CN1472271A - Paint composition and coating method - Google Patents
Paint composition and coating method Download PDFInfo
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- CN1472271A CN1472271A CNA031384234A CN03138423A CN1472271A CN 1472271 A CN1472271 A CN 1472271A CN A031384234 A CNA031384234 A CN A031384234A CN 03138423 A CN03138423 A CN 03138423A CN 1472271 A CN1472271 A CN 1472271A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F27/00—Details of transformers or inductances, in general
- H01F27/34—Special means for preventing or reducing unwanted electric or magnetic effects, e.g. no-load losses, reactive currents, harmonics, oscillations, leakage fields
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F27/00—Details of transformers or inductances, in general
- H01F27/06—Mounting, supporting or suspending transformers, reactors or choke coils not being of the signal type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F27/00—Details of transformers or inductances, in general
- H01F27/24—Magnetic cores
- H01F27/26—Fastening parts of the core together; Fastening or mounting the core on casing or support
Abstract
The coating composition essentially comprises (I) at least one modified epoxy resin selected from (d-1) a modified epoxy resin obtained by reaction of (a) an epoxy resin having in one molecule at least two epoxy groups with (b) a dibasic acid and (c-1) a carboxyl-functional acrylic resin and (d-2) the modified epoxy resin obtained by polyaddition of (b) the dibasic acid to (a) the epoxy resin and graft copolymerization of (c-2) a polymerizable unsaturated monomer, (II) a curing agent for said modified epoxy resin, and (III) an organic solvent which contains >=80 wt.% of a hydrocarbon solvent selected from the aliphatic hydrocarbon solvents and the high-boiling point aromatic hydrocarbon solvents.
Description
Technical field
The present invention relates to form dissolve in aliphatic hydrocarbon series solvent and high boiling point aromatic hydrocarbons series solvent, can not produce curing obstacle of coating film etc., the coating composition of following coating film that shock resistance, touch dry are good, and use it can form the coating process of multilayer film.
Background technology
All the time, Resins, epoxy is good because of erosion resistance, connecting airtight property, chemical proofing etc., so be widely used as the anticorrosive coating resin.When so existing Resins, epoxy is used in organic solvent diluting type coating; generally must make it be dissolved in toluene, dimethylbenzene, methyl ethyl ketone, ethyl acetate etc. and represent in the strong organic solvent of low flash point, lower boiling hazardous property and make coating, the security during application and the viewpoint of environment protection are seen the problem that existence is very big.Therefore, as diluting solvent, the soluble Resins, epoxy of this solvent there are all motions about the oil series solvents such as mineral turpentine that use high flash point, high boiling point and low Hazardous.
For example, as the method that Resins, epoxy is dissolved in mineral turpentine, can lift and make Resins, epoxy and induced by alkyl hydroxybenzene reaction modifying, (for example make alkyl bis-phenol and Epicholorohydrin polycondensation etc., Te Kaiping 3-115318 communique, Te Kaiping 4-39320 communique, the spy opens flat 10-87787 communique, the spy opens flat 11-199648 communique etc.).Though Resins, epoxy can be dissolved in the mineral turpentine according to this method, but exist shock resistance of filming and the touch dry obtain poor, inappropriate situation that obstacle takes place to solidify coating film on the oxidative cure type of phthalic acid system and so on during in addition as coating down.
Summary of the invention
The objective of the invention is to, the coating composition of the following coating film of provide and dissolve in aliphatic hydrocarbon series solvent and high boiling point aromatic hydrocarbons series solvent, can not produce curing obstacle of coating film etc., can form shock resistance, touch dry is good, further, other purpose is, provide and use this coating composition conduct coating down, no matter the middle coating film thereon and the kind of last coating film all do not produce on these are filmed and solidify obstacle etc., can form the coating process of multilayer film.
The present invention relates to a kind of coating composition, it is characterized in that, be selected from acrylic resin (c-1) the reaction formation modified epoxy (d-1) that makes Resins, epoxy (a) and the diprotic acid (b) that has 2 above epoxy group(ing) in 1 molecule and contain carboxyl to contain, make Resins, epoxy (a) and diprotic acid (b) addition polymerization, and form at least a modified epoxy (I) in the modified epoxy (d-2) with (c-2) graft polymerization of polymerizability unsaturated monomer or copolymerization, this modified epoxy solidifying agent (II), and the necessary composition of organic solvent (III) conduct, this organic solvent (III) contains more than the hydrocarbon system solvent 80 weight % that are selected from aliphatic hydrocarbon series solvent and high boiling point aromatic hydrocarbons series solvent; And the coating process that relates to coating (B) in coating (A) back application under the coated surface application, wherein, as this time coating (A), be selected from acrylic resin (c-1) the reaction formation modified epoxy (d-1) that makes Resins, epoxy (a) and the diprotic acid (b) that has 2 above epoxy group(ing) in 1 molecule and contain carboxyl to contain, make Resins, epoxy (a) and diprotic acid (b) addition polymerization, and form at least a modified epoxy (I) in the modified epoxy (d-2) with (c-2) graft polymerization of polymerizability unsaturated monomer or copolymerization, this modified epoxy solidifying agent (II), and the necessary composition of organic solvent (III) conduct, this organic solvent (III) contains more than the hydrocarbon system solvent 80 weight % that are selected from aliphatic hydrocarbon series solvent and high boiling point aromatic hydrocarbons series solvent.
Embodiment
Among the present invention, modified epoxy (I) forms modified epoxy (d-1) for being selected from acrylic resin (c-1) reaction that makes Resins, epoxy (a) and diprotic acid (b) and contain carboxyl, makes Resins, epoxy (a) and diprotic acid (b) addition polymerization and forms at least a in the modified epoxy (d-2) with (c-2) graft polymerization of polymerizability unsaturated monomer or copolymerization.
Above-mentioned Resins, epoxy (a) is, has 2 above epoxy group(ing) in 1 molecule, and further, average epoxy equivalent (weight) is in about scope of 150～about 1000, in further preferred about scope of 150～about 500.For example, when using about about 1500 the Resins, epoxy of epoxy equivalent (weight), as a whole, so long as with its average epoxy equivalent (weight)s of mixture of other Resins, epoxy in about 150～about 1000 scopes, just can use.
