JP4436276B2 - Paint composition - Google Patents

Description

  The present invention relates to a coating composition comprising an inorganic filler and a resin. More specifically, the present invention relates to a coating composition that prevents sedimentation of an inorganic filler without impairing physical properties of the coating film.

  Conventionally, a coating composition has been blended with an inorganic filler for the purpose of matting, coloring, antistatic and wear resistance, but the inorganic filler has a higher specific gravity than the resin component, and the coating composition There was a problem that sedimentation occurred during storage or use of the product, coating could not be performed, transparency of the coating film was impaired, and color separation occurred. Therefore, in order to improve the dispersion stability of the inorganic filler, a method of increasing the viscosity of the coating composition by adding silica or the like, a method of adding a dispersion stabilizer (for example, see Patent Document 1) and an inorganic filler A method of treating with a silane coupling agent (see, for example, Patent Document 2) has been proposed.

Japanese Patent Laid-Open No. 2000-262883 Japanese Patent Laid-Open No. 5-25422

However, in the method of increasing the viscosity of the paint by adding silica or the like, it is difficult to uniformly apply the coating. Therefore, at the time of coating, it is necessary to reduce the viscosity by diluting with an organic solvent, and thus prevention of sedimentation cannot be achieved after all. In addition, the method of adding a dispersion stabilizer has a drawback in that the physical properties of the coating film are deteriorated because the bondability between the dispersion stabilizer, the inorganic filler, and the resin component is weak. Further, the method of treating an inorganic filler with a silane coupling agent has a problem that the applicable inorganic filler is limited and the treatment process is complicated and a large amount of silane coupling agent is required.
An object of the present invention is to provide a coating composition having a relatively low viscosity and imparting excellent dispersion stability of an inorganic filler without impairing physical properties of the coating film.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention relates to an inorganic filler (A) comprising silica (a1) having a volume average particle diameter of 0.002 to 20 μm , or an inorganic filler (a2) other than (a1) and (a1 ), in the resin (B) and an organic solvent (C) Tona Ru coating composition, (a), based on the total weight of (B) and (C), (a) is 12 to 50%, the (B) 20 to 70%, (C) is 10 to 50%, the weight ratio of (a1) and (a2) is 100: 0 to 17:83, and (C) is the solubility of water at 25 ° C. 3 to 20 g / 100 g of organic solvent, an organic solvent selected from the group consisting of an ester having 4 to 5 carbon atoms, a ketone having 4 to 6 carbon atoms and an alcohol having 8 to 16 carbon atoms, and the composition is 0 A coating composition characterized by containing 2 to 5% by weight of water.

The coating composition of the present invention has the following effects.
(1) It has a relatively low viscosity and excellent dispersion stability of the inorganic filler.
(2) A coating film using the composition is excellent in mechanical properties.

  Although the kind of silica (a1) which is an essential component constituting (A) in the present invention is not particularly limited, for example, synthetic silica (wet method precipitated silica, gel silica, colloidal silica, ultrafine anhydrous silica, etc.) and Examples include natural silica (crystalline silica, crushed fused silica, spherical fused silica, and the like). Among these, from the viewpoint of dispersion stability in the coating composition, synthetic silica is preferable, and wet-method precipitated silica and ultrafine anhydrous silica are particularly preferable.

The volume average particle diameter of (a1) is 0.002 to 20 μm, preferably 0.01 to 10 μm, more preferably 0.05 to 8 μm. When the volume average particle size is less than 0.002 μm, the coating stability is deteriorated, and when it exceeds 20 μm, the dispersion stability is deteriorated.
Here, the volume average particle diameter is a value obtained by measuring by the following method using a SK laser particle size distribution measuring instrument [manufactured by Seishin Enterprise Co., Ltd.].
(Volume average particle diameter measurement method)
50 to 100 mg of a sample is added to 100 g of a dispersion medium (ion exchange water), and the sample is dispersed by irradiating with ultrasonic waves (output 200 Hz) for 60 seconds, and then measured using a SK laser particle size distribution measuring machine.

  (A1) may be subjected to surface treatment if necessary. As a surface treatment method, a method of spraying polyethylene wax or the like on silica at a high temperature (see JP-A-7-166091, etc.), a silane coupling agent is sprayed on silica, and a hydrophobic group, a hydrophilic group or a reactive group is applied to the surface. And the like (see JP 2002-146232 A).

  (A) is preferably 0.5 to 50 (more preferably 1 to 30) other than (a1) in order to color the paint or impart antistatic properties, abrasion resistance and other performances. It is preferable to further contain an inorganic filler (a2) having a volume average particle diameter of μm and preferably having a true specific gravity of 1.5 to 7 (more preferably 2 to 5).

  As (a2), for example, when coloring is intended, a white pigment (titanium dioxide, alumina white, white carbon, clay, talc, precipitated barium sulfate, barite powder, calcium carbonate, lead white, aluminum powder, lithopone, Black pigment (zinc oxide, chromium oxide, iron black, carbon black), red pigment (iron oxide, vermilion, cadmium red), blue pigment (cobalt blue, ultramarine blue, bitumen), yellow pigment (iron oxide yellow, cadmium yellow, yellow) Lead, zinc sulfide, zinc chromate, strontium chromate), other pigments (molybdate orange, viridian, manganese violet, pearl pigments) and the like can be used.

