • a dispersion was obtained by circulating and grinding for 45 minutes according to the circulation cycle shown in FIG.
  • Coating transparency test Method for making cured coating film The coating material is applied onto a polyethylene terephthalate (PET) film (film thickness 125 um) with a bar coater (film thickness 3-4 ⁇ m), dried at 70 ° C. for 1 minute, and a high-pressure mercury lamp under nitrogen.
  • PET polyethylene terephthalate
  • the test piece which has a cured coating film was obtained by making it pass and harden
  • Transparency Test Method The haze value of the coating film was measured using “Haze Computer HZ-2” manufactured by Suga Test Instruments Co., Ltd. The lower the haze value, the higher the transparency of the coating film.
  • Examples 2 to 6 A paint was obtained in the same manner as in Example 1 except that the composition of the composition was as shown in Table 1. About these, the test similar to Example 1 was done. The results are shown in Table 1.
  • Footnote * 1 “Irganox 1010” in Table 1 is a product name of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] manufactured by BASF.
  • dispersion was performed in the same manner as in Example 1 to obtain a dispersion.
  • Comparative Examples 2-3 A paint was obtained in the same manner as in Example 1 except that the composition of the composition was as shown in Table 2. About these, the test similar to Example 1 was done. The results are shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
PCT/JP2015/074198 2014-10-24 2015-08-27 活性エネルギー線硬化性樹脂組成物、その製造方法、塗料、塗膜、及び積層フィルム WO2016063624A1 (ja)

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KR1020177008321A KR102350778B1 (ko) 2014-10-24 2015-08-27 활성 에너지선 경화성 수지 조성물, 그 제조 방법, 도료, 도막, 및 적층 필름
CN201580057729.5A CN107075049B (zh) 2014-10-24 2015-08-27 活性能量射线固化性树脂组合物、其制造方法、涂料、涂膜、及层叠薄膜

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JP2018015931A (ja) * 2016-07-26 2018-02-01 三菱ケミカル株式会社 樹脂積層体、ディスプレー前面板、携帯型情報端末装置及び移動体用グレージング

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JP6637950B2 (ja) * 2017-02-07 2020-01-29 Ｄｉｃグラフィックス株式会社 コーティング組成物、及びこれを用いた化粧シート
JP2019147885A (ja) * 2018-02-27 2019-09-05 パナック株式会社 樹脂組成物、未硬化樹脂層、樹脂フィルム、樹脂フィルムの製造方法、及び積層体の製造方法
KR102423463B1 (ko) * 2020-12-29 2022-07-21 주식회사 삼영특수인쇄 점착층의 용이 탈착으로 인한 페트병의 재활용을 가능하게 하는 점착 분리용 조성물, 이를 사용한 라벨 및 페트병의 재활용 방법
KR102425451B1 (ko) * 2021-09-15 2022-07-27 한진케미칼 주식회사 건축도료 부착증진용 내황변성 열가소성 수지의 제조방법

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CN107057332A (zh) * 2017-06-12 2017-08-18 深圳永昌和科技有限公司 一种可控性好的3d打印超材料及其制备方法

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