As above-mentioned Resins, epoxy (a), for example can lift, by the Resins, epoxy of dihydroxy-benzene class and epichlorohydrin derived, by the alkyl phenolic varnish type Resins, epoxy of alkylphenol novolac resin and epichlorohydrin derived; At least a above Resins, epoxy that is selected from Racemic glycidol ether type epoxy, glycidyl ester type epoxy resin, other Racemic glycidol ether type epoxies, the aliphatic epoxy resin passes through alkylphenol or/and the modified epoxy of fatty acid modified formation; Bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A epoxy resin, A Hydrogenated Bisphenol A F type Resins, epoxy etc., they can be used alone or as a mixture.
Above-mentioned Resins, epoxy (a) from the problem of exogen endocrine regulation chemical substance (environmental hormone), does not preferably contain the Resins, epoxy of free dihydroxyphenyl propane and nonylphenol, particularly as initial feed, does not preferably use dihydroxyphenyl propane or nonylphenol.
In the above-mentioned example, as Resins, epoxy (a), the dihydroxy-benzene class of preferred especially 4-tert-butyl catechol and so on and the derivative of Epicholorohydrin.
Among the present invention, diprotic acid (b) is with above-mentioned Resins, epoxy (a) polyaddition reaction, to make the material of Resins, epoxy chainpropagation.The modified epoxy that obtains thus (I) is the resin that polymer quantizes, improves the touch dry of filming.
As this diprotic acid (b), can give an example as, phthalate anhydride, m-phthalic acid, terephthalic acid, positive phthalate anhydride, 2,6-naphthalene dicarboxylic acids, tetrahydrochysene phthalate anhydride, hexahydrophthalic acid anhydride, dicarboxyl Hydrogenated Bisphenol A, hydrogenated dimer acids, hydrogenated naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, tristane dicarboxylic acid, succsinic acid, pentanedioic acid, fumaric acid, hexanodioic acid, sebacic acid, maleic anhydride, dimeracid etc.They can be used alone or as a mixture.
Acrylic resin that contains carboxyl (c-1) among the present invention or polymerizability unsaturated monomer (c-2) from touch dry, this point of shock resistance of filming, are for Resins, epoxy (a) is acrylic acid modified and material that use.
The above-mentioned common weight-average molecular weight of acrylic resin (c-1) that contains carboxyl is in 3000～50000 scope, and in preferred 5000～20000 the scope, the resin acid value is in the scope of 3～300mgKOH/g, in the scope of preferred 10～100mgKOH/g.If the weight-average molecular weight of acrylic resin that contains this carboxyl is less than 3000, and the processibility of cured coating film is bad, otherwise if surpass 50000, the viscosity of coating uprises, and is all inadvisable.If the resin acid value of acrylic resin that contains this carboxyl is not enough 3mgKOH/g, and the shock resistance of the modified epoxy that obtains reduces, otherwise if surpass 300mgKOH/g, the viscosity of coating uprises, and is all inadvisable.
Containing vinyl monomer that the acrylic resin (c-1) of this carboxyl can be by will having carboxyl and other vinyl monomer easily makes with the well-established law copolymerization.
As vinyl monomer with carboxyl, can give an example as, vinylformic acid, methacrylic acid, Ba Dousuan, methylene-succinic acid, toxilic acid, fumaric acid, 2-carboxy ethyl (methyl) acrylate, 2-carboxyl propyl group (methyl) acrylate, 5-carboxy pentyl (methyl) acrylate etc.
As other vinyl monomer, can give an example as, have the vinyl monomer of hydroxyl; (methyl) esters of acrylic acid; Ethylene series compound and diolefin; The unsaturated monomer that contains the hydrocarbon ring; Nitrogenous unsaturated monomer; The monomer that contains water-disintegrable alkoxysilyl; Contain the monomer of epoxy group(ing) etc.
As the vinyl monomer that contains hydroxyl, can give an example as, the hydroxyalkyl acrylate of the carbon number 2～8 of acrylic or methacrylic acid such as 2-hydroxyethyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate, hydroxybutyl (methyl) acrylate; The monoesters of unsaturated carboxylic acids such as the many alcohol of polyether-types such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol and (methyl) vinylformic acid; Many alcohol of polyether-types such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol and 2-hydroxyethyl (methyl) acrylate etc. contain the monomeric monoether of unsaturated carboxylic acid; Unsaturated compound that contains anhydride group of maleic anhydride or itaconic anhydride and so on and ethylene glycol, 1, the mono-esterification thing or two carboxylates of glycolss such as 6-hexylene glycol, neopentyl glycol; The hydroxyalkyl vinyl ethers of hydroxyethyl vinyl ether and so on; Allyl alcohol etc.; 2-hydroxypropyl (methyl) acrylate; α, the affixture of the monoepoxide of beta-unsaturated carboxylic acid and CARDURA E10 (Royal Dutch Shell chemistry (strain) system, trade(brand)name) or alpha-olefin epoxide and so on; The monacid affixture of (methyl) glycidyl acrylate and acetic acid, propionic acid, p-tert-butyl benzoic acid, fatty acid; Contain the monomer of above-mentioned hydroxyl and the affixture of lactone (for example, 6-caprolactone, γ-Wu Neizhi) etc.
As the example of (methyl) esters of acrylic acid, can lift methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, Ethyl acrylate, 2-EHA, the vinylformic acid n-octyl, decyl acrylate, the stearyl acrylate ester, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic tert-butyl acrylate, N-Hexyl methacrylate, methacrylic acid 2-ethylhexyl, Octyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate(LMA), the methacrylic acid stearyl ester, the alkyl ester or the cycloalkyl ester of the carbon number 1～24 of acrylic or methacrylic acid such as cyclohexyl methacrylate; The alkoxy alkyl of the carbon number 2～18 of acrylic or methacrylic acid such as vinylformic acid methoxyl group butyl ester, methacrylic acid methoxy base butyl ester, vinylformic acid methoxyl group ethyl ester, methacrylic acid methoxy base ethyl ester, vinylformic acid oxyethyl group butyl ester, methacrylic acid oxyethyl group butyl ester etc.
