CN106519938B - Coating composition - Google Patents
Coating composition Download PDFInfo
- Publication number
- CN106519938B CN106519938B CN201610708106.6A CN201610708106A CN106519938B CN 106519938 B CN106519938 B CN 106519938B CN 201610708106 A CN201610708106 A CN 201610708106A CN 106519938 B CN106519938 B CN 106519938B
- Authority
- CN
- China
- Prior art keywords
- mass parts
- coating composition
- hydroxyl
- methyl
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Abstract
The present invention relates to a kind of coating compositions, it is capable of forming finished appearance, hardness of film, the gloss stability of dumb light film, resistance to chemical reagents and the good film of corrosion protection, it and is the resin (a) containing hydroxyl, the barium sulfate (a1) that average grain diameter is 0.01 μm to 2.0 μm, talcum (a2) of the average grain diameter at 10 μm or more, the coating composition of organic resin particles (a3) and coloring pigment (a4) and polyisocyanate compound (b), wherein, add up to 100 mass parts as benchmark using the solid content of the resin (a) of hydroxyl, the coating composition contains the barium sulfate (a1) of 1 mass parts to 130 mass parts, the talcum (a2) of 1 mass parts to 50 mass parts, the organic resin particles (a3) of 0.1 mass parts to 20 mass parts, 1 matter Part is measured to the coloring pigment (a4) of 100 mass parts and the polyisocyanate compound (b) of 10 mass parts to 60 mass parts.
Description
Technical field
The present invention relates to a kind of coating compositions, and it is hard to be capable of forming finished appearance (finish property), film
Degree, the gloss stability of dumb light film, resistance to chemical reagents and the good film of corrosion protection.
Background technique
Recently, it is used in the coating of the construction implements such as bull-dozer, hydraulic crawler excavator, wheel loader or industrial machinery
Various coating compositions.But for construction implement or industrial machinery, in dry coating, exist such as inferior side
The project in face:
1. the thermal capacity of coated article is big, the heat of drying oven cannot be transmitted sufficiently, and curability is insufficient；
2. vertical position is more, the glossiness of dumb light film is unstable；
3. further, since construction implement or industrial machinery are for open air, therefore it is required that there is hardness of film, water-fast
Property, resistance to chemical reagents and corrosion protection etc..
So far, in order to complete the above subject, a kind of double groups by basic coating and curing agent component are being developed always
Divide the coating composition for being mixed and being used before i.e. by coating.
For example, in patent document 1, disclose it is a kind of by by specific 5 weight % of epoxy ester resin composition (a) extremely
60 weight %, the 40 weight % of alkyd resin composition (b) that oil content is 40% to 70% are heated after being mixed to 95 weight %,
And acrylic monomer (c) is added wherein come resin combination obtained (A) and addition solvent and the coloring of reacting
Coating composition made of agent；And it describes the coating composition and is used suitable for civil engineerings such as coating bull-dozer, power diggers
Big machinery, fork truck etc..
In addition, being the master by being formed by the resin of hydroxyl Patent Document 2 discloses a kind of coating composition
The coating composition that agent (I) and curing agent (II) are constituted, wherein host agent (I) contains aqueous high molecular polyalcohol, also, solid
Agent (II) contains polyisocyanates and organic solvent with water dispersible.
In addition, being containing polyester resin (A), acrylic resin Patent Document 3 discloses a kind of coating composition
(B), water dispersible polyisocyanate compound (C) and the painting by amorphous silica microparticle (D) made of ion exchange
Material is capable of forming storage stability good and hardness of film, finished appearance, gloss, water resistance and the excellent film of corrosion protection.
But the coating composition for being recorded in patent document 1 to 3, in finished appearance, hardness of film, dumb light film
Gloss stability, either in resistance to chemical reagents and corrosion protection there is problem in face, need to be improved.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 10-77442 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2006-257141 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2007-284480 bulletin
Summary of the invention
The technical problems to be solved by the invention
Technical problem to be solved by the present invention lies in provide a kind of coating composition, be capable of forming finished appearance, apply
Film hardness, the gloss stability of dumb light film, resistance to chemical reagents and the good film of corrosion protection.
The means to solve the problem
Inventor etc. has made intensive studies, as a result, it has been found that, it is by the resin (a) containing hydroxyl, average grain diameter
0.01 μm to 2.0 μm of barium sulfate (a1), average grain diameter are in 10 μm or more of talcum (a2), organic resin particles (a3) and coloring
The coating composition of pigment (a4) and polyisocyanate compound (b), is able to solve the above subject, so as to complete this hair
It is bright.
That is, the present invention relates to following technical solutions:
1. a kind of coating composition is the resin (a) containing hydroxyl, the sulphur that average grain diameter is 0.01 μm to 2.0 μm
Sour barium (a1), average grain diameter are in 10 μm or more of talcum (a2), organic resin particles (a3) and coloring pigment (a4) and polyisocyanate
The coating composition of cyanate esters (b), wherein
Add up to 100 mass parts as benchmark using the solid content of the resin (a) of the hydroxyl, the coating composition contains
There are the barium sulfate (a1), the talcum (a2) of 1 mass parts to 50 mass parts, 0.1 mass of 1 mass parts to 130 mass parts
The organic resin particles (a3), the coloring pigment (a4) of 1 mass parts to 100 mass parts, 10 matter of the part to 20 mass parts
Measure the polyisocyanate compound (b) of part to 60 mass parts.
2. the coating composition as described in the 1st, wherein with the solid content of the resin (a) of the hydroxyl total 100
For mass parts as benchmark, the coating composition contains the silane coupling agent (b1) of 0.1 mass parts to 10 mass parts.
3. the coating composition as described in the 1st or the 2nd, wherein with the solid content of the resin (a) of the hydroxyl
Add up to 100 mass parts as benchmark, the coating composition contains resistance to represented by the formula (1) of 0.1 mass parts to 10 mass parts
Pollutant (b2),
(R1)n-Si-(OR2)4-n... formula (1)
In formula (1), R1It is the alkyl or phenyl that the carbon atom number that can be replaced by epoxy group or sulfydryl is 1 to 18, R2It is carbon original
The alkyl that subnumber is 1 to 6, n is 0 or 1.
4. a kind of construction implement or industrial machinery, wherein on the coated article of the construction implement or industrial machinery
With the cured coating film formed by coating composition described in any one of the 1st to the 3rd.
Invention effect
Coating composition of the invention, be capable of forming finished appearance, hardness of film, dumb light film gloss stability,
Resistance to chemical reagents and the good film of corrosion protection.
Specifically, coating composition of the invention can play following invention effect:
1. even can also cure sufficiently in the short time at low temperature coated article with large heat capacity；
2. for the coated article of the cured coating film with coating composition, can obtain 60 degree of mirror surface lusters be 10 to
70, be preferably 25 to 65 lackluster deviation, dumb light film that gloss stability is excellent, especially (hung down by coating position
Straight portion), the variation of glossiness caused by sintering temperature it is also few；
3. it is also useful for being used in outdoor since resistance to chemical reagents and corrosion protection are excellent.Coating group of the invention
Close object, for example, can be adapted to be used as construction implement with or industrial machine coating.
Specific embodiment
The present invention is the resin (a) of the hydroxyl containing predetermined amount, the barium sulfate that average grain diameter is 0.01 μm to 2.0 μm
(a1), average grain diameter is in 10 μm or more of talcum (a2), organic resin particles (a3) and coloring pigment (a4) and polyisocyanic acid
The coating composition of ester compounds (b).In the following, being described in detail.