  In order to impart antistatic properties, carbon powder (for example, carbon black, graphite), metal oxide (for example, tin / antimony composite oxide, antimony / indium / tin composite oxide, indium / tin composite oxide, Sn) Conductive indium oxide, tin oxide, zinc oxide doped with F, Cl, etc.) metal [for example, various metal particles (powder) or metal fibers such as copper, nickel, silver, gold, aluminum, etc.], etc .;

  To provide wear resistance, alumina, zirconia, tungsten carbide, titanium carbide, silicon carbide, boron carbide, diamond, etc .;

  In addition, silicates (eg finely divided magnesium silicate, soapstone, stearite, calcium silicate, magnesium aluminosilicate and aluminosilicate can be used to provide other performance (heat resistance, dimensional stability, flame retardancy, etc.). Acid soda), carbonates [eg sedimentary (active, dry, heavy or light) magnesium carbonate], sulfates [eg aluminum sulfate (eg sulfate bands and satin white), magnesium sulfate and calcium sulfate (stone koji) (eg Anhydrous stone and hemihydrate stone)], lead white, mica powder, activated calcium fluoride, cement, lime, calcium sulfite, molybdenum disulfide, asbestos, glass fiber, rock fiber and the like can be used.

  The lower limit of the volume average particle diameter of (a2) is preferably from 0.5 to 50 μm, more preferably from 1 to 30 μm, from the viewpoint of aggregation of (A), and the upper limit from the viewpoint of dispersion stability.

  The true specific gravity of (a2) is preferably 1.5 to 7, more preferably 2 to 5, from the viewpoint of dispersion stability.

  The weight ratio of (a1) to (a2) in (A) is preferably 100: 0 to 1:99, more preferably 100: 0 to 10:90, from the viewpoints of dispersion stability and other functions. .

  The resin (B) in the present invention is not particularly limited as long as it is a resin used for a paint. For example, the resin (B) described in “Paints and painting (enlarged edition), published by Power Co., Ltd. (1973)”. Natural resin (rosin, copal, dammar rubber, ceramics, ester rubber, etc.), synthetic resin {thermoplastic resin [eg, cellulose resin (nitrocellulose, acetylcellulose, benzylcellulose, etc.), polyurethane resin, thermoplastic acrylic resin, vinyl resin ( Vinyl chloride, vinyl acetate, vinyl chloride-vinyl acetate copolymer, etc.), chlorinated rubber, fluororesins (polyvinylidene fluoride, polytrifluoroethylene chloride, polytetrafluoroethylene, etc.)] and thermosetting resins [e.g. Two-component curable urethane resin, thermosetting epoxy resin, unsaturated polyester resin, photosensitive resin [eg (poly) Meth) acrylate, alicyclic epoxy resins]]} and mixtures of two or more thereof.

  Among these, a thermosetting resin is preferable from the viewpoint of mechanical properties of the coating film, a photosensitive resin is more preferable, and (poly) (meth) acrylate is particularly preferable.

  As the two-component curable urethane resin, an equivalent ratio (OH / NCO ratio) of a hydroxyl group and an isocyanate group in a liquid I consisting of a polyol having two or more hydroxyl groups in the molecule and a liquid II consisting of polyisocyanate. What was mix | blended so that it might be set to 0.7-1.5, for example, the thing as described in a "polyurethane resin handbook, the Nikkan Kogyo Shimbun (1987)" is mentioned.

  Examples of the thermosetting epoxy resin include an epoxy resin having two or more epoxy groups in the molecule, and a mono- or poly-amine having two or more active hydrogens in the molecule that react with the epoxy group as an epoxy group. What was mix | blended so that the equivalent ratio with the active hydrogen of an amino group might be 0.7-1.5, for example, the thing as described in "Epoxy resin handbook, the Nikkan Kogyo Shimbun (1987)" is mentioned.

  Examples of the unsaturated polyester resin include unsaturated polybasic acids [carbon number (hereinafter abbreviated as C) 4 to 10, such as maleic acid and fumaric acid] and polyhydric alcohols [C2 to 30 such as ethylene glycol and glycerin (hereinafter, respectively). EG, abbreviated as GR) etc.] and the like, such as those obtained by reacting so that the equivalent ratio of hydroxyl group to carboxyl group is 0.7 to 1.5, for example, “Polyester Resin Handbook, published by Nikkan Kogyo Shimbun (1988)”. Those described are mentioned.

Among the photosensitive resins, examples of the (poly) (meth) acrylate include the following.
(1) Mono (meth) acrylate (1-1) Aliphatic (C1-30), alicyclic (C6-30) and araliphatic (C7-10) monohydric alcohol (meth) acrylate Lauryl (meth) Acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, etc .;
(1-2) Aliphatic (C1-30), alicyclic (C6-30) and araliphatic (C7-10) monohydric alcohol alkylene oxide (hereinafter abbreviated as AO) 1-30 mol adduct (Meth) acrylate (meth) acrylate of lauryl alcohol ethylene oxide (hereinafter abbreviated as EO) 2 mol adduct, (meth) acrylate of lauryl alcohol propylene oxide (hereinafter abbreviated as PO) 3 mol adduct, and other ( (Meth) acrylates of AO adducts of monohydric alcohols in 1-1);
(1-3) (Meth) acrylate of C6-30 [alkyl (C1-20)] phenol AO 1-30 mol adduct (meth) acrylate of phenol PO3 mol adduct, EO 1 mol adduct of nonylphenol ( (Meth) acrylate, etc .;