As olefin(e) compound and diolefin, can give an example as, ethene, propylene, butylene, vinylchlorid, divinyl, isoprene, chloroprene etc.
As the unsaturated monomer that contains the hydrocarbon ring, can give an example as, vinylbenzene, alpha-methyl styrene benzyl (methyl) acrylate, phenoxy group ethyl (methyl) acrylate, cyclohexyl (methyl) acrylate, iso-borneol (methyl) acrylate etc.
As nitrogenous unsaturated monomer, can give an example as, N, N-dimethyl aminoethyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N-tertiary butyl amino-ethyl (methyl) acrylate etc. contain azanyl (methyl) acrylate; Polymerizable amide classes such as acrylamide, Methacrylamide, N-methyl (methyl) acrylamide; Aromatic series nitrogen containing monomers such as 2-vinyl pyridine, l-vinyl-2-pyrrolidone, 4-vinylpridine; Polymerizability such as vinyl cyanide, methacrylonitrile nitrile; Allyl amine etc.
As the monomer that contains water-disintegrable alkoxysilyl, can give an example as, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, γ-(methyl) acryloxy propyl trimethoxy silicane, vinyltriacetoxy silane, γ-(methyl) acryloxy propyl-triethoxysilicane etc.
As the monomer that contains epoxy group(ing), can give an example as, (methyl) glycidyl acrylate, (methyl) vinylformic acid methyl glycidyl ester etc.
The method of copolymerization can be used the polymerization of general vinyl monomer, considers versatility and cost etc., most preferably the solution-type radical polymerization in the organic solvent.That is, in the solvent of organic dissolving described later (III) example, in the presence of polymerization starters such as Diisopropyl azodicarboxylate, benzoyl peroxide, in 60～150 ℃ scope, carry out copolyreaction, can easily obtain purpose polymers.
Among the present invention, for acrylic resin (c-1) reaction that makes Resins, epoxy (a) and diprotic acid (b) and contain carboxyl obtains modified epoxy (d-1), should (a) composition and (b) and (c-1) composition, from the touch dry of filming, solidified nature, dope viscosity, equivalence ratio with the carboxyl in the epoxy group(ing) in (a) composition and (b) composition is 1: 0.05～1: 0.5, ratio in preferred 1: 0.1～1: 0.3 scope, further, equivalence ratio with the carboxyl in the epoxy group(ing) in (a) composition and (c-1) composition is 1: 0.05～1: 0.5, mixed in preferred 1: 0.1～1: 0.3 scope, for example in the presence of epoxy group(ing)/carboxyl reaction catalyzer, heat usually and made its reaction in 1～10 hour better.As epoxy group(ing)/carboxyl reaction catalyzer, can give an example as, level Four salt catalysts such as tetraethylammonium bromide, Tetrabutylammonium bromide, chlorination tetraethyl-amine, bromination tetrabutyl phosphine, chlorinated triphenyl base benzyl phosphine; Amine such as triethylamine, Tributylamine etc.In addition, temperature of reaction is more suitable 120～150 ℃ of scopes.
On the other hand, above-mentioned polymerizability unsaturated monomer (c-2) is, with the material of Resins, epoxy (a) graft polymerization or copolyreaction formation propenyl chain.As this polymerizability unsaturated monomer (c-2), for example can use the suitable aforementioned vinyl monomer that contains the middle example of acrylic resin (c-1) of carboxyl that is selected from carboxyl; The vinyl monomer that contains hydroxyl; (methyl) esters of acrylic acid; Ethylene series compound and diolefin; The unsaturated monomer that contains the hydrocarbon ring; The unsaturated monomer that contains nitrogen; The monomer that contains water-disintegrable alkoxysilyl; Contain the material in the monomer etc. of epoxy group(ing).Wherein, the vinyl monomer that will contain carboxyl is during as polymerizability unsaturated monomer (c-2), epoxy reaction in carboxyl of their origin and above-mentioned diprotic acid (b) and the Resins, epoxy (a).
Among the present invention, in order to obtain modified epoxy (d-2), with with respect to Resins, epoxy (a) 100 weight parts, with the mixed polymerizability unsaturated monomer (c-2) in the scope of 10～2000 weight parts, at polymerization starters such as Diisopropyl azodicarboxylate, benzoyl peroxide, preferably carry out reacting in 1～10 hour at 60～150 ℃ scope internal heating under the existence of peroxidation system polymerization starters such as benzoyl peroxide of grafting for high-level efficiency.Further, equivalence ratio with the carboxyl in the epoxy group(ing) in (a) composition and (b) composition is 1: 0.05～1: 0.5, this Resins, epoxy of mixed (a) composition and diprotic acid (b) in preferred 1: 0.1～1: 0.3 scope, for example in the presence of epoxy group(ing)/carboxyl reaction catalyzer, heat usually and made its reaction in 1～10 hour better.When containing the vinyl monomer with carboxyl in the polymerizability unsaturated monomer (c-2), preferably making the epoxy group(ing) in (a) composition is 1: 0.05～1: 0.5 with (c-2) equivalence ratio of the carboxyl of composition origin.As epoxy group(ing)/carboxyl reaction catalyzer, the suitable selection that can exemplify from aforementioned (d-1) is used.In addition, temperature of reaction is more suitable 120～150 ℃ of scopes.
Among the present invention, from the angle of solidified nature, above-mentioned modified epoxy (I) also can contain the phenol hydroxyl.The introducing of phenol hydroxyl is carried out with the carboxyl reaction that contains the phenol of carboxyl by the epoxy group(ing) of Resins, epoxy usually.As the phenol that contains carboxyl, can give an example as, Whitfield's ointment, P-hydroxybenzoic acid, 4-hydroxymethyl-benzoic acid etc.By the introducing of this phenol hydroxyl, be that curing catalyst also can improve curing even do not use amine, the bleeding that can not produce amine and be curing catalyst causes the problem of coating film flavescence on the oxidative cure type of phthalic acid and so on.