The resin (a) of hydroxyl:
The resin (a) of hydroxyl is the resin in a molecule at least one hydroxyl.Resin as hydroxyl
(a), for example, can enumerate: polyester resin, acrylic resin, polycarbonate resin, polyurethane resin, the asphalt mixtures modified by epoxy resin of hydroxyl
The resin of the hydroxyls such as rouge, alkyd resin.They can be used individually or are used in combination.Wherein, from painting
From the perspective of film hardness and against weather, the resin (a) of the preferably described hydroxyl is the acrylic resin of hydroxyl.
For the acrylic resin of hydroxyl, the usually polymerism unsaturated monomer of hydroxyl and poly- with the hydroxyl
The copolymer of conjunction property other copolymerizable polymerism unsaturated monomers of unsaturated monomer.It, can be with as the method for obtaining copolymer
Itself known method is enumerated, for example, the emulsion polymerization etc. in the solution polymerization process, water in organic solvent.
The polymerism unsaturated monomer of hydroxyl is to be respectively provided with more than one hydroxyl and polymerism in a molecule
The compound of unsaturated bond, specifically, for example, can enumerate: (methyl) acrylic acid 2- hydroxyl ethyl ester, (methyl) acrylic acid 2- hydroxyl
Propyl ester, (methyl) acrylic acid 3- hydroxypropyl acrylate, (methyl) acrylic acid 4- hydroxy butyl ester, (methyl) acrylic acid 5- hydroxy pentane ester, (methyl) third
(methyl) acrylic acid and the carbon atoms such as the own ester of olefin(e) acid 6- hydroxyl, (methyl) acrylic acid 7- hydroxyl heptyl ester, (methyl) acrylic acid 8- hydroxyl monooctyl ester
The monoester compound of the dihydric alcohol of number 2 to 8 (preferably 2 to 4)；Should (methyl) acrylic acid and carbon atom number 2 to 8 dihydric alcohol it
Between monoester compound 6-caprolactone modified body；N- methylol (methyl) acrylamide；Allyl alcohol；Molecular end is hydroxyl
, (methyl) acrylate with polyoxyethylene chain etc..In addition, in the present invention, there is aftermentioned 2- hydroxyl -4- (3- first
Base acryloxy -2- hydroxy propyloxy group) the ultraviolet-absorbings functional group such as benzophenone polymerism unsaturated monomer not by
It is contained in the polymerism unsaturated monomer of hydroxyl, but is contained in copolymerizable with the polymerism unsaturated monomer of hydroxyl
Other polymerism unsaturated monomers in.
In addition, as other polymerism unsaturated monomers that can be copolymerized with the polymerism unsaturated monomer of hydroxyl, for example,
Can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) acrylic acid are different
Propyl ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid are just
Own ester, (methyl) n-octyl, (methyl) 2-EHA, (methyl) nonyl acrylate, (methyl) acrylic acid
Tridecane base ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate acyl ester, " acrylic acid isostearate
(Isostearyl Acrylate) " (product name, Osaka Organic Chemical Industry Co., Ltd.'s manufacture), (methyl) acrylic acid ring
Own ester, (methyl) acrylic methyl cyclohexyl, (methyl) t-butylcyclohexyl ester, ten diester of (methyl) acrylic acid ring etc.
(methyl) alkyl acrylate or (methyl) acrylate base ester；(methyl) isobornyl acrylate etc. has isobornyl
Polymerism unsaturated monomer；(methyl) adamantyl acrylate etc. has the polymerism unsaturated monomer of adamantyl；Benzene second
The vinyl aromatic compounds such as alkene, α-methylstyrene, vinyltoluene；Vinyltrimethoxysilane, three second of vinyl
Oxysilane, vinyl three (2- methoxy ethoxy) silane, γ-(methyl) acryloyloxypropyltrimethoxysilane, γ-
(methyl) acryloxypropyl triethoxysilane etc. has the polymerism unsaturated monomer of alkoxysilane group；(methyl) third
(methyl) perfluoroalkyl acrylates such as olefin(e) acid perfluoro butyl ethyl ester, (methyl) perfluoroethyl octyl ethyl ester；Fluoro alkene
Hydrocarbon etc. has the polymerism unsaturated monomer of fluorinated alkyl；Dimaleoyl imino etc. has the polymerism of optical polymerism functional group not
It is saturated monomer；N- vinylpyrrolidone, ethylene, butadiene, chlorobutadiene, vinyl propionate, vinylacetate etc. are vinylated
Close object；The carboxylic polymerism unsaturated monomer such as (methyl) acrylic acid, maleic acid, crotonic acid, β-acryloxypropionic acid；(first
Base) acrylonitrile, (methyl) acrylamide, (methyl) acrylic acid N, N- dimethylamino ethyl ester, N, N- dimethylamino-propyl (first
Base) acrylamide, (methyl) glycidyl acrylate and amine compounds the nitrogenous polymerism unsaturated monomer such as addition product；
(methyl) allyl acrylate, 1,6-hexylene glycols two (methyl) acrylate etc. have more than two polymerizations in a molecule
The polymerism unsaturated monomer of property unsaturated group；(methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl
Glyceride, (methyl) acrylic acid 3,4- expoxycyclohexyl methyl esters, (methyl) acrylic acid 3,4- expoxycyclohexyl ethyl ester, (first
Base) the polymerism unsaturated monomer containing epoxy group such as acrylic acid 3,4- expoxycyclohexyl propyl ester, allyl glycidyl ether；Point
Sub- end is alkoxy, (methyl) acrylate with polyoxyethylene chain；2- acrylamide -2- methyl propane sulfonic acid, third
Olefin sulfonic acid, styrene sulfonic acid sodium salt, sulfoethyl methacrylate and its sodium salt, ammonium salt etc. have sulfonic polymerism not
It is saturated monomer；2- acryloyl-oxyethyl phosphate ester acid, 2- methacryloxyethyl phosphate ester acid, 2- acryloyl-oxy
Base propyl phosphate ester acid, 2- methacryloxypropyl phosphate ester acid etc. have the polymerism of phosphate unsaturated single
Body；2- hydroxyl -4- (3- methacryloxy -2- hydroxy propyloxy group) benzophenone, 2- hydroxyl -4- (3- acryloxy -2-
Hydroxy propyloxy group) benzophenone, 2,2 '-dihydroxy -4- (3- methacryloxy -2- hydroxy propyloxy group) benzophenone, 2,
2 '-dihydroxy -4- (3- acryloxy -2- hydroxy propyloxy group) benzophenone, 2- (2 '-hydroxyls -5 '-methacryloxy
Ethylphenyl) the polymerism unsaturated monomer with ultraviolet-absorbing functional group such as -2H- benzotriazole；4- (methyl) propylene
Acyloxy -1,2,2,6,6- pentamethvl, 4- (methyl) acryloxy -2,2,6,6- tetramethyl piperidine, 4- cyano -4-
(methyl) Acryloyl amino -2,2,6,6- tetramethyl piperidine, 1- (methyl) acryloyl group -4- (methyl) Acryloyl amino -
2,2,6,6- tetramethyl piperidine, 1- (methyl) acryloyl group -4- cyano -4- (methyl) Acryloyl amino -2,2,6,6- tetramethyl
Phenylpiperidines, 4- crotons acyloxy -2,2,6,6- tetramethyl piperidine, 4- crotonocyl amino -2,2,6,6- tetramethyl piperidine, 1- crotons
The UV stables polymerism unsaturated monomers such as acyl -4- crotons acyloxy -2,2,6,6- tetramethyl piperidine；Methacrylaldehyde, double third
Ketone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formoxyl styrene, have 4 to
Vinyl alkyl ketone (for example, ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) of 7 carbon atoms etc. has carbonyl
Polymerism unsaturated monomer compound of base etc..They can be used individually or are used in combination of two or more.