(2) Di (meth) acrylate (2-1) polyoxyalkylene (C2-4) [molecular weight 106 to number average molecular weight [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method. ] 3,000] di (meth) acrylate polyethylene glycol (hereinafter abbreviated as PEG) (Mn400), polypropylene glycol (hereinafter abbreviated as PPG) (Mn200) and polytetramethylene glycol (hereinafter abbreviated as PTMG) (Mn650) ) Each di (meth) acrylate, etc .;
(2-2) Di (meth) acrylate of bifunctional phenolic compound AO (2 to 30 mol) adduct Bifunctional phenolic compound [C6-18, such as monocyclic phenol (catechol, resorcinol, hydroquinone, etc.), condensed polycyclic AO adduct of phenol (dihydroxynaphthalene, etc.), bisphenol compound] [di (meth) acrylate of resorcinol EO 4 mol adduct, di (meth) acrylate of PO4 mol adduct of dihydroxynaphthalene, bisphenol A, -F and -S , 2 mol of EO, and 4 mol of each adduct of PO, etc.]
(2-3) Di (meth) acrylate of aliphatic dihydric alcohol (C2-30) Each of di (meta) of neopentyl glycol (hereinafter abbreviated as NPG) and 1,6-hexanediol (hereinafter abbreviated as HD) ) Acrylate, etc .;
(2-4) Di (meth) acrylate of alicyclic dihydric alcohol (C6-30) Di (meth) acrylate of dimethyloltricyclodecane, di (meth) acrylate of cyclohexanedimethanol and dihydrogen bisphenol A (Meth) acrylate and the like;

(3) Poly (trivalent to hexavalent or higher) (meth) acrylate (3-1) C3-40 polyvalent (trivalent to hexavalent or higher) alcohol and poly (meth) of its AO adduct Acrylate Trimethylolpropane (hereinafter abbreviated as TMP) Tri (meth) acrylate, GR tri (meth) acrylate, EO 3 mol of TMP and PO3 mol adduct tri (meth) acrylate, pentaerythritol (hereinafter abbreviated as PE) Tri (meth) acrylate of PE, tetra (meth) acrylate of PE, tetra (meth) acrylate of PE EO 4 mol adduct, hexa (meth) acrylate of dipentaerythritol (hereinafter abbreviated as DPE), and the like;

(4) Polyester (meth) acrylates A plurality of esters obtained by esterification reaction of polyvalent (2 to 4 valent) carboxylic acids, polyvalent (2 to 8 valent or more) alcohols and (meth) acryloyl group-containing compounds A polyester (meth) acrylate having a molecular weight of 150 to Mn4,000 having a bond and a plurality of terminal (meth) acryloyl groups;

(5) Urethane (meth) acrylate A plurality of urethane bonds and a plurality of urethane bonds obtained by urethanization reaction of polyvalent (2 to 4 valent) alcohol, poly (2 to 4 or more) isocyanate and hydroxyl group-containing (meth) acrylate. A polyurethane (meth) acrylate having a molecular weight of 500 to Mn7,000 having a terminal (meth) acryloyl group;

(6) Epoxy (meth) acrylate Epoxy (meth) acrylate having a molecular weight of 400 to Mn5,000 obtained by reaction of a polyvalent (2 to 4 valent) epoxide and (meth) acrylic acid;

(7) butadiene polymer having a (meth) acryloyl group in the main chain and / or side chain, polybutadiene poly (meth) acrylate (Mn500 to 500,000), etc. (8) in the main chain and / or side chain of dimethylpolysiloxane Siloxane polymer having a (meth) acryloyl group [Mn 300 to 20,000, for example, dimethylpolysiloxane poly (meth) acrylate]
Of these (1) to (8) (poly) (meth) acrylates, (2) to (6) are preferable from the viewpoint of the toughness of the cured product described later.

The following are mentioned as an alicyclic epoxy resin among the said photosensitive resins. Among these, a bifunctional alicyclic epoxy resin is preferable from the viewpoint of curability and rigidity of the cured product.
(1) Monofunctional alicyclic epoxy resin cyclohexane oxide, cyclopentane oxide, α-pinene oxide 3,4-epoxyvinylcyclohexane, etc .;
(2) Bifunctional alicyclic epoxy resin 2- (3,4-epoxy) cyclohexyl-5,5-spiro- (3,4-epoxy) cyclohexane-m-dioxane, 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, vinylcyclohexane dioxide, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, exo-exobis (2,3-epoxycyclopentyl) ether, endo-exobis (2,3-epoxycyclopentyl) ether, 2,2-bis (4- ( 2,3-epoxypropoxy) Rohexyl) propane, 2,6-bis (2,3-epoxypropoxycyclohexyl-p-dioxane), 2,6-bis (2,3-epoxypropoxy) norbornene, limonene dioxide, 2,2-bis (3 4-epoxycyclohexyl) propane, dicyclopentadiene dioxide, 1,2-epoxy-6- (2,3-epoxypropoxy) hexahydro-4,7-methanoindane, p- (2,3-epoxy) cyclopentylphenyl-2 , 3-epoxypropyl ether, 1- (2,3-epoxypropoxy) phenyl-5,6-epoxyhexahydro-4,7-methanoindane, o- (2,3-epoxy) cyclopentylphenyl-2,3-epoxy Propyl ether), 1,2-bis [5- (1,2-epoxy) -4,7-hex Hydro meth Noin Dano cyclohexyl] ethane, cyclopentenyl phenyl glycidyl ether;
(3) Polyfunctional (trivalent to 20-valent or higher) alicyclic epoxy resin ε-caprolactone (1-10 mol) adduct of 3,4-epoxycyclohexanemethanol and polyvalent (3-20 valent) alcohol ( Esterified products of GR, TMP, PE, DPE, hexapentaerythritol), and the like.