Modified epoxy among the present invention is the interior solidifying agent of 50～500 scopes with solidifying agent (II) for Ahew.
As above-mentioned solidifying agent, can use existing known hardener for epoxy resin, specifically, can give an example as, aliphatic poly amines such as m-xylene diamine, isophorone diamine, Diethylenetriaminee (DETA), triethylenetetramine, diaminodiphenyl-methane; The epoxy resin derivant of this aliphatic polyamines, ketoimine thing, polymeric amide amine, polyamide resin etc., they may be used singly or in combination of two or more.Wherein, preferred dimer acid modified polyamide resin, the dimer acid modified polyamide resin of ketoimineization.In the dimer acid modified polyamide resin of this ketoimineization, from the unit elongation and the tack aspect of filming, the ketoimine rate is more than 80%, and is preferred more than 90%.
Organic solvent among the present invention (III) is each composition for homogeneous decomposition or dispersion paints, adjust viscosity etc., and when on old coating film, repeating coating composition to not causing that the old coating film peeling is essential, in this organic solvent, contain be selected from aliphatic hydrocarbon series solvent and high boiling point aromatic hydrocarbons series solvent the hydrocarbon system solvent with more than the 80% weight %.The preferred boiling point of aromatic hydrocarbons series solvent is more than 148 ℃.
Concrete example as above-mentioned aliphatic hydrocarbon series solvent and high boiling point aromatic hydrocarbons series solvent for example can use VM﹠amp; P petroleum naphtha, mineral turpentine, solvent lam-oil, aromatic series petroleum naphtha, solvent naphtha, Solvesso100, Solvesso150, Solvesso200 (Solvesso is the registered trade mark of Esso Standard Oil Co.Ltd), SWASOL310, SWASOL1000, SWASOL1500 relatively little fatty family or the fragrant family hydro carbons of dissolving power such as (SWASOL are the registered trade mark of Cosmo Oil Co.Ltd); Aliphatic hydrocarbons such as normal butane, normal hexane, normal heptane, octane, isononane, n-decane, n-dodecane, pentamethylene, hexanaphthene, tetramethylene etc.
Organic solvent in the present composition preferably all is aliphatic hydrocarbon series solvent or high boiling point aromatic hydrocarbons series solvent, in organic solvent, can contain other organic solvent beyond aliphatic hydrocarbon series solvent or the high boiling point aromatic hydrocarbons series solvent below 20%, preferred below 10%.If the amount of other organic solvent increases, cause the peeling and the dissolving of old coating film when repeating to be coated with easily.
In the coating composition of the present invention, further, can mix pigment class such as tinting pigment, pigment extender, corrosion-inhibiting pigment according to necessity; Coating such as upgrading resin, tackifier, dispersion agent, curing catalyst are with additive etc.
Coating process of the present invention as following coating (A), is coated with the above-mentioned coating composition that obtains and is contained on applied, then the following last coating (B) of application with it.
As applied, for example comprise the inorganic building material face and the surperficial adjustment face thereof of metal material faces such as iron, aluminium, zinc and surface treatment face, concrete or plaster, slabstone, plank, profiled sheeting etc., also comprise old coating film face on these material faces etc.
General methods such as the above-mentioned application of coating (A) down can be coated with by bristle, spraying, roller coat, blade coating, various coating machine applications are carried out, and its glue spread does not have specific restriction, is generally 10～2000g/m
2, preferred 80～500g/m
2In the scope.
On the above-mentioned following coating film that obtains, can be according to necessary application middle coating intermediate.As middle coating intermediate, have no particular limits, can suitably use the middle coating intermediate of existing known organic solvent type or water-based, can give an example as, hard such as epoxy resin, acrylic resin, urethane resin system are middle coating intermediate, multilayer precision work middle coating intermediates such as acrylic resin, urethane resin system, acrylic rubber system, epoxy resin.
As being coated with the last coating (B) that is contained in above-mentioned lower floor coated surface or middle level coated surface, have no particular limits, can suitably use the last coating of existing known organic solvent type or water-based, can give an example as the coating of, acrylic resin, urethane resin system, silicone resin system, fluoro-resin system.
General methods such as above-mentioned application of going up coating (B) can be coated with by bristle, spraying, roller coat, blade coating, various coating machine applications are carried out, and its glue spread does not have specific restriction, can suit to select according to the coating that uses.
According to the present invention, the coating composition that contains diprotic acid and acrylic modified epoxy resin by use, can form and dissolve in aliphatic hydrocarbon series solvent and high boiling point aromatic hydrocarbons series solvent, can not produce the curing obstacle of coating film on the oxidative cure type of phthalic acid and so on, shock resistance, the good following coating film of touch dry.Further, by in this this epoxy resin, introducing the phenol hydroxyl, can improve solidified nature.
Embodiment
Below, exemplify Production Example, embodiment and comparative example the present invention is made more specific description.In addition, " part " in each example and " % " all are weight basis.
The manufacturing of modified epoxy
Production Example 1
With SWASOL 310 (Cosmo Oil Co., Ltd makes solvent) 87 parts, 210 parts of Epikote828EL (Japan Epoxy Resins Co.Ltd system, bisphenol A type epoxy resin, epoxy equivalent (weight) 187), and HARIDIMER200 (HARIMA CHEMICALS, INC, dimeracid) 90 parts under nitrogen gas stream, in 135 ℃ of heating, with dripping the following vinyl monomer and the mixture of polymerization initiator in 2 hours, after the dropping, slaking 1 hour.Then, add 0.6 part of Tetrabutylammonium bromide, reacted about 2 hours, reach 1mgKOH/g when following, add " SWASOL 310 " 295 parts, obtain acrylic modified epoxy resin (I-1) in the resin acid value.This resin solution nonvolatile component 60%, epoxy equivalent (weight) 826 (solids component).