From the viewpoint of hardness of film, corrosion protection, preferably the resin (a) of hydroxyl has 30mgKOH/g extremely
Hydroxyl value, the particularly preferred hydroxyl value within the scope of 40mgKOH/g to 250mgKOH/g within the scope of 300mgKOH/g.
From the perspective of the reactivity of polyisocyanate compound (b), the resin (a) of preferably hydroxyl has
20mgKOH/g acid value below, the particularly preferred acid value within the scope of 1mgKOH/g to 15mgKOH/g.
For the resin (a) of hydroxyl, it is usually preferred to the weight average molecular weight in 3000 to 100000 ranges, spy
Not preferably in 3000 to 50000 ranges weight average molecular weight, further particularly preferably have 4000 to 30000 ranges in
Weight average molecular weight.
" weight average molecular weight " in this specification is, according to method described in JIS K 0124-2011, according to using gel
The chromatography of permeation chromatography device measurement value calculated on the basis of the molecular weight of standard polystyren.
Gel permeation chromatography device uses " HLC8120GPC " (Japanese TOSOH Co., Ltd manufactures).It is used as chromatographic column
“TSKgel G-4000HXL”、“TSKgel G-3000HXL”、“TSKgel G-2500HXL”、“TSKgel G-2000HXL”
(product name is the manufacture of Japanese TOSOH Co., Ltd) this 4 columns, mobile phase is tetrahydrofuran, measurement temperature is 40 DEG C,
Flow velocity is 1mL/ minutes, and detector measures under conditions of being RI.
Wherein, in the present invention, the resin of hydroxyl corresponding with aftermentioned organic resin particles (a3) is excluded
Except " resin (a) of hydroxyl ".
Barium sulfate (a1):
It is 0.01 μm to 2.0 μm, preferably 0.02 μm to 1.0 of average grain diameter that coating composition of the invention, which contains average grain diameter,
μm barium sulfate (a1).
As the market sale product of this barium sulfate (a1), can enumerate: BARIFINE BF-20 (product name, it is average
0.03 μm of partial size, Sakai chemical industry corporation manufacture), SS-50 (product name, 0.5 μm of average grain diameter, Sakai chemical industry corporation manufacture),
Barium sulfate 100 (product name, 0.6 μm of average grain diameter, the manufacture of Sakai chemical industry corporation), precipitability barium sulfate PS-07 (trade name
Claim, 0.74 μm of average grain diameter, Guangxi Xiangzh manufacture), precipitability barium sulfate Blanc Fixe HD80 (product name,
0.8 μm of average grain diameter, Solvay Barice Derivati SpA manufacture), barium sulfate HF (product name, 0.9 μ of average grain diameter
M, the manufacture of Jia Xin chemical company of Shenzhou City).
In addition, the average grain diameter in this specification refers to that carrying out particle size distribution measurement by using dynamic light scattering method is obtained
More specifically the value obtained refers to using value measured by UPA-EX250 (product name, Nikkiso Company Limited's manufacture).
In addition, adding up to 100 mass parts as benchmark, the barium sulfate using the solid content of the resin (a) of the hydroxyl
(a1) combined amount is 1 mass parts to 130 mass parts, and for preferably 20 mass parts to 110 mass parts, thereby, it is possible to obtain finished product
Appearance, hardness of film, the gloss stability of dumb light film, resistance to chemical reagents and the excellent film of corrosion protection.
Talcum (a2):
Coating composition of the invention contains the talcum (a2) that average grain diameter is 10 μm or more, preferably comprises average grain diameter
11 μm to 20 μm of talcum (a2).
Above-mentioned talcum (a2) is the flake shaped particle with layer structure, is hydrous magnesium silicate in chemical composition, usually
With chemical formula 4SiO2·3MgO·2H2O is indicated, usually by 56 mass % to the SiO of 65 mass %2, 28 mass % to 35
The H of the MgO of quality %, about 5 mass % or so2O is constituted.
As other a small amount of ingredients, Fe2O3Contain 0.03 mass % to 1.2 mass %, Al2O3Extremely containing 0.05 mass %
1.5 mass %, CaO contain 0.05 mass % to 1.2 mass %, K2O contains 0.2 mass % hereinafter, Na2O contains 0.2 mass %
Such as the following, specific gravity is about 2.7, Mohs' hardness 1.
In addition, the market sale product as talcum (a2), for example, can enumerate: Talc GTA (product name, average grain
10 μm of diameter, consonance mining industry society manufacture), Talc CTA-2 (product name, 11 μm of average grain diameter, KIHARA be melted into Co. Ltd. system
It makes, S Talc (product name, 11 μm of average grain diameter, the manufacture of Japanese talcum Zhi Lian society), TALCAN POWDER PK-S (trade name
Claim, 11 μm of average grain diameter, woods be melted into society manufacture), Talc 1 (product name, 11 μm of average grain diameter, bamboo original chemical industry corporation system
Make), Talc 2 (product name, 11 μm of average grain diameter, the manufacture of bamboo original chemical industry corporation), Talc T-1 (product name, it is average
11 μm of partial size, talcum industry society of Fuji manufacture), Talc SW-D (product name, 12 μm of average grain diameter, Qian Tianzhi powder society manufacture),
Talc SSS (product name, 12 μm of average grain diameter, Japanese talcum society manufacture), Talc DNB (product name, 12 μ of average grain diameter
M, the manufacture of Japanese talcum society), PS Talc (product name, 14 μm of average grain diameter, the manufacture of bamboo original chemical industry corporation), Talc MA
(product name, 14 μm of average grain diameter, Japanese talcum society manufacture), Talc M (product name, 16 μm of average grain diameter, Japanese talcum
Society manufacture), TTK Talc (product name, 17 μm of average grain diameter, bamboo original chemical industry corporation manufacture), T Talc (product name, put down
Equal 17 μm of partial size, the manufacture of bamboo original chemical industry corporation), Crown Talc 3S (product name, 18 μm of average grain diameter, loose village's industry society
Manufacture) etc..
In order to obtain hardness of film, the gloss stability of dumb light film and the excellent film of resistance to chemical reagents, of the invention
In coating composition, the solid content of the resin (a) relative to the hydroxyl adds up to 100 mass parts, it is desirable to the talcum
(a2) combined amount is in the range of 1 mass parts to 50 mass parts, preferably in the range of 10 mass parts to 40 mass parts.
Organic resin particles (a3):
Coating composition of the invention contains organic resin particles (a3).Wish the average grain diameter of organic resin particles (a3)
It is 6 μm to 22 μm, preferably 8 μm to 20 μm.As organic resin particles (a3), acrylic resin particle etc. can be enumerated.
Also, by by 6 μm to 15 μm of average grain diameter and 16 μm to 22 μm both described organic resins of average grain diameter
Grain (a3) is mixed, and the raising of the gloss stability of dumb light film can be further realized.