  The organic solvent (C) in the present invention has a water solubility of 0.3 to 20 g with respect to 100 g of (C) at 25 ° C. [preferably 1 to 15 g from the viewpoint of dispersion stability of (A) in the coating composition. ] Is an organic solvent.

  Examples of (C) include esters (C4-5, such as ethyl acetate, butyl acetate), ketones (C4-6, such as methyl ethyl ketone, methyl propyl ketone, cyclohexanone), ethers (C2-4, such as diethyl ether), alcohols ( C8-16, such as decanol), and mixtures thereof.

  The ratio (% by weight) of (A), (B) and (C) constituting the composition of the present invention is based on the total weight of (A), (B) and (C), and (A) is dispersed. From the viewpoint of imparting stability and other performances (coloring, antistatic properties, abrasion resistance, etc.), preferably 0.5 to 50%, more preferably 1 to 40%, (B) is the toughness and function of the coating film From the viewpoint of expression, it is preferably 20 to 80%, more preferably 25 to 70%, and (C) is preferably 10 to 70%, more preferably 15 to 50% from the viewpoint of coating property and dispersion stability.

If necessary, the composition of the present invention may further contain various additives (D) used for paints and inks as long as the effects of the present invention are not impaired. (D) includes organic pigment (D1), dispersant (D2), antifoaming agent (D3), leveling agent (D4), silane coupling agent (D5), thixotropic agent (thickening agent) (D6). ), A slip agent (D7), an antioxidant (D8) and at least one additive selected from the group consisting of an ultraviolet absorber (D9).
The total amount of (D) used is usually 20% or less, preferably 0.005 to 10%, based on the total weight of the composition of the present invention.

Examples of (D1) include the following.
(1) Azo pigments Insoluble monoazo pigments (toluidine red, permanent carmine FB, fast yellow G, etc.), insoluble disazo pigments (disazo yellow AAA, disazo orange PMP, etc.), azo lakes (soluble azo pigments) (lake red C, brilliant carmine) 6B etc.), condensed azo pigments, chelate azo pigments, etc. (2) polycyclic pigments phthalocyanine blue, indanthrone blue, quinacridone red, dioxazine violet, etc. (3) dyed lake basic dyes (Victoria Pure Blue BO lake, etc.), (4) Others Azine pigments (aniline black, etc.), daylight fluorescent pigments, nitroso pigments, nitro pigments, natural pigments, etc. (D1) is used based on the total weight of the composition Usually less than 10% Preferably from FLEXIBLE aspect it is 5% or less.

  Examples of (D2) include organic dispersants [polymer dispersants (Mn 2,000 to 500,000) and low molecular dispersants (molecular weight 100 to less than Mn 2,000)] and inorganic dispersants.

  As the polymer dispersing agent, naphthalene sulfonate [alkali metal (Na and K etc.) salt, ammonium salt etc.] formalin condensate, polystyrene sulfonate (same as above), polyacrylate (same as above) , Poly (2-4) carboxylic acid (maleic acid / glycerin / monoallyl ether copolymer etc.) salt (same as above), carboxymethylcellulose (Mn2,000-10,000) and polyvinyl alcohol (Mn2,000-100) , 000) and the like.

The following are mentioned as a low molecular weight dispersing agent.
(1) Polyoxyalkylene type AO (C2-4) of aliphatic alcohol (C4-30), [alkyl (C1-30)] phenol, aliphatic (C4-30) amine and aliphatic (C4-30) amide 1-30 mol adducts As aliphatic alcohols, n-, i-, sec- and t-butanol, octanol, dodecanol etc .; (alkyl) phenols as phenol, methylphenol and nonylphenol etc .; as aliphatic amines , Laurylamine, methylstearylamine and the like; and aliphatic amides include stearic acid amide and the like.
(2) Polyhydric alcohol type Monoester compound of C4-30 fatty acid (lauric acid, stearic acid, etc.) and polyhydric (2-6 or more) alcohol (eg GR, PE, sorbitol and sorbitan) (3) Carvone Salt type C4-30 fatty acid (same as above) alkali metal (same as above) salt (4) sulfate ester type C4-30 aliphatic alcohol (same as above) and aliphatic alcohol AO (C2-4) ) 1-30 mol adduct sulfate alkali metal (same as above) salts, etc.

(5) Sulfonate type [Alkyl (C1-30)] Phenol (same as above) sulfonic acid alkali metal salt (same as above) (6) Phosphate ester type C4-30 aliphatic alcohol (same as above) ) And fatty alcohol AO (C2-4) 1-30 mol adduct mono- or diphosphate salts [alkali metal (same as above) salts, quaternary ammonium salts, etc.]
(7) C1-30 aliphatic amines [primary (laurylamine, etc.), secondary (dibutylamine, etc.) and tertiary amine (dimethylstearylamine, etc.) hydrochloride, triethanolamine And C4-30 fatty acid (same as above) monoester inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) salt (8) quaternary ammonium salt type C4-30 quaternary ammonium (butyltrimethylammonium, diethyl) Inorganic acid (same as above) salts of laurylmethylammonium, dimethyldistearylammonium and the like.