6 parts in vinylformic acid
45 parts of 2-ethylhexyl acrylate
45 parts of 2-ethylhexyl methacrylic esters
204 parts of vinylbenzene
18 parts of t-butyl peroxy-2-ethylhexanoate
Production Example 2
With " SWASOL 310 " 87 parts, 210 parts of Epikote 828EL, and " HARIDIMER200 " 90 parts under nitrogen gas stream, in 135 ℃ of heating, with the following vinyl monomer of dropping in 2 hours and the mixture of polymerization initiator, after the dropping, slaking 1 hour.Then, add 0.6 part of Tetrabutylammonium bromide, reacted about 2 hours.Further add 12 parts of Whitfield's ointments, reacted about 1 hour, reach 1mgKOH/g when following, add " SWASOL 310 " 303 parts, obtain acrylic modified epoxy resin (I-2) in the resin acid value.This resin solution nonvolatile component 60%, epoxy equivalent (weight) 940 (solids component).
6 parts in vinylformic acid
45 parts of 2-ethylhexyl acrylate
45 parts of 2-ethylhexyl methacrylic esters
204 parts of vinylbenzene
18 parts of t-butyl peroxy-2-ethylhexanoate
Production Example 3
With " SWASOL 310 " 87 parts, EPICLON HP-820 (big Japanese ink chemical company system, 4-tert.-butyl pyrocatechol/1-chloro-2, the 3-epoxy propane copolymer, epoxy equivalent (weight) 211) 276 parts, 24 parts of hexanodioic acids are under nitrogen gas stream, in 135 ℃ of heating, with dripping the following vinyl monomer and the mixture of polymerization initiator in 2 hours, after the dropping, slaking 1 hour.Then, add 0.6 part of Tetrabutylammonium bromide, carry out reaction in about 1 hour.Reach 1mgKOH/g when following in the resin acid value, add " SWASOL 310 " 295 parts, obtain acrylic modified epoxy resin (I-3).This resin solution nonvolatile component 60%, epoxy equivalent (weight) 749 (solids component).
9 parts in vinylformic acid
51 parts of 2-ethylhexyl acrylate
240 parts of vinylbenzene
18 parts of t-butyl peroxy-2-ethylhexanoate
Production Example 4
93 parts of mineral turpentine under nitrogen gas stream, in 135 ℃ of heating, are dripped the following vinyl monomer and the mixture of polymerization initiator with 3 hours, after the dropping, slaking 1 hour.Then, add 0.6 part of 300 parts of EPICLON HP-820, " HARIDIMER200 90 " part and Tetrabutylammonium bromide, 135 ℃ of heating, reacted about 1 hour, reach 1mgKOH/g when following in the resin acid value, add 294 parts of mineral turpentine, obtain acrylic modified epoxy resin (I-4).This resin solution nonvolatile component 60%, epoxy equivalent (weight) 623 (solids component).
6 parts in vinylformic acid
36 parts of 2-ethylhexyl acrylate
168 parts of vinylbenzene
13 parts of t-butyl peroxy-2-ethylhexanoate
Production Example 5
240 parts of 52 parts of mineral turpentine, " EPICLON HP-820 " under nitrogen gas stream, in 135 ℃ of heating, are dripped the following vinyl monomer and the mixture of polymerization initiator with 2 hours, after the dropping, slaking 1 hour.Then, add 0.6 part of 45 parts of mineral turpentine, " HARIDIMER200 " 60 parts and Tetrabutylammonium bromide, 135 ℃ of heating, reacted about 1 hour, reach 1mgKOH/g when following in the resin acid value, add 294 parts of mineral turpentine, obtain acrylic modified epoxy resin (I-5).This resin solution nonvolatile component 60%, epoxy equivalent (weight) 680 (solids component).
60 parts of 2-ethylhexyl acrylate
240 parts of vinylbenzene
9 parts of t-butyl peroxy-2-ethylhexanoate
Production Example 6
600 parts of 102 parts of mineral turpentine, " EPICLON HP-820 " under nitrogen gas stream, in 135 ℃ of heating, are dripped the following vinyl monomer and the mixture of polymerization initiator with 2 hours, after the dropping, slaking 1 hour.Then, add 1.2 parts of 97 parts of mineral turpentine, " HARIDIMER200 " 180 parts and Tetrabutylammonium bromides, 135 ℃ of heating, reacted about 1 hour, reach 1mgKOH/g when following in the resin acid value, add 588 parts of mineral turpentine, obtain acrylic modified epoxy resin (I-6).This resin solution nonvolatile component 60%, epoxy equivalent (weight) 623 (solids component).
12 parts in vinylformic acid
72 parts of 2-ethylhexyl acrylate
336 parts of vinylbenzene
13 parts of t-butyl peroxy-2-ethylhexanoate
Production Example 7
588 parts of 100 parts of mineral turpentine, " EPICLON HP-820 " under nitrogen gas stream, in 135 ℃ of heating, are dripped the following vinyl monomer and the mixture of polymerization initiator with 2 hours, after the dropping, slaking 1 hour.Then, add 100 parts of mineral turpentine, " HARIDIMER200 " and be 1.2 parts of 168 parts and Tetrabutylammonium bromides,, reacted about 1 hour 135 ℃ of heating.Further add 24 parts of Whitfield's ointments, reacted about 1 hour, reach 1mgKOH/g when following, add 587 parts of mineral turpentine, obtain acrylic modified epoxy resin (I-7) in the resin acid value.This resin solution nonvolatile component 60%, epoxy equivalent (weight) 690 (solids component).
12 parts in vinylformic acid
72 parts of 2-ethylhexyl acrylate
336 parts of vinylbenzene
13 parts of t-butyl peroxy-2-ethylhexanoate
Production Example 8 (comparative example is used)
With " SWASOL 310 " 965 parts, 840 parts of Epikote 828EL drip the following vinyl monomer and the mixture of polymerization initiator with 3 hours under nitrogen gas stream, in 135 ℃ of heating, after the dropping, and slaking 1 hour.Then, add 1.2 parts of Tetrabutylammonium bromides, carry out reaction in about 1 hour, reach 1mgKOH/g when following, add " SWASOL310 " 573 parts, obtain acrylic modified epoxy resin (I-8) in the resin acid value.This resin solution nonvolatile component 60%, epoxy equivalent (weight) 662 (solids component).