In addition, the market sale product as organic resin particles (a3), specifically, can enumerate: TECHPOLYMER
(テ Network Port リ マ ー) MBX-12 (12 μm of average grain diameter, acrylic resin, ponding finished industrial society manufacture), TECHPOLYMER
MBX-15 (15 μm of average grain diameter, acrylic resin, ponding finished industrial society manufacture), TECHPOLYMER MBX-20 are (average
20 μm of partial size, acrylic resin, ponding finished industrial society manufacture), TECHPOLYMER MB30X-20 (20 μm of average grain diameter,
Acrylic resin, ponding finished industrial society manufacture), TECHPOLYMER BM30X-20 (20 μm of average grain diameter, acrylic acid tree
Rouge, ponding finished industrial society manufacture), Diasphere MPB-X10 (product name, 10 μm of average grain diameter, acrylic resin,
KOLON society manufacture).
In addition, the resin (a) in order to obtain the excellent film of the gloss stability of dumb light film, relative to the hydroxyl
Solid content add up to 100 mass parts, it is also desirable to the mixed proportion of the organic resin particles (a3) is in 0.1 mass parts to 20 matter
In the range of amount part, preferably in the range of 1 to 10 mass parts.
By mixing above-described barium sulfate (a1), talcum (a2) and organic resin particles (a3), can obtain this
Excellent film in terms of finished appearance, hardness of film, the gloss stability of dumb light film, resistance to chemical reagents and the balance of corrosion protection.
Coloring pigment (a4)
With adjust the cured coating film of coating composition of the invention tone, lightness as a purpose, coloring face can be mixed
Expect (a4).It as the coloring pigment (a4), is not particularly limited, specifically, can enumerate: the coloring of the white groups such as titanium oxide
Pigment；The black class coloring pigment such as carbon black, graphite (graphite), iron black (iron black)；Prussian blue, ultramarine blue, cobalt
The blue class coloring pigment such as indigo plant, copper phthalocyanine blue, indanthrene blue；Synthetic iron oxide is yellow, transparent iron oxide red (Huang), pucherite,
Titan yellow, monoazo yellow, dual-azo yellow, isoindolinone Huang, metal complex azophosphine, quinoline phthalein ketone Huang, benzimidazolone yellow etc.
Yellow class coloring pigment；Iron oxide red, it is transparent iron oxide red it is (red), monoazo is red, monoazo is red, unsubstituted quinacridone is red,
Azo lake (manganese salt), quinacridone red (quinacridone magenta), anthanthrone orange (anthanthrone
Orange), bi-anthraquinone base red (dianthraquinonyl red), brown red (perylene maroon), red
(perylene red), diketopyrrolo-pyrrole (diketo-pyrrolo-pyrrole), molybdate red (chrome
The pink groups coloring pigment such as vermilion)；Chlorination phthalocyanine green, the brominated phthalocyanine green class coloring pigment such as green；Pyrazolone orange,
The others coloring pigment such as benzimidazolone orange, dioxazine violet, purple.They can be used individually or are combined two kinds with
Upper use.
Add up to 100 mass parts as benchmark, Coating material composition of the invention using the solid content of the resin (a) of the hydroxyl
The mixed proportion of the coloring pigment (a4) in object is the range of 1 mass parts to 100 mass parts, preferably 10 mass parts to 60
The range of mass parts, thus, it is possible to obtain finished appearance, the gloss stability of dumb light film and the excellent film of corrosion protection.
Polyisocyanate compound (b):
Polyisocyanate compound (b) in coating composition of the invention is in a molecule with more than two
The compound of free isocyanate group, and isocyanate group applies sealing endization without end-capping reagent.
Specifically, being able to use the compound for polyurethane manufacture all the time.In above-mentioned polyisocyanates, packet
Include aliphatic polyisocyanate compound, ester ring type polyisocyanate compound, aromatic-aliphatic polyisocyanate compound, virtue
Fragrant race's polyisocyanate compound and its crude object, these polyisocyanate compounds modifier (containing carbamate groups,
It is carbodiimide-based, allophanate group, urea groups, biuret base, uretdion, urea ketimine base (ウ レ ト イ ミ Application base), different
Cyanurate ester group, modifier of oxazolidine ketone group etc.) and two or more mixtures in them.
It as the specific example of above-mentioned aliphatic polyisocyanate compound, can enumerate: ethylidene diisocyanate, four
Methylene diisocyanate, hexamethylene diisocyanate (HDI), ten dimethylene diisocyanates, 1,6,11- hendecane three
Isocyanates, 2,2,4- trimethyl hexamethylene diisocyanate, lysine diisocyanate, 2,6- diisocyanate Ji Jisuanjia
Ester, bis- (2- isocyanatoethyl) fumarates, bis- (2- isocyanatoethyl) carbonic esters, 2- isocyanatoethyl -2,6- two
Isocyanic acid capronate etc..
As the specific example of above-mentioned ester ring type polyisocyanate compound, can enumerate: isophorone diisocyanate
(IPDI), dicyclohexyl methyl hydride -4,4 '-diisocyanate (hydrogenation MDI), cyclohexylene diisocyanate, methylcyclohexylidene
Diisocyanate (hydrogenation TDI), bis- (2- isocyanatoethyl) -4- cyclohexene -1,2- dicarboxylic esters, 2,5- and/or 2,6- drop
Bornylane diisocyanate etc..
As the specific example of above-mentioned aromatic-aliphatic polyisocyanate compound, can enumerate: xyxylene two is different
Cyanate or terephthaldehyde's group diisocyanate (XDI), α, α, α ', α '-tetramethyl xylylene diisocyanate (TMXDI)
Deng.
It as the specific example of above-mentioned aromatic polyisocyanate compound, can enumerate: m- or p- benzene diisocyanate
Ester, 2,4 toluene diisocyanate or 2,6- toluene di-isocyanate(TDI) (TDI), thick TDI, 2,4 '-or 4,4 '-biphenyl methane two are different
Cyanate (MDI), 4,4 '-diisocyanate base biphenyl, 3,3 '-dimethyl -4,4 '-diisocyanate base biphenyl, 3,3 '-dimethyl -
It is 4,4 '-diisocyanate base diphenyl-methanes, thick MDI, 1,5- naphthalene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanates, m-
Or p- isocyanatophenyl sulfonylisocyanates etc..
In addition, the modifier of above-mentioned polyisocyanate compound (b) includes: modified MDI (polyurethane-modified MDI, carbonization two
The phosphate modified MDI of imine modified MDI, trialkyl), it is polyurethane-modified TDI, the modified HDI of biuret, isocyanurate-modified
The modifier of the polyisocyanates such as HDI, isocyanurate-modified IPDI；And the two or more mixture [examples in them
Such as, modified MDI and polyurethane-modified TDI (prepolymer containing isocyanate group) are used in combination].It is preferably isocyanurate-modified
HDI etc..
It is preferably aliphatic polyisocyanate as above-mentioned polyisocyanate compound (b) in terms of resistance to chemical reagents, corrosion protection
Cyanate esters, ester ring type polyisocyanate compound.The number-average molecular weight of polyisocyanate compound (b), is preferably in
3000 or less, particularly preferably in the range of 100 to 1500.
It as the market sale product of this polyisocyanate compound (b), can enumerate: Bayhydur (バ イ ヒ ジ ュ
ー Le) TP-LS2550, Sumidur (ス ミ ジ ュ ー Le) N3300 (it is above Sumika Bayer Urethane Co.,
Ltd. (firmly change バ イ エ Le ウ レ タ Application Co., Ltd.) manufacture), TPA100 (Asahi Kasei Chemicals
Corporation (ケ ミ カ Le ズ Co., Ltd. of Asahi Chemical Industry) manufacture), BASONAT (バ ソ ナ ー ト) HI100 (BASF plants of formula meetings
Society's manufacture) etc..