Examples of inorganic dispersants include alkali metal salts of polyphosphoric acid (same as above) and phosphoric acid dispersants (such as phosphoric acid, monoalkyl phosphate ester, dialkyl phosphate ester).
The amount of (D2) used is usually 5% or less, preferably 0.05 to 3%, based on the total weight of the composition of the present invention.

(D3) includes lower alcohols (C1-6) (methanol, butanol, etc.), higher alcohols (C8-18) (octyl alcohol, hexadecyl alcohol, etc.), higher fatty acids (C10-20) (oleic acid, stearic acid) Etc.), higher fatty acid ester (C11-30) (glycerin monolaurate), phosphate ester (tributyl phosphate etc.), metal soap (calcium stearate, aluminum stearate etc.), polyether [PEG (Mn 200-10,000) , PPG (Mn 200 to 10,000), etc.], silicone (dimethylsilicone oil, alkyl-modified silicone oil, fluorosilicone oil, etc.) and mineral oil (silica powder dispersed in mineral oil).
The amount of (D3) used is usually 3% or less, preferably 0.01-2%, based on the total weight of the composition of the present invention.

Examples of (D4) include PEG type nonionic surfactants (nonylphenol EO 1-40 mol adducts, stearic acid EO 1-40 mol adducts, etc.), polyhydric alcohol type nonionic surfactants (sorbitan palmitic acid monoester, sorbitan) Stearic acid monoester, sorbitan stearic acid triester, etc.), fluorine-containing surfactant (perfluoroalkyl EO 1-50 mol adduct, perfluoroalkyl carboxylate, perfluoroalkyl betaine, etc.), modified silicone oil [polyether modified Silicone oil, (meth) acrylate-modified silicone oil, etc.].
The amount of (D4) used is usually 3% or less, preferably 0.1 to 2%, based on the total weight of the composition of the present invention.

Examples of (D5) include amino group-containing silane coupling agents (γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-phenylaminopropyl trimethoxysilane, etc.), ureido group-containing silane coupling agents ( Ureidopropyltriethoxysilane, etc.), vinyl group-containing silane coupling agents [vinylethoxysilane, vinylmethoxysilane, vinyltris (β-methoxyethoxy) silane, etc.], methacrylate groups-containing silane coupling agents (γ-methacryloxypropyltrimethoxy) Silane, γ-methacryloxypropylmethyldimethoxysilane, etc.), epoxy group-containing silane coupling agent (γ-glycidoxypropyltrimethoxysilane, etc.), isocyanate group-containing silane coupling agent (γ-isocyanate propylene). Rutriethoxysilane, etc.), polymer type silane coupling agents (polyethoxydimethylsiloxane, polyethoxydimethylsiloxane, etc.), cationic silane coupling agents [N- (N-benzyl-β-aminoethyl) -γ-aminopropyltri Methoxysilane hydrochloride, etc.].
The amount of (D5) used is usually 5% or less, preferably 0.5 to 3%, based on the total weight of the composition of the present invention.

Examples of (D6) include inorganic thixotropy imparting agents (such as bentonite, organically treated bentonite, and ultrafine surface-treated calcium carbonate) and organic thixotropic properties imparting agents (hydrogenated castor oil wax, calcium stearate, aluminum oleate, polymerized linseed oil, etc. ).
The amount of (D6) used is usually 5% or less, preferably 0.5 to 3%, based on the total weight of the composition of the present invention.

(D7) includes higher fatty acid esters (such as butyl stearate), higher fatty acid amides (such as ethylene bis stearic acid amide and oleic acid amide), metal soaps (such as calcium stearate and aluminum oleate), and wax [paraffin wax, polyolefin And wax (polyethylene wax, polypropylene wax, carboxyl group-containing polyethylene wax, etc.) and silicone (for example, dimethyl silicone oil, alkyl-modified silicone oil and fluorosilicone oil).
The amount of (D7) used is usually 5% or less, preferably 0.01-2%, based on the total weight of the composition of the present invention.

As (D8), hindered phenol compounds [triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl -4-hydroxybenzylphosphonate diethyl ester] and amine compounds (n-butylamine, triethylamine, diethylaminomethyl methacrylate, etc.).
The amount of (D8) used is usually 3% or less, preferably 0.005 to 2%, based on the total weight of the composition of the present invention.

(D9) includes benzotriazole compounds [2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 , 5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, etc.], triazine compounds [2- ( 4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol], benzophenone (such as 2-hydroxy-4-n-octyloxybenzophenone), oxalic anilide And compounds (such as 2-ethoxy-2′-ethyloxalic acid bisanilide).
The amount of (D9) used is usually 3% or less, preferably 0.005 to 2%, based on the total weight of the composition of the present invention.

  When the additives are the same and overlap between (D1) to (D9) above, the amount of each additive having the corresponding additive effect is not used regardless of the effect as the other additive, Considering that the effects as other additives can be obtained at the same time, the amount used is adjusted according to the purpose of use. The same applies to the case where (B) and (D) overlap.

  The composition of the present invention may further contain a thermosetting catalyst and / or a photopolymerization initiator when (B) is an unsaturated polyester or a photosensitive resin [(meth) acrylate, alicyclic epoxy resin, etc.]. it can.

  Examples of the thermosetting catalyst include organic peroxides (t-butyl peroxybenzoate, benzoyl peroxide, methyl ethyl ketone peroxide, etc.) and azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.). Of these, t-butyl peroxybenzoate and methyl ethyl ketone peroxide are preferred from the viewpoint of stability of the composition (which does not gel during storage) and reactivity.