62 parts in vinylformic acid
624 parts of 2-ethylhexyl methacrylic esters
874 parts of vinylbenzene
62 parts of t-butyl peroxy-2-ethylhexanoate
Production Example 9 (comparative example is used)
210 parts of 127 parts of mineral turpentine, " EPICLON HP-820 " under nitrogen gas stream, in 135 ℃ of heating, are dripped the following vinyl monomer and the mixture of polymerization initiator with 3 hours, after the dropping, slaking 1 hour.Then, add 0.3 part of Tetrabutylammonium bromide, reacted about 1 hour, reach 1mgKOH/g when following, add 250 parts of mineral turpentine, obtain acrylic modified epoxy resin (I-9) in the resin acid value.This resin solution nonvolatile component 60%, epoxy equivalent (weight) 785 (solids component).
16 parts in vinylformic acid
39 parts of tertiary butyl methacrylic esters
117 parts of 2-ethylhexyl acrylate
218 parts of vinylbenzene
23 parts of t-butyl peroxy-2-ethylhexanoate
The making of coating
Embodiment 1～7 and comparative example 1～6
Mixing as shown in table 1 below is formed, and hybrid pigment and additive etc. carry out dispersion treatment in each resin solution that obtains in above-mentioned Production Example, makes coating host.Then, mix solidifying agent as shown in table 1, making the epoxy group(ing) in the host and the equivalence ratio of the active hydrogen in the solidifying agent is 1.0, mixes and stirs, and makes each coating, supplies with following performance test.In addition, 6 coating uses ESCO (Northwest paint company system, strong solvent dilution type 2 liquid type epoxy coating) as a comparative example.(annotating 1) in the table 1～(annotating 7) is as following.
(annotating 1) EPICLON 5900-60: big Japanese ink chemical industry (strain) system, phenolic varnish modified epoxy liquid (solids component 60%)
(annotating 2) ferric oxide KP-105: new Japanese metallochemistry industry (strain) system, the red rust tinting pigment of ferric oxide main body (effective constituent 97%)
(annotating 3) water-ground limestone A: the former chemical industry of bamboo (strain) system, lime carbonate (pigment extender)
(annotating 4) STALC: Japanese talcum refining (strain), the pigment extender of magnesium oxide, aluminum oxide principal constituent
(annotating 5) DISPARLON6900-10X: nanmu originally changes into (strain), and amide waxe (amidewax) is the anti-agent of hanging down
(annotating 6) BYK-066:BYK-Chemie Japan (strain) system, defoamer
(annotating 7) VERSAMINE K-13:Cogins Japan (strain) system, ketimine compound, Ahew 91.0
(annotating 8) EXA-6496:EPICLON EXA-6496, big Japanese ink chemical industrial company system, Resins, epoxy, epoxy equivalent (weight) 748
Table 1
| Embodiment | Comparative example | ||||||||||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | |||
| Host | Modified epoxy | Production Example 1 | ????36 | ????E ????S ????C ????O | |||||||||||
| Production Example 2 | ????36 | ||||||||||||||
| Production Example 3 | ????36 | ||||||||||||||
| Production Example 4 | ????36 | ||||||||||||||
| Production Example 5 | ????36 | ||||||||||||||
| Production Example 6 | ????36 | ||||||||||||||
| Production Example 7 | ????36 | ||||||||||||||
| Production Example 8 | ????36 | ||||||||||||||
| Production Example 9 | ????36 | ||||||||||||||
| EPICLON 5900-60 (annotating 1) | ????36 | ||||||||||||||
| ????EPICLON?HP-820 | ????21.6 | ||||||||||||||
| (annotating 8) EXA-6946 | ????36 | ||||||||||||||
| (annotating 2) ferric oxide KP-105 | ????4.5 | ????4.5 | ????4.5 | ????4.5 | ????4.5 | ????4.5 | ????4.5 | ????4.5 | ????4.5 | ????4.5 | ????4.5 | ????4.5 | |||
| (annotating 3) water-ground limestone A | ????9 | ????9 | ????9 | ????9 | ????9 | ????9 | ????9 | ????9 | ????9 | ????9 | ????9 | ????9 | |||
| (annotating 4) STALC | ????27 | ????27 | ????27 | ????27 | ????27 | ????27 | ????27 | ????27 | ????27 | ????27 | ????27 | ????27 | |||
| (annotating 5) DISPARLON6900-10X | ????4 | ????4 | ????4 | ????4 | ????4 | ????4 | ????4 | ????4 | ????4 | ????4 | ????4 | ????4 | |||
| (annotating 6) BYK-066 | ????0.5 | ????0.5 | ????0.5 | ????0.5 | ????0.5 | ????0.5 | ????0.5 | ????0.5 | ????0.5 | ????0.5 | ????0.5 | ????0.5 | |||
| Oil through-stone cerebrol | ????9 | ????9 | ????9 | ????9 | ????9 | ????9 | ????9 | ????9 | ????9 | ????9 | ????9 | ????9 | |||
| Solidifying agent | (annotating 7) VERSAMINE K-13 | ????2.4 | ????2.1 | ????2.6 | ????3.2 | ????2.9 | ????3.2 | ????2.9 | ????3 | ????2.5 | ????2.8 | ????9.3 | ????2.6 | ||
| Oil through-stone cerebrol | ????7.6 | ????7.9 | ????7.4 | ????6.9 | ????7.1 | ????6.9 | ????7.2 | ????7 | ????7.5 | ????7.2 | ????0.7 | ????7.4 | |||
Performance test
Each coating to above-mentioned making carries out following performance test.The results are shown in table 2.
(* 1) Weak solvent solubility
In the resin that is used in 5 ℃ of each coating under the environment, with HAWS (ShellChemicals Japanese firm system, oil is a hydrocarbon solvent), Visual Confirmation solubility.If produce muddy HAWS addition constantly with respect to weight resin more than 300%, be designated as " zero ", at 100～300% o'clock, be designated as " △ ", 100% when following, is designated as " * ".
(* 2) go up the curing obstruction property of coating film
Scraper with gap 6mil on sheet glass is coated with each coating, is statically placed under 5 ℃ of environment.After 6 hours, the scraper with identical gap on it is filmed repeats to be coated with SD FORCE1000 (Northwest paint company system, phthalic acid cold coating).With it after leaving standstill 24 hours under 5 ℃ of environment, according to the solidified nature of following benchmark evaluation film coated surface.
Zero: not unusual, solidified nature is good
△: remaining adhesivity
*: adhesivity is remarkable
(* 3) shock resistance
Benchmark according to the 8.3.2 (Du Pont's formula) of JIS K5400, the condition (quality of weight: 500g in the record of the goods specification (JIS K5551) of epoxypaint, the height of weight: 30cm) carry out shatter test, estimate because the shock-produced deformation of test board breaking of causing filming.Confirm not peel off, be designated as when tack is no problem " zero ", be designated as " △ " when tack is bad, be coated with film rupture, be designated as " * " when peeling off.
(* 4) touch dry
On tin plate, as lower floor, with each coating of bristle application, making glue spread is 120g/cm
2, after dry 4 hours, thereon, as the upper strata, with bristle application SD FORCE1000 (Northwest paint company system, phthalic acid cold coating), making glue spread is 100g/cm in room temperature (under 20～24 ℃ of environment)
2In room temperature place, with the touch dry of following benchmark evaluation film coated surface thereafter.
Zero: non-viscous paint on the finger does not have tackiness yet
△: non-viscous paint on the finger, but residual tackiness
*: stick coating on the finger
Table 2
| Embodiment | Comparative example | ||||||||||||
| 1 | ?2 | ?3 | ?4 | ?5 | ?6 | ?7 | ?1 | ?2 | ?3 | ?4 | ?5 | ?6 | |
| The Weak solvent solubility | ○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?× |
| The curing of last coating film obstruction property | ○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?△ | ?× | ?○ | ?○ |
| Shock resistance | ○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?△ | ?○ | ?○ | ?○ |
| Touch dry | ○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?○ | ?△ | ?△ | ?○ | ?× | ?△ | ?○ |
The making of coated plate
Embodiment 8～31 and comparative example 7～18
On the zinc-plated corrosion resistant plate face of phosphatizing, as following coating, shown in table 3～table 5, with each coating that bristle application the foregoing description 1～7 and comparative example 1～6 obtain, making glue spread is 120g/cm
2, under 20 ℃ of environment, carried out 8 hours and health in 24 hours,, reach upward coating thereon with the middle coating intermediate in bristle application table 3～table 5, making glue spread is 100g/cm
2, at this moment, Visual Confirmation oozing out on middle coating film and last coating film (zero: fully and do not find to ooze out △: find that some ooze out, *: find significantly to ooze out).
The middle coating intermediate that uses reaches goes up coating a～q such as following.
A:CELA MILD GLOSS, Northwest coating society system, coating on organic solvent (Weak solvent) the dilution type acrylic resin
B:ECO RETAN, Northwest coating society system, organic solvent (Weak solvent) dilution type urethane resin is fastened coating
C:CELA M RETAN, Northwest coating society system, organic solvent (Weak solvent) dilution type urethane resin is fastened coating
D:Ecosilicone, Northwest coating society system, organic solvent (Weak solvent) dilution type silicone resin is fastened coating
E:MUKI FUSSO, Northwest coating society system, the silicone cross-linked fluoro-resin of organic solvent (Weak solvent) dilution type is fastened coating
F:CELA ACRYL, Northwest coating society system, organic solvent (Weak solvent) dilution type acrylate resin is fastened coating
G:RABATECT, Northwest coating society system, organic solvent diluting type chlorinated rubber is fastened coating
The h:RABATECT middle coating intermediate, Northwest coating society system, organic solvent diluting type chlorinated rubber is a middle coating intermediate
I:Epomarine, Northwest coating society system, organic solvent diluting type epoxy resin coating
J:RETAN 6000, Northwest coating society system, coating on the organic solvent diluting type polyurethane resin system
K:CELA TECT U, Northwest coating society system, coating on the organic solvent diluting type polyurethane resin system
L:SILICO TECI AC, Northwest coating society system, organic solvent diluting type silicone resin is fastened coating
M:KANPE-FRON HD, Northwest coating society system, organic solvent diluting type fluoro-resin is fastened coating
N:CELA TECT F, Northwest coating society system, organic solvent diluting type fluoro-resin is fastened coating
O:AQUA GLOSS, Northwest coating society system, coating on the water dilution type acrylic resin
P:AQUA RETAN, Northwest coating society system, water dilution type urethane resin is fastened coating
Q:AQUA Silicone, Northwest coating society system, water dilution type silicone resin is fastened coating
R:UNITECT 20 MILD, Northwest coating society system, organic solvent (Weak solvent) dilution type epoxy acrylic resin is a coating
S:UNITECT 30 MILD, organic solvent (Weak solvent) dilution type propylene oxide silicon acid resinous is a coating
T:UNITECT 20, Northwest coating society system, and organic solvent diluting type epoxy acrylic resin is a coating
U:UNITECT 30, and organic solvent diluting type propylene oxide silicon acid resinous is a coating
Table 3
| Embodiment | |||||||||||||
| ????8 | ????9 | ????10 | ????11 | ????12 | ????13 | ????14 | ????15 | ????16 | ????17 | ????18 | ????19 | ||
| Lower floor's coating type | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 3 | |
| The upper strata coating type | ????a | ????b | ????c | ????d | ????e | ????f | ????g | ????h | ????i | ????j | ????k | ????l | |
| Last coating suitability | After 8 hours | ???○ | ???○ | ???○ | ????○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ |
| After 24 hours | ???○ | ???○ | ???○ | ????○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | |
Table 4
| Embodiment | |||||||||||||||||
| ??20 | ??21 | ??22 | ??23 | ??24 | ??25 | ??26 | ??27 | ??28 | ??29 | ??30 | ??31 | ??32 | ??33 | ??34 | ??35 | ||
| Lower floor's coating type | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| The upper strata coating type | ????m | ????n | ???o | ????p | ???q | ???r | ???s | ???t | ???u | ???a | ???a | ??a | ???a | ????f | ????f | ???f | |
| Last coating suitability | After 8 hours | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ??○ | ???○ | ???○ | ???○ | ???○ |
| After 24 hours | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ???○ | ??○ | ???○ | ???○ | ???○ | ???○ | |
Table 5
| Comparative example | |||||||||||||
| ????7 | ????8 | ????9 | ????10 | ????11 | ????12 | ????13 | ????14 | ????15 | ????16 | ????17 | ????18 | ||
| Lower floor's coating type | Comparative example 2 | Comparative example 2 | Comparative example 4 | Comparative example 4 | Comparative example 4 | Comparative example 5 | Comparative example 5 | Comparative example 5 | Comparative example 5 | Comparative example 5 | Comparative example 5 | Comparative example 5 | |
| The upper strata coating type | ????a | ????b | ????a | ????f | ????j | ????f | ????g | ????i | ????j | ????k | ????m | ????n | |
| Last coating suitability | After 8 hours | ????× | ????× | ????× | ????× | ????× | ????× | ????× | ????× | ????× | ????× | ???× | ????× |
| After 24 hours | ????× | ????× | ????○ | ????○ | ????○ | ????× | ????× | ????× | ????× | ????× | ???× | ????× | |
Claims (7)
1. coating composition, it is characterized in that, to contain the modified epoxy (d-1) of acrylic resin (c-1) the reaction formation that is selected from Resins, epoxy (a) and the diprotic acid (b) that has 2 above epoxy group(ing) in 1 molecule and contains carboxyl, make this Resins, epoxy (a) and diprotic acid (b) addition polymerization, and at least a modified epoxy (I) in the modified epoxy (d-2) that forms with (c-2) graft polymerization of polymerizability unsaturated monomer or copolymerization, this modified epoxy solidifying agent (II), and the necessary composition of organic solvent (III) conduct, this organic solvent contains more than the hydrocarbon system solvent 80 weight % that are selected from aliphatic hydrocarbon series solvent and high boiling point aromatic hydrocarbons series solvent.
2. the described coating composition of claim 1, wherein, the average epoxy equivalent (weight) of Resins, epoxy (a) is in about 150～about 1000 scopes.
3. the described coating composition of claim 1, wherein, Resins, epoxy (a) is the Resins, epoxy that does not contain free dihydroxyphenyl propane and nonylphenol.
4. the described coating composition of claim 1, wherein, polymerizability unsaturated monomer (c-2) comprises the vinyl monomer that contains carboxyl.
5. the described coating composition of claim 1, wherein, (a) equivalence ratio of the carboxyl in the epoxy group(ing) in the composition and (b) composition is in 1: 0.05～1: 0.5 scope.
6. the described coating composition of claim 1, wherein, modified epoxy (I) has the phenol hydroxyl.
7. use the coating process of aforementioned coating composition, it is coating (B) in coating (A) back application under the application on the coated surface, wherein, as this time coating (A), to contain the modified epoxy (d-1) of acrylic resin (c-1) the reaction formation that is selected from Resins, epoxy (a) and the diprotic acid (b) that has 2 above epoxy group(ing) in 1 molecule and contains carboxyl, make this Resins, epoxy (a) and diprotic acid (b) addition polymerization, and at least a modified epoxy (I) in the modified epoxy (d-2) that forms with (c-2) graft polymerization of polymerizability unsaturated monomer or copolymerization, this modified epoxy solidifying agent (II), and the necessary composition of organic solvent (III) conduct, this organic solvent contains more than the hydrocarbon system solvent 80 weight % that are selected from aliphatic hydrocarbon series solvent and high boiling point aromatic hydrocarbons series solvent.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP221291/2002 | 2002-07-30 | ||
| JP2002221291A JP2003246963A (en) | 2001-12-17 | 2002-07-30 | Coating composition |
| JP2002221292 | 2002-07-30 | ||
| JP221292/2002 | 2002-07-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1472271A true CN1472271A (en) | 2004-02-04 |
| CN1215137C CN1215137C (en) | 2005-08-17 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031384234A Expired - Fee Related CN1215137C (en) | 2002-07-30 | 2003-05-27 | Paint composition and coating method |
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| Country | Link |
|---|---|
| KR (1) | KR20040030215A (en) |
| CN (1) | CN1215137C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070991A (en) * | 2009-11-19 | 2011-05-25 | 古河电气工业株式会社 | Lamelliform adhesive and adhesive tape for wafer processing |
| CN101560358B (en) * | 2008-03-19 | 2012-05-30 | 关西涂料株式会社 | Anticorrosive coating composition |
| CN111621211A (en) * | 2019-02-28 | 2020-09-04 | 中国涂料株式会社 | Anticorrosive coating composition |
| CN112029381A (en) * | 2020-09-09 | 2020-12-04 | 溧阳市永新绝缘粉末有限公司 | Insulating powder with good flexibility and mechanical impact resistance, preparation method and application method |
-
2003
- 2003-05-27 CN CNB031384234A patent/CN1215137C/en not_active Expired - Fee Related
- 2003-05-30 KR KR1020030034649A patent/KR20040030215A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560358B (en) * | 2008-03-19 | 2012-05-30 | 关西涂料株式会社 | Anticorrosive coating composition |
| CN102070991A (en) * | 2009-11-19 | 2011-05-25 | 古河电气工业株式会社 | Lamelliform adhesive and adhesive tape for wafer processing |
| CN111621211A (en) * | 2019-02-28 | 2020-09-04 | 中国涂料株式会社 | Anticorrosive coating composition |
| CN112029381A (en) * | 2020-09-09 | 2020-12-04 | 溧阳市永新绝缘粉末有限公司 | Insulating powder with good flexibility and mechanical impact resistance, preparation method and application method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20040030215A (en) | 2004-04-09 |
| CN1215137C (en) | 2005-08-17 |
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