Add up to 100 mass parts as benchmark, polyisocyanate compound using the solid content of the resin (a) of the hydroxyl
(b) combined amount is the range of 10 mass parts to 60 mass parts, excellent from the angle of hardness of film, resistance to chemical reagents and corrosion protection
It is selected as the range of 15 mass parts to 45 mass parts.
Silane coupling agent (b1)
Coating composition of the invention can mixed silanes coupling agent (b1) as needed.
As above-mentioned silane coupling agent (b1), for example, can enumerate: 3- methacryloyloxypropyl methyl dimethoxy
Silane, 3- methyl allyl acyloxypropyl trimethoxysilane etc. have silane coupling agent containing methylacryloyl；3- aminopropyl three
Methoxy silane, 3- aminopropyltriethoxy dimethoxysilane, N-2- (aminoethyl) -3- aminopropyl trimethoxysilane, N- (ammonia second
Base) the amino-containing silane such as -3- aminopropyltriethoxy dimethoxysilane, N- (aminoethyl) -3- aminopropyl triethoxysilane is even
Join agent；3- glycidoxypropyl dimethoxysilane, 3- glycidoxy-propyltrimethoxy silane, 3- epoxypropoxy
Triethoxysilane, 2- (3,4- expoxycyclohexyl) ethyl trimethoxy silane etc. have silane coupling agent containing epoxy group；3-
The silane coupling agent containing isocyanate group such as isocyanate group propyl-triethoxysilicane；Three (trimethoxysilylpropyls) are different
The silane coupling agent containing isocyanurate group such as cyanurate；Vinyltrimethoxysilane, vinyltriethoxysilane etc.
Silane coupling agent etc. containing vinyl.In these silane coupling agents, from the angle for improving corrosion protection, preferably 3- epoxy third
The silane coupling agents containing epoxy group such as oxygen propyl group methyl dimethoxysilane, 3- epoxypropoxy triethoxysilane.In addition,
These silane coupling agents (b1) both can be used alone can also be simultaneously using two or more.
In addition, the market sale product as silane coupling agent (b1), can enumerate: KBM-402, KBM-403, KBM-502,
(product name is letter above by KBM-503, KBM-603, KBM-907, KBM-9659, KBE-903, KBE-602, KBE-603
More organosilicon company (シ リ コ ー Application society of SHIN-ETSU HANTOTAI) manufactures) etc..
In order to improve finished appearance, corrosion protection, when mixing above-mentioned silane coupling agent (b1), with the resin of the hydroxyl
(a) solid content adds up to 100 mass parts as benchmark, it is desirable to which the combined amount of the silane coupling agent (b1) contains 0.1 mass
Part to 10 mass parts, preferably 0.2 mass parts to 8 mass parts.
Resistant stain (b2)
It, as needed, can be represented containing following formula (1) as resistant stain (b2) for coating composition of the invention
Organosilicate compound or its condensation product.
(R1)n-Si-(OR2)4-n... formula (1)
In formula (1), R1Be can be replaced by sulfydryl, carbon atom number be 1 to 18 alkyl or phenyl, R2Be carbon atom number be 1
To 6 alkyl, n is 0 or 1.
It is to effectively keep stain resistance on substrate surface after coating for above-mentioned resistant stain (b2)
It is used, from the viewpoint of the effect, the condensation product of more preferably above-mentioned organosilicon acid esters.
As the R in above-mentioned general formula1Specific example, can enumerate: methyl, ethyl, n-propyl, isopropyl, normal-butyl,
Isobutyl group, amyl, hexyl, heptyl, n-octyl, 2- ethylhexyl, nonyl, decyl, undecyl, dodecyl, myristyl,
Cetyl, octadecyl, glycidyl, methylglycidyl (2- methylglycidyl), mercapto methyl, 2- sulfydryl
Ethyl, 2- mercaptopropyi, 3- mercaptopropyi, 4- mercaptobutyl, phenyl, to mercaptophenyl etc..
As organosilicon acid esters and/or the specific example of the organosilicon acid esters of its condensation product, can enumerate: tetramethoxy-silicane
Four officials such as alkane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, tetraisobutoxy-silicane alkane
It can silane；Methyltrimethoxysilane, methyltriethoxysilane, methyl tripropoxy silane, three isopropoxy silane of methyl,
Three n-butoxy silane of methyl, three isobutoxy silane of methyl, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl
Tripropoxy silane, three isopropoxy silane of phenyl, three n-butoxy silane of phenyl, three isobutoxy silane of phenyl, hexyl three
Methoxy silane, hexyl triethoxysilane, dodecyltrimethoxysilane, dodecyl triethoxysilane, sulfydryl first
Base trimethoxy silane, mercaptoethyl trimethoxy silane, mercapto methyl triethoxysilane, mercaptoethyl triethoxysilicane
The trifunctionals silane such as alkane, mercaptopropyi trimethoxy silane, Mercaptopropyltriethoxysilane.As above-mentioned organosilicon acid esters
Condensation product can enumerate the condensation product etc. combined by one or more of their tetrafunctional or trifunctional silane.
The market sale product of condensation product as organosilicon acid esters, for example, can enumerate: MKC esters of silicon acis MS51, MKC silicon
Acid esters MS56, MKC esters of silicon acis MS57, MKC esters of silicon acis MS56S, MKC esters of silicon acis MS56SB5, MKC esters of silicon acis MS58B15, MKC silicon
(product name is Mitsubishi to acid esters MS58B30, MKC esters of silicon acis ES40, MKC esters of silicon acis EMS31, MKC esters of silicon acis BTS above
Learn Co., Ltd. manufacture), methyl silicate 51, ethyl silicate 40, ethyl silicate 40T, 48 (trade name of ethyl silicate
Claim, be above COLCOAT CO., LTD. (U ル コ ー ト Co., Ltd.) manufacture), KR500, KR9218, X-41-1805, X-
(product name is Shin-Etsu Chemial Co., Ltd's system above by 41-1810, X-41-1818, X-41-1053, X-41-1056
Make) etc..
In coating composition of the invention, resistant stain (b2), which both can be used alone, can also combine two or more make
With.In organosilicon acid esters and/or its condensation product shown in aforementioned formula, as OR2Base have methoxyl group and carbon atom number 2 to
6 alkoxy, and from storage stability angle, the preferably ratio of number of methoxyl group/carbon atom number 2 to 6 alkoxy
In the range of 95/5 to 30/70.
In coating composition of the invention, from the angle of finished appearance, stain resistance, with the tree of the hydroxyl
The solid content of rouge (a) adds up to 100 mass parts as benchmark, and the combined amount of the resistant stain (b2) is suitble to be set as 0.1 mass
Part is preferably set to 0.2 mass parts to 8 mass parts to 10 mass parts.
Other compositions
In coating composition of the invention, as other compositions, mixing: clay, mica, calcium carbonate can according to need
Equal extender pigments；Zinc oxide, fine silica powder end, bismuth hydroxide, basic bismuth carbonate, bismuth nitrate, bismuth silicate, trbasic zinc phosphate, phosphorus
The rust resisting pigment of sour aluminium, zinc molybdate, calcium molybdate etc.；Ultraviolet absorbing agent, light stabilizer, defoaming agent, pigment dispersing agent, surface tune
Whole dose, surfactant, curing catalysts, tackifier, preservative, antifreezing agent, other delustering agent, other resins etc..
The manufacture of coating composition of the invention
As coating composition of the invention, basic coating (I) is mixed with curing agent component (II) preferably and is obtained
The two-component-type coating composition obtained.For two-component-type coating composition, such as can be carried out by following processes 1 to process 3
Manufacture.