  Photopolymerization initiators include hydroxybenzoyl compounds (2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzoin alkyl ether, etc.), benzoylformate compounds (methylbenzoylformate) Etc.), thioxanthone compounds (such as isopropylthioxanthone), benzophenone compounds (such as benzophenone), phosphate ester compounds (such as 1,3,5-trimethylbenzoyldiphenylphosphine oxide), and benzyldimethyl ketal. Among these, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone and 1,3,5-trimethylbenzoyldiphenylphosphine oxide are preferable from the viewpoint of light resistance of the coating film. is there.

  The usage-amount of a thermosetting catalyst and a photoinitiator is 20% or less normally based on the total weight of the composition of this invention, respectively, Preferably it is 0.1 to 10%.

  When (B) is an alicyclic epoxy resin, the composition of the present invention can further contain a photocationic polymerization initiator in advance and can be cured by various methods (such as ultraviolet irradiation) after drying.

  Various photocationic polymerization initiators such as allylsulfonium salt [triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenyl Sulfonium hexafluoroantimonate, etc.], allyl iodonium salts [diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, etc.], sulfonic acid esters [o-nitrobenzyl tosylate, dimethoxyanthracenesulfonic acid p-nitrobenzyl ester, tosylate Acetophenone, etc.], ferrocene [(2,4-cyclopentadien-1-yl) [(1-methylethyl Benzene] -Fe (II) hexafluorophosphate, etc.] and the like.

  The amount of the cationic photopolymerization initiator used is preferably 0.1 to 20%, more preferably 0.3 to 10%, particularly preferably 0.3 to 10%, from the viewpoint of curability of the composition, based on the total weight of the composition of the present invention. Preferably it is 0.5 to 5%.

The composition of the present invention can be used in combination with other solvents other than (C) if necessary within a range not inhibiting the effects of the present invention.
Examples of the solvent include aromatic hydrocarbons (C7-10, such as toluene, xylene and ethylbenzene), esters or ether esters (C4-10, such as methoxybutyl acetate), ethers (C4-10, such as tetrahydrofuran, EG). Monoethyl ether, EG monobutyl ether, PG monomethyl ether and DEG monoethyl ether), ketones (C3-10, eg methyl isobutyl ketone, di-n-butyl ketone), alcohols (C1-10, eg methanol, Ethanol, n- and i-propanol, n-, i-, sec- and t-butanol, 2-ethylhexyl alcohol), amides (C3-6, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), Sulfoxide (C2-4, such as dimethyl sulfoxide), and mixed solvent of two or more thereof.
The amount of these solvents used is usually 50% or less, preferably 30% or less, based on the weight of (C).

Although it does not specifically limit as a manufacturing method of the coating composition of this invention, In order to remove the foam which arises at the time of mixing and to improve the wetting of (A) and (B), it is performed under reduced pressure (13 kPa or less). The mixing device is preferably a universal mixer or a planetary mixer capable of reducing the pressure in the kettle. The temperature at the time of mixing is usually 0 to 60 ° C., preferably 5 to 40 ° C., more preferably 15 to 35 ° C. from the viewpoint of uniform mixing property and dispersion stability of the composition.
The order of mixing is not particularly limited, and (A), (B) and (C) are simultaneously mixed at the same time, (A) is mixed with (B) or (C), and then (C) or (B ), (A) is mixed with (B) and (C) and then mixed, or (B) and (C) are mixed and then (A) is mixed. This method may be used. Other components added as necessary other than (A), (B) and (C) can be mixed at any stage of any of the above methods.

The content (% by weight) of water in the coating composition of the present invention is 0.2 to 5%, preferably 0.5 to 4%, and more preferably 1 to 3%. When the water content is less than 0.2%, the dispersion stability is deteriorated, and when it exceeds 5%, the coating property is deteriorated.
Here, moisture is a value measured by the following method using a Karl Fischer moisture meter [MKS-500, manufactured by Kyoto Electronics Industry Co., Ltd.].
(Moisture measurement method)
A solvent (for example, methanol / pyridine, or EG / pyridine when the measurement sample contains a ketone) is put into a titration tank, and is made anhydrous with a Karl Fischer titration solution. About 1 g of the sample is accurately weighed and quickly added to the titration tank. Titrate with Karl Fischer titration solution with stirring.

  The method for containing water in the composition of the present invention is not particularly limited. For example, each component of [1] (A), (B) and / or (C) is preliminarily made to contain water. A method of adding water, [2] a method of adding water at the time of blending (A), (B), (C) and other components, and [3] a method of adding water immediately before coating the composition, etc. Can be mentioned. In any method, the water content in the composition is finally measured immediately before coating.

The viscosity ratio (η ¹ / η ² ) of the following viscosity η ¹ and η ² obtained by the method specified in JIS K-7117 of the composition of the present invention is preferably from the viewpoint of dispersion stability and coatability. Is 2 to 15 (more preferably 5 to 11), and η ¹ is preferably 10 to 8,000 mPa (more preferably 300 to 4,000 mPa) from the same viewpoint.
η ¹ : Viscosity at a rotational speed of 6 revolutions / minute (25 ° C.)
η ² : Viscosity at a rotational speed of 60 revolutions / minute (25 ° C.)