Process 1:
The process is the process for manufacturing basic coating (I).Basic coating (I) can be by by the resin (a) of hydroxyl, average
Talcum (a2), organic resin particles (a3) of the barium sulfate (a1), average grain diameter that partial size is 0.01 μm to 2.0 μm at 10 μm or more
It is mixed with coloring pigment (a4) to manufacture.
In basic coating (I), can mix as needed coloring pigment, rust resisting pigment, extender pigment than that described above,
Ultraviolet absorbing agent, light stabilizer, defoaming agent, pigment dispersing agent, surface conditioner, surfactant, curing catalysts, thickening
Agent, preservative, antifreezing agent, other delustering agents, other resins etc..
In addition, above-mentioned basic coating (I) is even if be 65 mass % to 80 mass %, preferably 68 matter in solid content concentration
In the case where measuring % to 75 mass %, storage stability is also excellent compared with previous basic coating.
Process 2:
The process is the process for manufacturing curing agent component (II).It, can as needed will be aforementioned for curing agent component (II)
Silane coupling agent (b1), aforementioned resistant stain (b2), surfactant, surface conditioner etc. and polyisocyanate compound (b)
It is mixed to manufacture.
Process 3:
The process is the process of manufacture coating composition of the invention.Before can be by the way that above-mentioned curing agent component (II) be added
It states in basic coating (I) and obtains coating composition.In addition, in coating composition of the invention, comprising: unmixed above-mentioned base
The state of plinth coating (I) and curing agent component (II)；The state of mixed base coating (I) and curing agent component (II).
Coating film-forming methods
In addition, the coating film-forming methods for using coating composition of the invention, for example, can enumerate including following work
The method of sequence: being directed to coated article, the process of coating aforementioned coatings composition in the case where applying or not applying bottom-coating；It connects
, the process that coated article sintering and drying 10 minutes to 120 minutes at 50 DEG C to 160 DEG C of the coating composition will be coated with.
In addition, can be enumerated as above-mentioned coated article: cold-rolled steel sheet, mill scale steel plate, alloy galvanized steel plate,
Plated steel sheet, aluminium etc..In turn, bead, surface adjustment, chemical synthesis processing etc. can be applied as needed.In addition, opposite
In can not in a manner of with large heat capacity for the coated article that film is sufficiently heated, can to the coated article carry out low-temperature solid
Change (50 DEG C to 100 DEG C).
Embodiment
In the following, based on Production Example, embodiment and comparative example, present invention be described in more detail, but the present invention does not limit to
In this." portion " in each example indicates that mass parts, " % " indicate quality %.
Production Example 1
The manufacture of acrylic resin soln
In the reaction vessel, it is packed into 113 parts of mixed solvents (dimethylbenzene/n-butanol=80/20), is maintained in 80 DEG C, it will
Following " mixtures " were added dropwise by 4 hours, then added 8 parts of di-t-butyl hydroperoxides, kept carrying out for 3 hours at 80 DEG C
Reaction, in turn, is adjusted by mixed solvent (dimethylbenzene/n-butanol=80/20), and producing solid content is 60 mass %
Acrylic resin soln.Obtained acrylic resin soln has hydroxyl value 94.9mgKOH/g, acid value 3.9mgKOH/g, again
Average molecular weight 11000.
" mixture "
(note 1) Placcel FM-3: product name, Daisel chemical industry Co., Ltd's (ダ イ セ Le chemical industry strain
Formula commercial firm) manufacture；The 6-caprolactone modified vinyl monomer of acrylic acid 2- hydroxyl ethyl ester.
The manufacture of coating composition
1 coating composition No.1 of embodiment
Coating composition No.1 is obtained by following procedures 1 to 3.
Process 1: using ball mill, be added by 20 parts of acrylic resin soln (solid content) obtained in Production Example 1,
BARIFINE (バ リ Off ァ イ Application) 40 parts of BF-20 (note 2) (solid content), 30 parts of talcum MA (note 6) (solid content),
TIPAQUE (タ イ ペ ー Network) 6 parts of CR-95 (note 10) (solid content), 0.5 part of FASTONGN BLUE RSK (note 11) and suitable
Amount ethyl acetate carries out dispersion 12 hours, obtains pigment dispersion paste agent.
Process 2: it in 80 parts of acrylic resin soln (solid content) obtained by Production Example 1, is added by above-mentioned
The pigment dispersion paste agent that process 1 obtains is stirred, and then mixes TECHPOLYMER (テ Network Port リ マ ー) MBX-8 (note 15) 8
Part, ethyl acetate is added to adjust solid content, obtains the base coating that solid content is 65 mass %.
Process 3: in the pigment dispersion paste agent obtained by above-mentioned operation 1,50 parts of mixing Sumidur N3300 (note 18)
(solid content) adjusts solid content with ethyl acetate, obtains the coating composition No.1 that solid content is 60 mass %.
2 to 31 coating composition No.2 to No.31 of embodiment
It other than the mixing content of Tables 1 and 2, is similarly operated with embodiment 1, obtains coating composition
No.2 to No.31.
1 to 15 coating composition No.32 to No.46 of comparative example
It other than the mixing content of table 3, is similarly operated with embodiment 1, obtains coating composition No.32 extremely
No.46.Also, it shows obtain breadboard and the production according to breadboard for testing obtained result together.
(note 2) BARIFINE BF-20: product name, the manufacture of Sakai chemical industry corporation, the sulfuric acid that average grain diameter is 0.03 μm
Barium
(note 3) precipitability barium sulfate PS-07: product name, the manufacture of Guangxi Xiangzh society, average grain diameter are 0.74 μ
The barium sulfate of m
(note 4) SPARWITE W-5HB: product name, the manufacture of Wilbur-Ellis (ウ ィ ル バ ー エ リ ス) society are average
Partial size is 1.6 μm
(note 5) LAKABAR SF: product name, the manufacture of LAKAVISUTH (ラ カ ヴ ィ ッ シ ュ) society, barium sulfate powder are put down
Equal partial size is 14 μm of g
(note 6) talcum MA: product name, Japanese talcum Co., Ltd. (Japanese タ ルク society) manufacture, talcum, 14 μm
(note 7) TTK talcum: product name, the manufacture of bamboo original chemical industry corporation, talcum, average grain diameter are 17 μm
(note 8) T talcum: product name, the manufacture of bamboo original chemical industry corporation, talcum, average grain diameter are 9 μm
(note 9) High rack: product name, the manufacture of bamboo original chemical industry corporation, talcum, average grain diameter are 7 μm
(note 10) TIPAQUE (タ イ ペ ー Network) CR-95: product name, Ishihara Sangyo Kaisha, Ltd.'s manufacture, titanium dioxide
(note 11) FASTONGN BLUE RSK: product name, the manufacture of DIC society, copper phthalocyanine blue
(note 12) SYLYSIA (サ イ リ シ ア) 445: product name, chemistry of silicones Co., Ltd. of Fuji (Fuji's シ リ シ アization
Learn society) manufacture, fine silica powder end, delustering agent
(note 13) NEOLIGHT (ネ オ ラ イ ト) SA-200: product name, the manufacture of bamboo original chemical industry corporation, calcium carbonate are inhaled
Oil mass 32mL/100g
(note 14) TECHPOLYMER MBX-8: the manufacture of ponding finished industrial society, acrylic resin microparticle are average
Partial size is 8 μm
(note 15) TECHPOLYMER MBX-15: the manufacture of ponding finished industrial society, acrylic resin microparticle are average
Partial size is 15 μm
(note 16) TECHPOLYMER MBX-20: product name, the manufacture of ponding finished industrial society, acrylic resin are micro-
Particle, 20 μm of average grain diameter
(note 17) TECHPOLYMER MB30X-20: the manufacture of ponding finished industrial society, acrylic resin microparticle are put down
Equal 20 μm of partial size
(note 18) Sumidur N3300: product name, SUMITOMO CHEMICAL Bayer polyurethane Co., Ltd. (Sumika Bayer
Urethane Co., Ltd.) it manufactures, the isocyanuric acid ester body of hexamethylene diisocyanate, NCO (isocyanate group) equivalent is
193
(note 19) BASONAT HI100: product name, the manufacture of BASF society, the isocyanuric acid of hexamethylene diisocyanate
Ester body, NCO equivalent are 190
(note 20) KBM-403: product name, the manufacture of SHIN-ETSU HANTOTAI's Chemical Co., Ltd., the silane coupling agent containing epoxy group
(note 21) KBM-603: product name, the manufacture of SHIN-ETSU HANTOTAI's Chemical Co., Ltd., amino-containing silane coupling agent
(note 22) MKC SILICATE MS56S: product name, Mitsubishi chemical Co., Ltd's manufacture, esterification esters of silicon acis
(condensation product of tetramethoxy-silicane).
(note 23) MKC SILICATE MS58B30: product name, Mitsubishi chemical Co., Ltd's manufacture, esterification/butyl ester
Change mixing esterification (methyl/butyl mixing esterification) esters of silicon acis (it is the condensation product of tetraalkoxysilane), methyl/butyl number ratio
Rate is 70/30.
In addition, for the preparation of breadboard and performance evaluation, breadboard is prepared in the following manner, and by the test
The result that plate is used to test and obtain is shown together in table 1 into table 3.
The preparation of breadboard
On the cold-rolled steel sheet (100mm × 300mm × 2.0mm) for applying trbasic zinc phosphate processing chemical synthesis processing, so that dry
The mode that dry film thickness reaches 50 μm sprays coating composition No.1 to No.48 obtained in above-described embodiment and comparative example.It connects
, using electric hot-air drying machine at 95 DEG C heat drying 20 minutes, obtain each breadboard.
Performance evaluation
The storage stability of (note 24) basic coating:
Each basic coating is fitted into the glass container of 250mL, stores 4 hours and inspection state at 20 DEG C in the dark.
◎: gelation, the mutually separation, deposited phenomenon for being showed no coating composition；
Zero: have no gelation, the phenomenon of phase separation of coating composition, though deposited phenomenon can be slightly seen through being slowly stirred
It can restore；
△: the gelation of coating composition and at least any one phenomenon in mutually separation can slightly be seen；
×: it can obviously see the gelation of coating composition and mutually at least one of separation phenomenon.
(note 25) finished appearance: for 20 minutes breadboards of heat drying at 95 DEG C, by visual assessment coating surface outside
It sees.
Zero: flatness is good and there is no problem；
△: the finished appearance that can slightly see fluctuating, loss of gloss, point etc. reduces phenomenon；
×: the finished appearance of fluctuating, loss of gloss, point etc. reduces larger.
(note 26) hardness of film: for 20 minutes breadboards of heat drying at 95 DEG C, foundation JIS K 5600-5-4 will
The core of pencil is close to test with about 45 ° of angle and applies plate face, and on one side so that the degree strength that core does not fracture presses on examination
It tests and applies in plate face, about 10mm is moved forwards with uniform speed on one side.The hardness that the most hard pencil of film will not destroyed is made
For pencil hardness.
The gloss stability of (note 27) dumb light film: for the cold-rolled steel sheet for having carried out trbasic zinc phosphate chemical synthesis processing
(70mm × 300mm × 2.0mm), carries out electrodeposition coating in a manner of making dry film thickness reach 20 μm, be sintered it is dry and
Obtain electrodeposition coating plate.
Then, using through the foregoing embodiment, the obtained each coating composition of comparative example so that dry film thickness reaches 50
μm mode sprayed perpendicular to coated article face, find out be sintered at 60 DEG C 20 minutes coated plate glossiness at 160 DEG C
" low in glossiness (△) " of the glossiness of the coated plate of lower sintering 20 minutes.
In addition, for the glossiness of each film, according to " the 60 degree of mirror surface lusters " of JIS K 5600-4-7 (1999),
It is anti-when measuring incidence angle on the longitudinal direction of breadboard with the interval about 2.5cm and n=10 and light acceptance angle is respectively 60 degree
Rate is penetrated, so as to find out " average value ", and is evaluated according to following benchmark.
◎: low in glossiness (△) is within ± 2；
〇: the absolute value of low in glossiness (△) is more than 2 and within 5；
△: the absolute value of low in glossiness (△) is more than 5 and within 10；
×: the absolute value of low in glossiness (△) is more than 10.
(note 28) resistance to chemical reagents: 20 minutes breadboards of heat drying at 95 DEG C are impregnated in 40 DEG C of deionized water
It is taken out after 240 hours, according to JIS K 5600-5-6 (1999) gridiron pattern-tape method, using blade to the coated surface of coated plate
11 seams are cut out in parallel respectively in a manner of being cut into base material (green compact) and by being spaced on longitudinal and transverse direction for about 2mm
Gap pastes cellophane (registered trademark) jointing tape to form gridiron pattern on the surface thereof, and adhesive tape is fiercely removed
Afterwards, it is evaluated for gridiron pattern coating surface according to following benchmark:
◎: the peeling of film is had no completely
Zero: slightly seeing peeling in the part of the film at knife wound
The gridiron pattern being completely exfoliated in △: 100 gridiron patterns is 1 to 20
×: the gridiron pattern being completely exfoliated in 100 gridiron patterns is 21 or more.
(note 29) corrosion protection: using 20 minutes breadboards of heat drying at 95 DEG C, cutting out crosscutting scar with blade, will
It is carried out salt water resistance spray testing 120 hours according to JIS Z-2371, according to the rust occurred from knife wound, heaves width according to as follows
Benchmark is evaluated:
The maximum width that ◎: becoming rusty or heaves is lower than 2mm (unilateral side) away from cutting part；
Zero: the maximum width for becoming rusty or heaving is away from cutting part in 2mm more than or lower than 3mm (unilateral side)；
The maximum width that △: becoming rusty or heaves is away from cutting part in 3mm more than or lower than 4mm (unilateral side)；
×: the maximum width for becoming rusty or heaving is away from cutting part in 4mm or more (unilateral side).
(note 30) stain resistance: by breadboard by make coated surface toward the north in a manner of with from vertical direction 4 degree angle pacify
In the setting table modeled to eaves end, and the roof of the Kansai Paint Co., Ltd of Niqi City, Hyogo Prefecture, Japan into
Row exposure test from starting to expose to the open air after 1 month, according to JIS Z8370 and uses Suga Test Instruments Co.,
Ltd. color difference (the △ of multiple light courcess spectral colorimetric meter the MSC-5N measurement and initial stage coated plate of (ス ガ tries OmenJi Co., Ltd.) manufacture
E), evaluated by following benchmark.
◎: △ E is lower than 1；
Zero: △ E is 1 more than or lower than 2；
△: △ E is 2 more than or lower than 5；
×: △ E is 5 or more.
Industrial applicibility
Coating composition of the invention is capable of providing finished appearance, hardness of film, the gloss stability of dumb light film, drug resistance
Moral character and the excellent coated article of corrosion protection.