The composition of this invention can obtain the coating which has a film in at least one part of the surface and / or back surface of a base material by applying to a base material and making it dry as needed.
In the coating, various apparatuses such as a coating machine [bar coater, gravure coater, roll coater (size press roll coater, gate roll coater, etc.), air knife coater, spin coater, blade coater, etc.] can be used. The coating film thickness is usually 0.5 to 300 μm as the film thickness after drying, the lower limit is preferably from the viewpoint of wear resistance, solvent resistance, and contamination resistance, and the upper limit is preferably 1 from the viewpoint of drying characteristics and curability. ˜250 μm.

  The base material that can be used is not particularly limited as long as it can be applied with ordinary paints, but the material is, for example, paper, wood, metal, plastic, etc. The shape is, for example, a film, a plate Shape.

  The composition of the present invention can be formed into a coating film by a known method of using a paint. For example, when (B) is a thermoplastic resin, a coating film is obtained by drying after coating. When (B) is a thermosetting resin, a coating film is obtained by curing with heat and / or active energy rays (ultraviolet rays, electron beams, X-rays, etc.) after coating. For example, when (B) is an unsaturated polyester or (meth) acrylate, the thermosetting catalyst and / or photopolymerization initiator is contained in the composition, and heat and / or active energy rays (ultraviolet rays, electron beams, X-ray or the like), and when (B) is an alicyclic epoxy resin, the photocationic polymerization initiator can be contained in the composition and cured with ultraviolet rays.

  Examples of the drying method after applying the composition of the present invention to the base material include hot air drying (such as a dryer). The drying temperature is usually from 10 to 200 ° C, the lower limit is preferably from 30 to 150 ° C from the viewpoint of the drying rate, and the upper limit is preferably from the viewpoint of the surface smoothness of the coating film. The drying time is usually 10 minutes or less, and preferably 1 to 5 minutes from the viewpoint of productivity.

When it is cured by heat after the drying, it is usually heat-treated in an oven at 50 to 200 ° C., preferably 80 to 180 ° C. for 1 minute to 20 hours.
When curing with an electron beam, various electron beam irradiation devices [for example, an electron beam [manufactured by Iwasaki Electric Co., Ltd.]] can be used. The amount of electron beam irradiation is usually 0.5 to 20 Mrad, the lower limit is from the viewpoint of curability of the composition, and the upper limit is the flexibility of the cured product (coating film), as well as avoiding damage to the cured product or substrate. From the viewpoint, it is preferably 1 to 15 Mrad.

When the composition of the present invention is cured by ultraviolet irradiation, various ultraviolet irradiation apparatuses [for example, Eye Grandage [manufactured by Eye Graphic Co., Ltd., the same shall apply hereinafter]. ]] Can be used. The dose of the ultraviolet radiation is typically 10~10,000mJ / cm ^2, the lower limit from the viewpoint of curability of the composition, from the viewpoint of the flexibility of the upper limit cured product, preferably 100~5,000J / cm ² is there.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. The part in an Example shows a weight part and% shows weight%.

Production Example 1
In a glass reaction vessel equipped with a dropping funnel, thermometer, reflux condenser and stir bar, 100 parts of PTMG of Mn 1,000, 9.0 parts of 1,4-butanediol, and 66.6 parts of isophorone diisocyanate were charged. The reaction was carried out at 120 ° C. for 3 hours. After cooling to 40 ° C., add 300.2 parts of ethyl acetate and 150.1 parts of isopropyl alcohol, adjust the temperature to 25 ° C., add 15.4 parts of isophoronediamine and 2 parts of diethanolamine, and react at 40 ° C. for 2 hours to make polyurethane A composition (U) was obtained. (U) had an NCO content of 0.001% and Mn of 20,000.

Examples 1-8
According to the composition of Table 1, it knead | mixed for 30 minutes with the planetary mixer, and the composition for coatings of Examples 1-8 was obtained. Table 1 shows the results of evaluating the water content, viscosity at 25 ° C. and dispersion stability of the composition. The evaluation method is as follows.
[1] Moisture 1 g of a sample was precisely weighed and dispersed in about 30 ml of methanol, and the moisture was measured by the Karl Fischer method.
[2] Viscosity and viscosity ratio (η ¹ / η ² )
In accordance with JIS K-7117, the following viscosities were measured using a BL type viscometer [manufactured by Tokyo Keiki Co., Ltd.] to determine the viscosity ratio (η ¹ / η ² ).
η ¹ : Viscosity at a rotational speed of 6 revolutions / minute (25 ° C.)
η ² : Viscosity at a rotational speed of 60 revolutions / minute (25 ° C.)
[3] Dispersion stability A cylindrical glass container having a diameter of 2 cm and a height of 10 cm is filled with the sample up to a height of 9 cm and left at 25 ° C., and after 4 hours, the ratio of the supernatant height to the total height of the sample (% ) Was measured.

Examples 9-11
According to the composition of Table 2, it knead | mixed for 30 minutes with the planetary mixer, and the composition for coatings of Examples 9-11 was obtained. Table 2 shows the results of evaluating the water content, viscosity at 25 ° C., dispersion stability, and physical properties of the coating film. The method for evaluating the physical properties of the coating film is as follows.
[4] Physical properties of coating film A sample was coated on a polymethylmethacrylate plate (base material, thickness 2 mm) with a bar coater, heated for 30 seconds with a dryer to dry and remove the solvent, and then irradiated with ultraviolet rays (Eye Grandage) Then, UV light is irradiated at 2,000 mJ / cm ² and cured. The pencil hardness, abrasion resistance, and contamination resistance of the obtained cured product (coating film) are evaluated by the following methods.
(1) Pencil hardness Pencil hardness is evaluated according to JIS K-5600.
(2) Abrasion resistance According to JIS K-6902, an abrasion resistance is evaluated by the following Taber abrasion test method.
[Taber abrasion test procedure]
<1> One side of the substrate opposite to the coating surface is attached to a cardboard that has been subjected to adhesive processing, cut into a size of 100 mm × 100 mm, and this is used as a test sample.
<2> According to JIS K-6902, a Taber abrasion test (rotation speed 200 / min) is performed on the coating surface. The abrasion amount (mg) of the coating film is calculated from the test sample weight (mg) before and after the test.
(3) Contamination resistance According to JIS K-6902, the contamination resistance is evaluated according to the following procedure. Contamination test items shall be 3 items (blue ink, red ink and mustard).
<1> One side of the substrate opposite to the coating surface is attached to a cardboard that has been subjected to adhesive processing, cut into a size of 100 mm × 100 mm, and this is used as a test sample.
<2> A contamination test product is dropped or adhered on the coating film surface, the dripping or adhesion portion is covered with a watch glass, and allowed to stand at room temperature for 24 hours.
<3> The coating film surface from which the watch glass has been removed is washed with water and methanol, wiped with a clean dry gauze, and then allowed to stand at room temperature for 1 hour.
<4> The appearance of the coating surface is evaluated according to the following criteria.
○ No stains remain.
△ Slight stains remain.
× Clear spots remain.

Comparative Examples 1-3
According to the composition of Table 1, it knead | mixed for 30 minutes with the planetary mixer, and the composition for coating materials of Comparative Examples 1-3 was obtained. The composition was evaluated in the same manner as the compositions of Examples 1-8. The results are shown in Table 1.

Comparative Examples 4-6
According to the composition of Table 2, it knead | mixed for 30 minutes with the planetary mixer, and the composition for coatings of Comparative Examples 4-6 was obtained. The compositions were evaluated in the same manner as the compositions of Examples 9-11. The results are shown in Table 2.

ED-50: wax-treated silica, volume average particle size 5.0 μm [produced by Grace Co., Ltd .:
Cyloid ED-50]
Aerosil 200: Silica, volume average particle size 0.2 μm [Nippon Aerosil Co., Ltd .: Aero
Jill 200]
Calcium carbonate: calcium bicarbonate, volume average particle size 10.3 μm [calcium Shiraishi (
Product: Whiteon A]
Alumina: spherical alumina, volume average particle size 20 μm [Showa Denko Co., Ltd .: Alumina
Bead CB-A20S]
EP828: Bisphenol A diglycidyl ether [Japan epoxy resin
[Epicoat 828]
Heroxy 107: cyclohexanedimethanol diglycidyl ether [Japan Epo
Xylesin Co., Ltd .: Heroxy 107]
BA-641: Bisphenol A (EO 4 mol adduct) diacrylate [Sanyo Kasei
Industrial Co., Ltd .: Neomer BA-641]
TMPTA: TMP triacrylate [Nippon Kayaku Co., Ltd .: Kayarad TMPTA
]
TEAI-2000: Hydrogenated butadiene urethane acrylate [Nippon Soda Co., Ltd .: TEA
I-2000]
VR-77: Bisphenol A diglycidyl ether diacrylate [Showa Takabun
Child manufactured by Lipoxy VR-77]
2021: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclo
Hexanecarboxylate [Daicel Chemical Industries, Ltd .: Celoxide 2
021]
3000: Limonene dioxide [manufactured by Daicel Chemical Industries, Ltd .: Celoxide 3000
]
D1173: 2-hydroxy-2-methyl-1-phenylpropan-1-one [
Ciba Specialty Chemicals Co., Ltd .: Darocur 1173]
Disperbyk-108: Dispersant [by Big Chemie Japan Co., Ltd.]
Disperbyk-174: Dispersant [by Big Chemie Japan Co., Ltd.]

  The coating composition of the present invention has a relatively low viscosity and excellent dispersion stability of the inorganic filler, and the coating film using the composition has excellent mechanical properties. Widely used in electrical equipment, packaging materials, building materials and automotive applications.

Claims (3)

Silica (a1) having a volume average particle diameter of 0.002 to 20 μm , or an inorganic filler (A) containing an inorganic filler (a2) other than (a1) and (a1 ), a resin (B), and in the organic solvent (C) Tona Ru coating composition, (a), based on the total weight of (B) and (C), (a) is 12 to 50% (B) 20 to 70% (C) is 10 to 50%, the weight ratio of (a1) and (a2) is 100: 0 to 17:83, and (C) has a water solubility of 0.3 to 20 g / organic at 25 ° C. 100 g of a solvent, an organic solvent selected from the group consisting of an ester having 4 to 5 carbon atoms, a ketone having 4 to 6 carbon atoms, and an alcohol having 8 to 16 carbon atoms, and the composition is 0.2 to 5 wt. A coating composition, comprising:% water. (A2) is It has a volume average particle diameter of 0.5 to 50 μm and a true specific gravity of 1.5 to 7 The composition according to claim 1, which is an inorganic filler. JIS K-7117 with the provisions viscosity ratio of the viscosity eta ¹ and eta ² obtained by the method of (eta ¹ / eta ²⁾ is according to claim 1, wherein 2 to 15, and eta ¹ is 10~8,000mPa Composition.
η ¹ : Viscosity at a rotational speed of 6 revolutions / minute (25 ° C.)
η ² : Viscosity at a rotational speed of 60 revolutions / minute (25 ° C.)