Claims (4)
1. a kind of coating composition is the resin (a) containing hydroxyl, the barium sulfate that average grain diameter is 0.01 μm to 2.0 μm
(a1), average grain diameter is in 10 μm or more of talcum (a2), organic resin particles (a3) and coloring pigment (a4) and polyisocyanic acid
The coating composition of ester compounds (b), wherein
Add up to 100 mass parts as benchmark using the solid content of the resin (a) of the hydroxyl, the coating composition contains 1
Mass parts to the barium sulfate (a1) of 130 mass parts, the talcum (a2) of 1 mass parts to 50 mass parts, 0.1 mass parts extremely
The organic resin particles (a3), the coloring pigment (a4) of 1 mass parts to 100 mass parts, 10 mass parts of 20 mass parts
To the polyisocyanate compound (b) of 60 mass parts.
2. coating composition as described in claim 1, wherein with the solid content of the resin (a) of the hydroxyl total 100
For mass parts as benchmark, the coating composition contains the silane coupling agent (b1) of 0.1 mass parts to 10 mass parts.
3. coating composition as claimed in claim 1 or 2, wherein total with the solid content of the resin (a) of the hydroxyl
For 100 mass parts as benchmark, the coating composition contains anti-pollution represented by the formula (1) of 0.1 mass parts to 10 mass parts
Agent (b2),
(R1)n-Si-(OR2)4-n... formula (1)
In formula (1), R1It is the alkyl or phenyl that can be 1 to 18 by the carbon atom number that sulfydryl replaces, R2Be carbon atom number be 1 to 6
Alkyl, n are 0 or 1.
4. a kind of construction implement or industrial machinery, wherein have on the coated article of the construction implement or industrial machinery
The cured coating film formed by coating composition described in any one of claims 1 to 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-177621 | 2015-09-09 | ||
| JP2015177621 | 2015-09-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106519938A CN106519938A (en) | 2017-03-22 |
| CN106519938B true CN106519938B (en) | 2019-02-22 |
Family
ID=58320428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610708106.6A Expired - Fee Related CN106519938B (en) | 2015-09-09 | 2016-08-23 | Coating composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6746417B2 (en) |
| CN (1) | CN106519938B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019067010A1 (en) * | 2017-09-28 | 2019-04-04 | Soundguard Products, Llc | Sound reducing coating composition |
| CN109679478B (en) * | 2018-12-29 | 2021-07-09 | 东来涂料技术（上海）股份有限公司 | High-pressure steam impact-resistant coating for metal materials and preparation method thereof |
| JP7438801B2 (en) | 2020-03-19 | 2024-02-27 | リケンテクノス株式会社 | Active energy ray-curable resin composition and decorative sheet |
| JP6994615B1 (en) | 2020-07-07 | 2022-01-14 | 東洋インキＳｃホールディングス株式会社 | Matte coating agent and laminate using it |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911563A (en) * | 2011-08-06 | 2013-02-06 | 关西涂料株式会社 | Thermosetting two-component coating composition coated articles |
| CN102924905A (en) * | 2012-10-22 | 2013-02-13 | 佛山佛塑科技集团股份有限公司 | Biaxially oriented matte BOPA (Biaxially oriented polyamide film) thin film and preparation method thereof |
| CN103360927A (en) * | 2012-03-30 | 2013-10-23 | 株式会社发尔特克 | Plastic formation body formed with coating preventing creaky sound |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3874401B2 (en) * | 2000-09-28 | 2007-01-31 | 関西ペイント株式会社 | Undercoat paint composition and repair coating method using the same |
| US20020061957A1 (en) * | 2000-09-28 | 2002-05-23 | Shinji Tomita | Coating composition for undercoat and coating method for repair employing the same |
| JP2003268297A (en) * | 2002-03-14 | 2003-09-25 | Dainippon Ink & Chem Inc | Coating composition and formation of coating film |
| WO2012086723A1 (en) * | 2010-12-24 | 2012-06-28 | 関西ペイント株式会社 | Contamination-resistant coating composition with excellent durability |
| JP2013159622A (en) * | 2012-02-01 | 2013-08-19 | Dainippon Toryo Co Ltd | Two-pack type urethane coating composition, and metal coated body |
| EP2835404A4 (en) * | 2012-04-03 | 2015-12-16 | Kansai Paint Co Ltd | Aqueous paint composition and method for forming coating |
| JP5818736B2 (en) * | 2012-04-03 | 2015-11-18 | 関西ペイント株式会社 | Water-based coating composition and coating film forming method |
-
2016
- 2016-07-26 JP JP2016146284A patent/JP6746417B2/en active Active
- 2016-08-23 CN CN201610708106.6A patent/CN106519938B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911563A (en) * | 2011-08-06 | 2013-02-06 | 关西涂料株式会社 | Thermosetting two-component coating composition coated articles |
| CN103360927A (en) * | 2012-03-30 | 2013-10-23 | 株式会社发尔特克 | Plastic formation body formed with coating preventing creaky sound |
| CN102924905A (en) * | 2012-10-22 | 2013-02-13 | 佛山佛塑科技集团股份有限公司 | Biaxially oriented matte BOPA (Biaxially oriented polyamide film) thin film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106519938A (en) | 2017-03-22 |
| JP6746417B2 (en) | 2020-08-26 |
| JP2017052931A (en) | 2017-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106519938B (en) | Coating composition | |
| EP3131937B1 (en) | Aqueous dispersion and coating composition comprising the same | |
| EP3060611B1 (en) | Aqueous coating composition and process of making the same | |
| EP2986681B1 (en) | An aqueous coating composition | |
| CN107163812B (en) | A kind of extra-weather-proof corrosion-resistant engineering machinery finishing coat of low VOC and preparation method | |
| CN102702878A (en) | Fluorine-containing water-based paint | |
| CN102911563B (en) | Thermosetting two-component coating composition and coated articles | |
| CN105400309B (en) | A kind of aerosil modification acrylate water-repellent paint and its production technology | |
| CN113652134B (en) | Stain-resistant matte aqueous coating composition and method for forming stain-resistant matte coating film | |
| CN109601001A (en) | Benzophenone derivates, aqueous copolymer dispersion liquid and water-based paint compositions | |
| EP1458821B1 (en) | Non-aqueous dispersion based antifouling paint composition | |
| CN110511625A (en) | A kind of extra-weather-proof normal temperature cure FEVE fluorocarbon coating | |
| EP2450410B1 (en) | Hase-thickened composition | |
| CN102161854B (en) | Low odor compositions and methods to attain low odor compositions | |
| CN102101975B (en) | Low odor compositions and low odor coating compositions | |
| US20160075906A1 (en) | Coatings that provide hydrophilic surface | |
| CN106634539A (en) | Double-component high-solid heavy anti-corrosion steel structure decorative finishing paint | |
| EP3519506B1 (en) | Aqueous polymer composition | |
| EP3601450B1 (en) | Coating composition and use thereof | |
| CN114989707B (en) | Polyurea coatings | |
| KR100584472B1 (en) | Acrylic emulsion resin composition, method of preparing the same and aqueous paint composition comprising the same | |
| CN111234642B (en) | Bi-component super-hydrophobic coating | |
| CN103183997A (en) | Water-soluble basecoat paint composition for automobiles and method of forming paint layer using the same | |
| JP2013006898A (en) | Heat ray highly reflective paint composition, kit for preparing heat ray highly reflective paint composition, heat ray highly reflective coated article, and production method of heat ray highly reflective coated article | |
| KR102600639B1 (en) | Temperature sensitive composition using water-based and oil-based binder resin and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190222 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |