CN1788059A - Lowly odorous solvent-based coating composition - Google Patents
Lowly odorous solvent-based coating composition Download PDFInfo
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- CN1788059A CN1788059A CNA038266903A CN03826690A CN1788059A CN 1788059 A CN1788059 A CN 1788059A CN A038266903 A CNA038266903 A CN A038266903A CN 03826690 A CN03826690 A CN 03826690A CN 1788059 A CN1788059 A CN 1788059A
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- coating composition
- low smell
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- based coating
- solvent based
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- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
A lowly odorous solvent-based coating composition characterized by comprising (a) at least one resin for coating materials which is selected from the group consisting of epoxy resins, urethane resins, and acrylic resins, (b) a lowly odorous organic solvent, (c) at least one compound selected from the group consisting of c8 and higher esters and/or lactones, and as an optional ingredient (d) a hardener for the resin (a), and by containing substantially no xylene and toluene as an organic solvent, and a container, building, or structure having a lowly odorous coating film formed from the coating composition. Due to the ingredient (c), which has the property of neutralizing odors, the coating composition has the effect of being significantly reduced in odor.
Description
Technical field
The present invention relates to low smell solvent based coating composition, the inside surface coating that is specifically related to be suitable for the freight container accommodate, transport goods etc., building construction thing etc. is with coating etc., and can significantly be suppressed at the low smell solvent based coating composition of the coating smell that occurs behind the dried coating film.
Background technology
At present, the coating that is suitable in the inside surface coating of freight container etc. peculiar smell will occur after application just, and when using the encased conveying goods, there is the possible impaired problem of commodity value of goods in this peculiar smell attached on the goods.
Therefore, by not using the dimethylbenzene of the major cause that is considered to produce the coating smell fully, wish to develop the low smell solvent based coating composition that can significantly suppress the coating smell.
In addition, up to now, existing various applications about low smell solvent based coating composition.
For example, the water-based odour remover coating that solid acid by water, acid adhesive and deodorizing composition forms is disclosed in the Japanese patent laid-open 2-180972 communique at least, as acid adhesive, can exemplify as cationic polymer, polyvinyl acetate resin, vinyl acetate between to for plastic copolymer resins (acrylic acid or the like, ethene, (the white acid of white vinyl acetate, versatic acide, a kind of alkanecarboxylic acid that side chain is arranged) etc. interpolymer).Use is by filming that these water-based odour remover coatings form, and can realize removing the malodorous purpose of alkaline gas etc. by chemisorption.
But the coating of putting down in writing in this communique is in the leeway that still has improvement aspect reduction and the inhibition solvent odor.
The Japanese Patent spy opens and discloses containing vegetable and animals oils or containing the printing-ink of light trigger of the catechin compounds, Weibull or the tannin compound that are added with as reodorant in the 2002-212484 communique, as the printing-ink that contains vegetable and animals oils, can exemplify the printing ink that contains pigment, lacquer, vegetable and animals oils, as the printing-ink that contains light trigger, can exemplify the printing ink that contains pigment, the aqueous compound of optical polymerism, light trigger.
But the coating of putting down in writing in this communique is in the leeway that still has improvement aspect the deodorizing effect of catechin compounds etc.
Also have, open in the clear 54-99140 communique the Japanese Patent spy, disclose and be dissolved with aluminium capsule (aluminium sach) the repairing quick-drying printing ink that in the solvent of low～mid-boiling point, has deliquescent resin, as resin, can exemplify as rosin as natural or synthetic resins, ketone resin, petroleum resin, Synolac, as solvent, from drip-dry viewpoint, can exemplify lacquer diluent, dimethylbenzene, the fragrant family of toluene etc., the ester system of N-BUTYL ACETATE etc., the ketone system of MEK etc., other volatile oil systems etc., but about smell without any the record and the prompting.
The purpose of invention
The objective of the invention is the problem that exists in the above-mentioned present technology in order to solve, the inside surface coating that the freight container, building construction thing etc. that are suitable as the transportation goods are provided uses with coating etc., and can significantly be suppressed at the low smell solvent based coating composition of the coating smell that occurs behind the dried coating film, and the various moldinies that provide this to film and have the freight container, building construction thing etc. of this low smell of filming.
The announcement of invention
The low smell solvent based coating composition that the present invention relates to.It is characterized in that, contain
(A) be selected from coating resin at least a in Resins, epoxy, urethane resin and the acrylic resin;
(B) low smell organic solvent;
(C) be selected from carbonatoms more than or equal at least a compound in 8 ester and/or the lactone;
And contain as required
(D) stiffening agent of coating resin (A) usefulness does not contain dimethylbenzene and toluene in fact as organic solvent.
Among the present invention, above-mentioned low smell organic solvent (B) is preferably the low smell organic solvent that is selected from N-BUTYL ACETATE, vinyl acetic monomer, cellosolve acetate, ethyl cellosolve, ethylene glycol butyl ether.
Above-claimed cpd among the present invention (group) better is to be selected from arbitrarily as the caproic acid-2-propylene ester (CH of carbonatoms more than or equal to 8 ester (C)
3(CH
2)
4COOCH
2CH=CH
2),
Enanthic acid-2-propylene ester (C
6H
13COOCH
2CH=CH
2), sad-2-propylene ester (C
7H
15COOCH
2CH=CH
2), acetic acid-4-(1, the 1-dimethyl ethyl) cyclohexyl
And as a kind of 5-heptyl dihydro-2 (3H)-furanone of lactone
In more than or equal to a kind compound.
Among the present invention, being preferably what contain 5～30 weight % in coating composition is the low smell organic solvent (B) of representative with the N-BUTYL ACETATE, in addition, is preferably the above-claimed cpd (C) that contains 0.01～1.0 weight % in coating composition.
Among the present invention, the stiffening agent of above-mentioned used for epoxy resin is the stiffening agent that is formed by polymeric amide or its modifier.
In addition, the host used of urethane resin is to be selected from resin at least a in polyester polyol, acrylic polyol and the polythiol;
The stiffening agent that urethane resin is used is preferably, and is selected from least a compound in hexamethylene diisocyanate (HDI), '-diphenylmethane diisocyanate (MDI), the tolylene diisocyanate (TDI).
The paint for container composition that the present invention relates to is to be formed by above-mentioned arbitrary middle low smell solvent based coating composition of putting down in writing.
The inner coating composition of the freight container that the present invention relates to is to be formed by above-mentioned arbitrary middle low smell solvent based coating composition of putting down in writing.
The freight container that the present invention relates to bottom coating composition is to be formed by above-mentioned arbitrary middle low smell solvent based coating composition of putting down in writing.
The freight container that the present invention relates to sealing ply coating composition is to be formed by above-mentioned arbitrary middle low smell solvent based coating composition of putting down in writing.
Buildings that the present invention relates to or structure coating composition are to be formed by above-mentioned arbitrary middle low smell solvent based coating composition of putting down in writing.
The low smell that the present invention relates to is filmed, and is to be coated with and to be formed by above-mentioned arbitrary middle coating composition of putting down in writing.
The freight container, buildings or the structure that are attached with low smell Tu film that the present invention relates to be characterised in that, forms above-mentioned low smell at the medial surface of freight container, buildings or structure and film.
By the present invention, provide the inside surface coating that is suitable as the freight container that holds, transport goods etc., building construction thing etc. to use with coating etc., and can significantly be suppressed at the low smell solvent based coating composition of the coating smell that occurs behind the dried coating film, and the various moldinies that provide this to film and have the freight container, building construction thing etc. of this low smell of filming.
The best mode that carries out an invention
Below, with the various moldinies that specify the low smell solvent based coating composition (being also referred to as coating, coating composition) that the present invention relates to, this is filmed and have the freight container, building construction thing etc. of this low smell of filming.
(low smell solvent based coating composition)
The low smell solvent based coating composition that the present invention relates to contains,
(A) be selected from coating resin at least a in Resins, epoxy, urethane resin and the acrylic resin;
(B) low smell organic solvent;
(C) be selected from carbonatoms more than or equal at least a compound in 8 ester and/or the lactone;
And contain as required
(D) stiffening agent of coating resin (A) usefulness does not contain dimethylbenzene and toluene in fact as organic solvent.
(coating resin (A))
As coating resin (A), can exemplify the cold setting that can be used for the low smell solvent based coating composition of gained and Resins, epoxy, urethane resin, acrylic resin (being also referred to as (methyl) acrylic resin), vibrin, Synolac, the fluorine resin of baking hardening, wherein, be preferably Resins, epoxy, urethane resin and acrylic resin from angle to the tack of base material, resistance to chemical reagents, coating decoration, non-corrosibility.
In addition, among the present invention, when speaking of in coating mixed hardening agent, mainly be not by the meaning of the 3 D cross-linked uncrosslinked thing of stiffening agent (unhardened thing) as " resin " this term.
Among the present invention, these resins (A) more than a kind or 2 kinds can be used in combination.
Below, the stiffening agent that will use suitable especially Resins, epoxy, urethane resin, (methyl) acrylic resin and these resins elaborates.
＜Resins, epoxy (a) 〉
The Resins, epoxy of using among the present invention (a) is the resin that has the epoxy group(ing) more than 2 in 1 molecule at least, and epoxy equivalent (weight) is 150～600, is preferably 180～500.As such Resins, epoxy, can exemplify as bisphenol-type epoxy resin, glycidyl ester is that Resins, epoxy, glycidyl amine are Resins, epoxy, linear phenolic resin varnish type epoxy resin, cresols type Resins, epoxy, dimeracid denaturation loop epoxy resins, aliphatic epoxy resin etc.Wherein better use bisphenol-type epoxy resin, particularly dihydroxyphenyl propane (BPA) type Resins, epoxy.Use bisphenol-type epoxy resin, can form excellent in adhesiveness De Tu film.
As bisphenol A type epoxy resin, can exemplify as bisphenol A-type diglycidylethers such as bisphenol A diglycidyl ether, polymer with bis phenol A propylene oxide diglycidylether, bisphenol-A epoxy ethane diglycidylether, hydrogenation bisphenol A diglycidyl ether, hydrogenation bisphenol-A epoxy propane diglycidylether etc.
Preferably in the embodiment, for example the epoxy equivalent (weight) as Resins, epoxy is 160～500 o'clock, is preferably the bisphenol A type epoxy resin of liquid～solid state in the present invention.
As wanting these Resins, epoxy preferably of more detailed example, can exemplify Resins, epoxy with bisphenol A-type, Bisphenol F type and be representative, the Resins, epoxy of dimer acid modified, polysulfide modification etc. also can use Resins, epoxy with aromatic ring structure resin by the hydrogenation gained.Be preferably the fragrant family Resins, epoxy of dihydroxyphenyl propane or Bisphenol F type etc.
Representative as Resins, epoxy, the liquid resin of normal temperature can exemplify " エ ピ コ one ト 828 (trade(brand)name) " (シ エ Le Co., Ltd. system, epoxy equivalent (weight) 180～190, viscosity 12000～15000cps/25 ℃), " " (East changes into Co., Ltd.'s system to エ Port ト one ト YDF-170 (trade(brand)name), epoxy equivalent (weight) 160～180, viscosity 2000～5000cps/25 ℃), " Off レ Star プ 60 (trade(brand)names) " (East レ チ オ コ one Le Co., Ltd. system, epoxy equivalent (weight) about 280, the about 17000cps/25 of viscosity ℃) etc., the resin of normal temperature semi-solid can exemplify, " " (East changes into Co., Ltd.'s system to エ Port ト one ト YD-134 (trade(brand)name), epoxy equivalent (weight) 230～270) etc., the resin of normal temperature solid state can exemplify, " エ ピ コ one ト 1001 (trade(brand)name) " (シ エ Le Co., Ltd. system, epoxy equivalent (weight) 450～500) etc.
The stiffening agent of＜Resins, epoxy (a) usefulness 〉
Stiffening agent as used for epoxy resin, as long as can react with above-mentioned Resins, epoxy, just there is no particular limitation to make it sclerosis, can use the material of amine, carboxylic-acid, acid anhydrides system, silanol system etc. arbitrarily, when normal temperature environment is constructed, particularly preferably use amine type hardeners.
As such amine type hardeners, be preferably the stiffening agent of the liquid～solid state of amine value 50～1000.These amine of example are stiffening agent more specifically, can exemplify as polyalkylenepolyamines (polyalkylenepolyamine), aromatic amine, polymeric amide, daiamid (polyamideamine) etc., can also use the modifier of acid amides modification body that epoxy adduct, Mannich (Mannich) modification body, carboxylic acid by addition epoxy compounds gained on above-mentioned amine form etc.
Can also use the stiffening agent that makes the ketoimine type of these amine compound modification gained by ketone.In these stiffening agents, as polymeric amide, specifically can exemplify " ラ Star カ マ イ De TD-966 (trade(brand)name) " (big Japanese イ Application キ chemical industry Co., Ltd. system, amine value 150～190) etc., as other amine compound, can be for example as " ア Application カ ミ Application MCA (trade(brand)name) " (ア Application カ one ケ ミ カ Le commercial firm system of the modification ester ring type polyamine of ketoimine type, amine value 250～350) etc., " PA-23 (trade(brand)name) " (big bamboo KCC system as epoxy adduct class amine, amine value 80～150) etc., " カ one De ラ イ ト 541L (trade(brand)name) " (ア Application カ one ケ ミ カ Le commercial firm system as modification Ben Aokaming (phenalkamine), amine value 260～350) etc., " ア デ カ Ha one De Na, one EH101 (trade(brand)name) " multiple compounds such as (rising sun electrification Co., Ltd. system, amine values 400～500) as modified aromatic adoption amine.These amine are in the stiffening agent, particularly preferably the epoxy adduct of polymeric amide, daiamid, modification Ben Aokaming.
＜urethane resin (b) 〉
As urethane resin, there is no particular limitation, the urethane esterised oil), in moisture-curable type, block type etc. any one can be the oily properties-correcting agent (example:, also can be any one in the catalyzer sclerotic type, polyvalent alcohol sclerotic type etc. of 2 liquid types of 1 liquid type.In addition, as stiffening agent or when sclerosis causes, oily properties-correcting agent uses oxygen, and the moisture-curable type uses moisture, and block type needs heating, and the catalyzer sclerotic type uses amine, and the polyvalent alcohol sclerotic type uses polyvalent alcohol etc.
Below, is the situation of stiffening agent to considering special good embodiment from the aspect of coating decoration, resistance to chemical reagents, tack, describe in detail to use as urethane resin with polymeric polyisocyanate with the polyvalent alcohol of host and/or polythiol, as the urethane resin of stiffening agent.
＜polyvalent alcohol 〉
As the polyvalent alcohol of the urethane resin of using among the present invention with host, specifically can exemplify, ethylene glycol, glycol ether, triglycol, polyoxyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butyleneglycol, two fourth glycol, three butyleneglycols, polytetramethylene glycol, 1,5-pentanediol, neopentyl glycol, 1, dibasic alcohol such as 6-hexylene glycol, decamethylene-glycol, alkanediol, cyclohexanedimethanol; Glycerine, TriMethylolPropane(TMP) (TMP), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxyl-3-methylol pentane, 1,1,1-three (two methylol) propane, 2, the trivalent alcohol of 2-two (methylol) butanols-3 grade; The tetravalent alcohol of tetramethylolmethane, Glycerol dimer etc.; Pentavalent alcohols (pentitol) such as arabitol, ribitol, Xylitol; Take off hexavalent alcohol (hexan-hexol) such as two water sorbyl alcohols (sorbide), N.F,USP MANNITOL, melampyrum, allose alcohol; The polyglycol compound of carbonatomss to 10 such as multi-hydroxy such as Polyglycerine, polytetramethylene glycol compound, polyester polyol, epoxy polyol (alkanolamine denaturation loop oxide compound), polyether glycol and the acrylic polyol etc. of deriving and forming by anhydrous phthalic acid, sebacic acid, lipid acid, Resins, epoxy etc.
Wherein, be preferably ethylene glycol, propylene glycol, 1,6-hexylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, polyester polyol, acrylic polyol, particularly preferably polyester polyol, acrylic polyol.
＜polythiol 〉
The polythiol of using among the present invention (many sulfhydryl compounds) is the compound with 2 above sulfydryls (SH yl).As polythiol, specifically can exemplify as 1, the 3-dimercaptopropane, 1, the 4-succinimide mercaptans, 1, the 6-ethanthiol, 2, the 3-dimercaprol dimercaptopropanol, Toluene-3,4-dithiol, the 4-dithiol, α, α '-dimercapto-p-xylol (α, α '-dimercapto-p-xylol), dimercaptoethane, glycol ether two mercaptan, triglycol two mercaptan, the dithio pyrocatechol, 3-chlorothio pyrocatechol, dithio-resorcin, dimercapto toluene, xylylene two mercaptan, 1,3,5-tri-thiol benzene, the dimercapto naphthalene, two dodecane two mercaptan, dithiol phenol (dithiolphenol), 4, and 4 '-dithio phenol (4,4-dithiophenol), 2,2 '-dimethyl-4,4 '-sulfo-biphenol, di-mercaptobenzothiazolby, dithio erythritol etc.
As the concrete example of the polythiol outside above-mentioned, can exemplify by aliphatic poly mercaptan and the sulfydryl low fatty acid ester that forms of esterification wholly or in part.As above-mentioned aliphatic poly mercaptan, can exemplify ethylene glycol, glycol ether, triglycol, polyoxyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butyleneglycol, two fourth glycol, three butyleneglycols, polytetramethylene glycol, 1,5-pentanediol, neopentyl glycol, 1, dibasic alcohol such as 6-hexylene glycol, decamethylene-glycol, alkanediol, cyclohexanedimethanol; Glycerine, TriMethylolPropane(TMP) (TMP), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxyl-3-methylol pentane, 1,1,1-three (two methylol) propane, 2, the trivalent alcohol of 2-two (methylol) butanols-3 grade; The tetravalent alcohol of tetramethylolmethane, Glycerol dimer etc.; Pentavalent alcohols (pentitol) such as arabitol, ribitol, Xylitol; Take off hexavalent alcohol (hexan-hexol) such as two water sorbyl alcohols, N.F,USP MANNITOL, melampyrum, allose alcohol.Wherein, be preferably glycerine, TriMethylolPropane(TMP), tetramethylolmethane.
In addition, also can use the Racemic glycidol ethers of dihydroxyphenyl propane glycidyl ether, hydrogenation dihydroxyphenyl propane glycidyl ether, Bisphenol F glycidyl ether, phenolic varnish type epoxide etc.
In addition, as above-mentioned sulfydryl lower fatty acid, specifically can exemplify as Thiovanic acid, thiohydracrylic acid, sulfydryl Whitfield's ointment, mercaptoethanol acid, N-(2-hydroxyethyl) thioglycolic acid, mercaptosuccinic acid, sulfydryl oxysuccinic acid etc.Wherein, be preferably Thiovanic acid (HSCH
2COOH), thiohydracrylic acid.
The special good polythiol that uses is among the present invention, form by tetramethylolmethane and Thiovanic acid or thiohydracrylic acid or by TriMethylolPropane(TMP) and Thiovanic acid or thiohydracrylic acid ester that form, that have 2～4 sulfydryls.
In addition, the mercaptan compound with 1 sulfydryl can be used as thinner or softening agent uses.Among the present invention, use the necessity and the smell of solvent little, be preferably the use polythiol owing to can reduce.
＜polymeric polyisocyanate is a stiffening agent 〉
Be the polymeric polyisocyanate that stiffening agent uses as polymeric polyisocyanate among the present invention, specifically can exemplify 1, hexamethylene-diisocyanate (HDI), xylene diisocyanate (XDI), 1,3-two (isocyanic ester ylmethyl) cyclohexane (hydrogenation XDI, H6XDI), tolylene diisocyanate (TDI), '-diphenylmethane diisocyanate (MDI), 4,4-two (isocyanate group cyclohexyl) methane (hydrogenation MDI), naphthalene diisocyanate (NDI), isophorone-vulcabond (IPDI), between xylene diisocyanate (MXDI), lysinediisocyanate (2, the diisocyanate based methyl caproate (2 of 6-, 6-diisocyanatemethylcaproate)) (LDI), methylcyclohexane-2,4 (or 2,6)-vulcabond (hydrogenation TDI or HTDI), trimethyl hexamethylene diisocyanate (TMDI), dimer acid diisocyanate (DDI), tolidine vulcabond (TODI), the p-phenylene diisocyanate, trans cyclohexane-1, the 4-vulcabond.Tetramethyl-xylene diisocyanate diisocyanates such as (TMXDI); Triphenylmethane triisocyanate, three (isocyanate group phenyl) thiophosphatephosphorothioate (tri (isocyanatephenyl) thiophosphate), Methionin ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-vulcabond-4-isocyanic ester methyloctane, 1,3, triisocyanate classes such as 6-hexylidene triisocyanate, norbornane triisocyanate etc.
By above-mentioned isocyanic ester derive gained urea acrylate structure body or add zoarium and all can be used as stiffening agent and use.
In addition, as the concrete example of the polymeric polyisocyanate except that above-mentioned, can exemplify following carbodiimide type polymeric polyisocyanate.
This carbodiimide type polymeric polyisocyanate has more than one-N=C=N-base, specifically can exemplify as carbodiimide type '-diphenylmethane diisocyanate, carbodiimide type tolylene diisocyanate, carbodiimide type dimethyl diphenyl group diisocyanate (dimethylbiphenylenediisocyanate), carbodiimide type xylylene diisocyanate, carbodiimide type naphthalene diisocyanate, carbodiimide type hexamethylene diisocyanate, carbodiimide type isophorone diisocyanate, carbodiimide type hydrogenation xylylene diisocyanate, carbodiimide type hydrogenation '-diphenylmethane diisocyanate etc.
By better be applicable to isocyanic ester of the present invention derive gained the urate body or add in the polymeric polyisocyanate of adult etc., carbodiimide type '-diphenylmethane diisocyanate, carbodiimide type tolylene diisocyanate, carbodiimide type dimethyl diphenyl group diisocyanate, carbodiimide type hexamethylene diisocyanate are arranged.The spy uses carbodiimide type '-diphenylmethane diisocyanate well.
In addition, have the carbodiimide type polymeric polyisocyanate of 1-N=C=N-base, can be represented by the formula.
(OCN-R
1)-N＝C＝N-(R
2-NCO)
[(OCN-R in the formula
1), (R
2-NCO) be polymeric polyisocyanate.]
Concrete example as the polymeric polyisocyanate except that above-mentioned polymeric polyisocyanate, can exemplify, aliphatic polyol (i) more than (1) 3 yuan and tolylene diisocyanate (TDI), xylene diisocyanate (XDI), between xylene diisocyanate (MXDI), 1, hexamethylene-diisocyanate (HDI or HMDI), isophorone-vulcabond (IPDI) or two (isocyanic ester methyl) hexanaphthene adducts (ii), and (2) are by hexamethylene diisocyanate (HDI or HMDI), isophorone-vulcabond (IPDI) or two (isocyanic ester methyl) hexanaphthene forms, has following formula (I)
Shown in the ring isocyanurate structure body (urate structure).
As the aliphatic polyol more than 3 yuan (i) that uses with the constituent of above-mentioned affixture, specifically can exemplify glycerine, TriMethylolPropane(TMP) (TMP), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxyl-3-methylol pentane, 1,1,1-three (two methylol) propane, 2, the trivalent alcohol of 2-two (methylol) butanols-3 grade; The tetravalent alcohol of tetramethylolmethane, Glycerol dimer etc.; Pentavalent alcohols (pentitol) such as arabitol, ribitol, Xylitol; Take off hexavalent alcohol (hexan-hexol) such as two water sorbyl alcohols, N.F,USP MANNITOL, melampyrum, allose alcohol.Wherein, particularly preferably TriMethylolPropane(TMP), tetramethylolmethane.
In addition, the tolylene diisocyanate (TDI), xylene diisocyanate (XDI), the xylene diisocyanate (MXDI), 1 that use as the constituent of above-mentioned affixture, hexamethylene-diisocyanate (HDI or HMDI), isophorone-vulcabond (IPDI), two (isocyanic ester methyl) hexanaphthene (hydrogenation XDI, H6XDI) (ii) in, be preferably, 1,3-two (isocyanic ester methyl) hexanaphthene, tolylene diisocyanate (TDI), xylene diisocyanate (XDI).
The affixture of above-mentioned (1) of using among the present invention, can by will as the above-mentioned aliphatic polyol more than 3 yuan (i) and two (isocyanic ester methyl) hexanaphthene (ii) addition polymerization obtain.
Affixture as better using among the present invention can exemplify the compound that can be represented by the formula.
(1) affixture of TMP and hydrogenation XDI
[R:1 in the formula, 3-cyclohexylidene]
(2) affixture of tetramethylolmethane and hydrogenation XDI
C-[CH
2O-CO-NH-CH
2-R-CH
2-NCO]
4
[R:1 in the formula, 3-cyclohexylidene]
In the molecule of the isocyanic ester structure (urate structure) that uses as polymeric polyisocyanate among the present invention, has the ring shown in the following formula (I) more than 1 or 2.
The isocyanurate structure body that uses among the present invention can obtain by carry out trimerization reaction, five poly-reactions, seven poly-reactions etc. as above-mentioned two (isocyanic ester methyl) hexanaphthene (hydrogenation XDI, H6XDI).
Among the present invention,, be preferably at least a kind the resin that is selected from polyester polyol, acrylic polyol and the polythiol as the host that urethane resin is used, in addition,
As the stiffening agent that urethane resin is used, be preferably and be selected from compound at least a among HDI, MDI, the TDI.
Among the present invention, in the coating composition contained polyvalent alcohol with and/or polythiol, each composition of polymeric polyisocyanate, according to the ratio [NCO base/(OH base+SH yl)] of the normal total amount of mercaptan base in the equivalent of institute's hydroxyl in the equivalent of contained isocyanate group in the polymeric polyisocyanate and the polyvalent alcohol and the polythiol usually 0.1～5, more fortunately 0.2～4, better 0.5～3, the amount of special 0.7～2 scope is fortunately used.
In addition, above-mentioned carbodiimide type polymeric polyisocyanate is when share as the polymeric polyisocyanate beyond the carbodiimide type isocyanic ester of polymeric polyisocyanate, total amount 100 weight parts corresponding to these polymeric polyisocyanates, carbodiimide type isocyanic ester is usually with more than 1 weight part and less than 200 weight parts, better with more than 5 weight parts and, better more than 20 weight parts and less than the amount of 100 weight parts, to use less than 150 weight parts.
As use carbodiimide type polymeric polyisocyanate according to above-mentioned amount, can obtain can snap cure Xing Cheng Tu film poly-urethane resin.Because it is the working life (pot life) of the above-mentioned coating composition that contains polyvalent alcohol and/or polythiol and polymeric polyisocyanate is long, therefore more easy to operate.
＜acrylic resin ((methyl) acrylic resin) (c) 〉
As acrylic resin (being called (methyl) acrylic resin again), can use the resin of record in [0021]～[0023] section as Japanese patent laid-open 11-171933 communique.
Be somebody's turn to do (methyl) acrylic resin as describing in detail, as (methyl) acrylic resin, though can exemplify the resin that uses in the present coating, but better be to contain the unitary interpolymer of (methyl) acrylate composition, be somebody's turn to do (methyl) acrylic ester unit has hydroxyl, carboxyl, epoxy group(ing), amino etc. at side chain and/or main chain end sclerotic type functional group.As the unitary interpolymer of such containing (methyl) acrylate composition, can exemplify and contain (methyl) Hydroxyethyl acrylate, 2-hydroxyethyl vinyl ether, (methyl) vinylformic acid, (methyl) glycidyl acrylate, 2-amino-ethyl propyl group (methyl) vinylformic acid etc. unitary interpolymer of gained composition of deriving.
The unitary interpolymer of (methyl) acrylate composition of this containing as commercially available has " ア Network リ デ イ Star Network A-430; ア Network リ デ イ Star Network A-810-45 " (Dainippon Ink. ﹠ Chemicals Inc's system), " テ ス ロ イ De 4211-46; テ ス ロ イ De 4212-46 " (Hitachi changes into polymkeric substance Co., Ltd. system), " ダ イ ヤ Na one Le LR-620; ダ イ ヤ Na one Le HR-656 " (レ イ ョ Application Co., Ltd. of Mitsubishi system), " ヒ ロ イ De 3046C; ヒ ロ イ De 3018; ヒ ロ イ De 3083-70B " (Hitachi Chemical Co., Ltd.'s system), " ダ イ ヤ Na one Le BR-106 " (レ イ ョ Application Co., Ltd. of Mitsubishi system), " Eterkydl401 BA-80; Eterdydl480 BA-65 " (Taiwan Etermal Chemical corporate system) etc.
Measure with GPC, the number-average molecular weight of (methyl) acrylic resin is 1000～15000, is preferably 5000～10000, as having a declining tendency than the big then solvability in solvent of this scope, the trend of reduction is arranged as the weather proofing than this scope Xiao Ze Tu film.
＜stiffening agent (D) 〉
As the stiffening agent that (methyl) vinylformic acid polyalcohols resin is used, can exemplify melamine resin (melamine stiffening agent), urea resin (urea resin stiffening agent), poly-basic organic acid and polyisocyanates etc.These stiffening agents more than a kind or 2 kinds can be used in combination among the present invention.
With stiffening agent (D), can use the compound of in [0023]～[0027] section of Japanese patent laid-open 11-171933 communique, putting down in writing as this (methyl) acrylic polyol resin.That is,, can exemplify, can select to use the compound of various modification degree, also can select suitable self the polymerization degree according to purposes as butylated melamines, methylated melamines, epoxy group(ing) distortion melamine etc. as melamine resin (melamine stiffening agent).
As urea resin (urea resin stiffening agent), can exemplify as the urea resin that methylates, butylation urea resin etc.As poly-basic organic acid, can exemplify as long-chain fat family omega-dicarboxylic acids, aromatic series polycarboxylic acid class and these sour acid anhydrides etc.As this polyisocyanates, can exemplify as 1, the vulcabond of no xanthochromia such as hexamethylene-diisocyanate, isophorone diisocyanate and affixture thereof, have multicomponent isocyanate by isocyanuric acid ester class deutero-group etc., wherein be preferably the polyisocyanates that has by isocyanuric acid ester class deutero-group.But this polyisocyanates is because cold setting, thereby very suitable, polymer (A) when having hydroxyl etc. for example, owing to can carry out cold setting by isocyanate group and urethane reaction, thereby very suitable.
Other, the block polyisocyanates also can better be used as stiffening agent, mainly is the stiffening agent of using as the heat hardening type.
＜hardening catalyst 〉
Among the present invention, also can contain hardening catalyst in the aforementioned coating composition, above-mentioned hardening catalyst is preferably metallic compound or acid.
As this metallic compound, can give an example as tin compound etc.; As acid, can give an example as phosphoric acid, sulfonic acid etc.For urethane resin is coating etc., when using polyisocyanates to carry out cold setting, can by add metallic compound for example well-known catalysts such as dibutyl tin laurate promote sclerosis.
In addition, when using the melamine stiffening agent that uses as hardener for epoxy resin etc. or urea resin stiffening agent, can promote sclerosis by an acidic catalyst that adds phosphoric acid system or sulfonic acid system.
[is the low smell organic solvent (B) of representative with the N-BUTYL ACETATE]
When modulating low smell solvent based coating composition of the present invention (coating composition), can remove dimethylbenzene, toluene of the major cause that becomes the coating smell etc., and can use the solvent (solvent) of various low smells, can use alcohols such as propyl carbinol; Ester such as N-BUTYL ACETATE, vinyl acetic monomer class; Ketone such as butanone, methyl iso-butyl ketone (MIBK); Gylcol ethers such as ethyl cellosolve; Commercially available various thinners etc.,
Be preferably ester classes such as N-BUTYL ACETATE, vinyl acetic monomer; Ketones such as butanone; Alcohols such as propyl carbinol,
Wherein, from low smell, solvability (in other words, being exactly the easy dissolving resin composition of solvent), evaporation rate (that is evaporation rate that solvent has appropriateness during coating process, to coating, the advantage of coating) aspect is considered, is preferably the N-BUTYL ACETATE of ester class.
Low smell solvent like this can be used in combination more than a kind or 2 kinds.Among the present invention, during the low smell solvent of combination more than 2 kinds,, be preferably the N-BUTYL ACETATE solvent and other above-mentioned low smell solvent share from the aspect of viscosity adjustment, homogeneity, preventing property of foaming.
Adjust the angle of property from coating decoration, viscosity, in coating composition, this is that the low smell solvent (B) of representative adds up to content usually in the scope of 5～30% weight % with the N-BUTYL ACETATE, is preferably the scope of 10～25 weight %.
In addition, when combination N-BUTYL ACETATE solvent and " other low smell solvent " use, consider, with in total 100 weight parts of low smell solvent from low smell, deliquescent angle, account for 30～80 weight parts, the content that better accounts for 40～70 weight parts uses the N-BUTYL ACETATE solvent.
In addition, consider,, be preferably the content of 10～60 weight % resins (A), use with the low smell solvent of this N-BUTYL ACETATE solvent as representative to contain the resin (A) that is generally 5～80 weight % in the coating from aspects such as coating decoration, Tu film properties.
[compound (C)]
Among the present invention, can use carbonatoms as compound (C) is ester and/or lactone more than 8.
As this compound (C), be preferably, can neutralize or reduce solvent odor in the coating, coating smell etc., and after Gai Tu film drying of coated article external coating coating, can reduce as much as possible, the compound of the remaining solvent in the Yi Zhi Tu film, solvent odor on every side, the smell of coating raw material etc., its mechanism all can for physical adsorption, chemical reaction etc.
As this compound (C), can exemplify
(a): (always) carbonatoms is more than 8, is preferably (always) carbonatoms and is 8～15 ester (the chain ester that particularly can have the ring structure of cyclohexyl ring etc.), perhaps,
(b): in the lactone contained part hydrogen atom can by carbonatoms be 1～15 metathetical α such as alkyl-, β-, γ-, delta-lactone, or in the ring structure of these lactones, have the lactone of the unsaturated lactone etc. of unsaturated link(age).
As this lactone (b), the lactone that becomes cyclic ester that forms with the hydroxycarboxylic acid of this ester (a) equal extent (always) carbonatoms, better be become α-, β-, γ-, the lactone of the cyclic ester of δ-hydroxycarboxylic acid, the spy be well become γ-, the lactone of the cyclic ester of δ-hydroxycarboxylic acid.
As compound of the present invention (C), from the smell and efficient, price, the aspects such as easiness that obtain considered, be preferably the ester (the chain ester that particularly, can have the ring structure of cyclohexyl ring etc.) and/or the lactone of carbonatoms 8～15.)
As this compound (C), the ester of above-mentioned carbonatoms (chain ester) can exemplify, and the ester that the saturated or unsaturated carboxylic acid of C1～10 and the monobasic unsaturated alcohol of C3～10 (particularly, can have the chain alcohol of the ring structure of cyclohexyl ring etc.) form etc. can exemplify,
(1): caproic acid-2-propylene ester [CH
3(CH
2)
4COOCH
2CH=CH
2],
(2): enanthic acid-2-propylene ester [C
6H
13COOCH
2CH=CH
2],
(3): sad-2-propylene ester [C
7CH
15COOCH
2CH=CH
2],
(4): acetic acid-4-(1, the 1-dimethyl ethyl) cyclohexyl [general name: the acetate p-tertiary butyl-cyclohexyl ester]:
In the above-mentioned lactone, specifically can be for example, general expression (c):
Deng (in the formula (c), R is the alkyl or the alkylidene group of H or C1～15, for example can be CH
3, C
2H
5, n-C
4H
9, n-C
8H
17, n-C
12H
25, n-C
14H
29, CH
3CH
2CH=CHCH
2Deng, perhaps also can combine ring structures such as forming phenyl ring with adjacent carbons.N is 0～5 integer.)。
As such lactone, remove in the formula (c) R=C
7H
15, n=1 (5): 5-heptyl dihydro-2 (3H)-furanone [general name: aldehyde C-14, γ-dodecalactone :]
Outside, can exemplify as saturated lactones (belonging to following formula (c)) such as butyrolactone, γ-Wu Neizhi, γ-Ji Neizhi, γ-Xin Neizhi, γ-lauryl lactone, γ-dodecalactone, γ-Shi Yineizhi, γ-palm lactone, γ-stearolactone, δ-Wu Neizhi, δ-caprolactones;
The unsaturated lactone such as crotons lactone, alpha-angelica lactone, β-angelica lactone, tonka bean camphor (δ lactone and phenyl ring condense thing) that does not below belong to formula (c);
Other have jasmine lactone, jasmone:
Deng.Also can use the Japanese Patent spy and open that 2002-275495 communique, Japanese Patent spy open that 2003-102819 communique, Japanese Patent spy open that the deodorizing of record in 2002-275495 communique, the special public table 2002-540853 communique of Japanese Patent, the special public table 2002-505720 communique of Japanese Patent etc. is used or the aliphatic ester of aromaticity, cyclic ester etc.
Wherein, the compound of record is owing to the neutralization excellence to smell, therefore better in (1)～(5).
In these compounds (C), being preferably and being selected from carbonatoms is at least a kind compound in ester more than 8 and/or the lactone, and these compounds (C) also can be used in combination more than a kind or 2 kinds.
Among the present invention, from the angle of smell neutral efficient, price is considered, in coating composition, contain 0.01～3.0 weight % usually, be preferably these compounds (C) of 0.01～1.0 weight % scope.
In addition, from to the smell and the angle of efficient, price consider, with respect to low smell organic solvent (B) 100 weight parts that contain in the coating, this compound (C), the spy be well be selected from carbonatoms be in ester more than 8 and/or the lactone at least a kind compound (C) usually according to, 0.03～5 weight parts are preferably 0.07～3 weight part, particularly preferably the content of 0.1～1.0 weight part uses.
＜other mixing element 〉
In the coating composition that the present invention relates to, except that mentioned component (A)～(D) waits, also can contain following " other compositions ".
As these other compositions, tinting material, filler pigment, viscosity modifier, leveler, defoamer, UV light absorber, the above-mentioned De Tu film in addition that can exemplify as softening agent, stablizer, the sagging anti-sedimentation agent of resistance, titanium oxide (titanium white) etc. are formed into the various compositions that grade.
＜hinder sagging anti-sedimentation agent (thixotropic agent) 〉
As resistance sagging anti-sedimentation agent (thixotropic agent), can exemplify as organic viscosity is that salt, polyethylene wax, amide waxe, hydrogenated castor oil wax system, polyamide wax system and both mixtures of the hard acid ester salt, Yelkin TTS salt, hydrocarbyl sulfonate etc. of Al, Ca, Zn, synthetic micro mist silica, oxidic polyethylene are wax etc., and better using polyamide wax, synthetic micro mist silica, oxidic polyethylene is wax, organic viscosity system.
As the sagging anti-sedimentation agent of this resistance, exemplifying except that nanmu originally changes into " デ イ ス パ ロ Application 305 " " デ イ ス パ ロ Application 4200-20 " etc. of Co., Ltd.'s system as product with the trade(brand)name listing of " デ イ ス パ ロ Application A630-20X " etc.
＜tinting material 〉
Tinting material can exemplify as pigment, dyestuff etc.As pigment, can use the various pigment of present known organic system, inorganic system.As organic system pigment, can exemplify carbon black as black, blue phthalocyanine blue, green phthalocyanine green, red insoluble azo colour (naphthols AS), xanchromatic monoazo series pigments etc.As inorganic series pigments, can exemplify neutrality, non-reacted inorganics as titanium white, colcother, barium sulfate, silica, lime carbonate, talcum, chalk, brown iron oxide etc.; The alkalescence that zinc oxide (ZnO), white lead powder, tri-lead tetroxide, zinc end, plumbous oxide etc. are such, with coating in the inorganics of acidic substance reaction (reactive pigment).
＜filler pigment 〉
As filler pigment, can exemplify as potassium felspar sand, barium sulfate, settleability barium sulfate, mica, lime carbonate, kaolin, talcum, silica powder etc.
(manufacturing of coating composition)
When making aforementioned coating composition, at above-mentioned resin (A), with the N-BUTYL ACETATE is the low smell organic solvent (B) of representative, has compound (C) as the odor neutralizer function, add hardening catalyst as required in the stiffening agent of Tian Jiaing (D), softening agent, inorganic dewatering agent (stablizer), hinder sagging anti-sedimentation agent, titanium oxide tinting materials such as (titanium whites), filler pigment, viscosity modifier, leveler, UV light absorber, Tu film beyond above-mentioned forms composition, weighting agent, fire retardant, thixotropy shape imparting agent, the thermal conduction modifying agent, bonding composition, spices etc. once or according to the random order interpolation mix according to a certain percentage, as long as can dissolve dispersion in solvent.
At this moment, the various mixed stirring devices that can use ball mill, coating vibrator, sand mill, 3 roller mashers, mixing machine etc. in coatingization, to use usually.When using the blocked polyisocyanates class, can obtain normal temperature hardened paint composite as stiffening agent composition (D).In such paint composite, be in harmonious proportion the stiffening agent composition in addition, form the two-pack type coating composition.
In addition, as stiffening agent composition (D),, can obtain the coating composition of heat hardening type, single-liquid type if use melamine resin, urea resin, blocked polyisocyanates class.
[purposes of coating composition]
Coating composition of the present invention like this, smell is little, is applicable to parts or position that application Hou Tu film evaporable smell is easily accumulated, uses as the application as the inside of application usefulness, particularly freight container in the freight container, bottom surface, sealing ply.Other suitable coated materials (coating composition) that are used as the surface-coated usefulness of various base materials such as engineering materials, building materials (example: typified form, partition wall, door, vehicle inside components etc.), electrical component, electronic unit, process article, dress ornament industry articles for use, medical treatment product, stationery, in addition, also suitable surface soiling coating as base material.Coating composition of the present invention like this can use at electric and electronic, building materials technology, dress ornament industry, medical treatment, agricultural water industry, generating, bay civil construction, shipbuilding or Ship's Repair vessel coating etc. widely in the industrial field particularly.
Below, for this paint composite, illustrate various that the substrate surface lining forms with the base material of filming.
＜with the base material of filming 〉
What the present invention relates to the base material of filming is, the covering of filming that the substrate surface by freight container, buildings, structure etc. is formed by above-mentioned specific coating composition forms.
As above-mentioned base material, from material face, structural plane classification, then can exemplify various metal sheets as aluminium face, iron plate, stainless steel plate, tin plate etc. as mainly; Calcium silicate board etc.In addition as mainly according to the purpose classification base material, then can exemplify as internal container portion material (internal container is bottom surface material, wall material, ceiling material for example), engineering materials, building materials typified form, partition wall particularly the lavatory with dividing plate, door, kitchen typified form, the interior dress portion of vehicle material etc.
Among the present invention, can directly form on the surface of these base materials by filming that aforementioned coating composition forms, also can be as required, the epoxy that is pre-formed as undercoat on the surface of this base material is priming paint agent layer or UV cured type layer, and lamination forms by filming that low smell solvent based coating composition of the present invention constitutes on this surface again.
In addition, also can be at sealing ply (sealant, the sealing material) external coating low smell solvent based coating composition of the present invention, and, also can be with low smell solvent based coating composition self of the present invention as sealing material, be filled into during internal container grades as the weld portion of the gap between the base material of base plate of pallet setting etc., freight container inner face.
Particularly, when the external coating of sealing ply low smell solvent based coating composition of the present invention, sealing ply is as the bottom of application, do not contain toluene, dimethylbenzene as solvent, and according to necessity add with the N-BUTYL ACETATE be representative low smell organic solvent (B), have above-claimed cpd (C) as the odor neutralizer function, for example, be preferably the sealing ply etc. of the neoprene system of such composition.
For example, surface at base material, the lamination epoxy is the base material of filming of having of priming paint layer, low smell solvent based coating composition layer formation of the present invention in order, has and films to character such as the adaptation of base material, the low smell of filming, preservative property, resistances to chemical reagents.
Particularly, when this moment used base material be metal system, and this indurative low smell solvent based coating composition (coating) direct baking is coated with when being contained on the respective metal portion material, perhaps on respective metal portion material preformed epoxy resin priming paint layer or by various resin system powder coatings form the layer the surface, when the coating that formation is formed by this curable adhensive compositions forms the curable adhensive compositions layer through toasting application, should hang down smell solvent based coating composition layer, tack to respective metal portion material etc. is good, and have and be difficult for speckling with Yi Shui and oil characteristics as all contaminations of principal constituent, promptly has repellency, scold oiliness, stain resistance is good, even and these pollutents temporarily adhere to also and can be wiped easily, so removing property of resistant excellence.
The invention effect
The invention provides the inside surface coating usefulness coating that is suitable for the freight container convey goods etc., building construction thing etc., can significantly suppress the coating smell that produces behind the dried coating film low smell solvent based coating composition, it is filmed and various moldinies such as freight container, buildings, structure with this low smell of filming.
Embodiment
Below, the low smell solvent based coating composition that detailed description be the present invention relates to, its method for making, coating process etc., but the present invention is not restricted to any qualification of related embodiment.
[embodiment 1]
The modulation 1 of the low smell solvent based coating composition of＜epoxy resin 〉
As shown in table 1, modulation is by the low smell solvent based coating composition of epoxy resin of remembering that down host and stiffening agent form.
＜host 〉
The N-BUTYL ACETATE solution of bisphenol A-type (BPA) Resins, epoxy (Mw=1001 of resin, NV=75%, big bamboo Ming Xin KCC system, article number: " E001-75B ") 30.00 weight parts,
The compound of smell neutrality (group) { is formed: (1): caproic acid-2-propylene ester [CH
3(CH
2)
4COOCH
2CH=CH
2], (2): enanthic acid-2-propylene ester [C
6H
13COOCH
2CH=CH
2], (3): sad-2-propylene ester [C
7H
15COOCH
2CH=CH
2], (4): acetic acid-4-(1, the 1-dimethyl ethyl) cyclohexyl [general name: the acetate p-tertiary butyl-cyclohexyl ester], (5): 5-heptyl dihydro-2 (3H)-furanone, Shanghai カ サ go one ユ ニ オ Application corporate system, trade(brand)name: " neutralizing agent 350120-1 " } 0.01 weight part
Sagging dose of (organic system, principal constituent: polyethylene wax, big bamboo Ming Xin KCC system) 4.00 weight parts of resistance fall in anti-Shen,
Hinder sagging dose of (inorganic system, principal constituent: wilkinite, hectorite (hectorite), aluminum stearate etc.) (RHEOX corporate system) 1.00 weight parts,
Tinting pigment (white, titanium dioxide (rutile-type, Detitanium-ore-type), DUPONT corporate system) 18.00 weight parts,
Filler pigment 1 (barium sulfate, Sakai KCC system), 8.00 weight parts,
Filler pigment 2 (talcum, talcum Co., Ltd. of Fuji system), 18.00 weight parts,
Filler pigment 3 (silica powder, the former KCC of bamboo system) 7.00 weight parts,
N-BUTYL ACETATE solvent ( イ セ Le Co., Ltd. system) 7.99 weight parts,
Organic solvent is [except that toluene, dimethylbenzene, N-BUTYL ACETATE.MEK (butanone), MIBK (methyl iso-butyl ketone (MIBK)), isopropylcarbinol, IPA (Virahol), N-butanols, butanols, turps, ethyl cellosolve, ethylene glycol butyl ether (Network ラ レ Co., Ltd. system)] 5.80 weight parts and,
Additive (the vinylformic acid vinyl ether is defoamer, common prosperity KCC system) 0.20 weight part (adding up to 100.00 weight parts).
＜stiffening agent 〉
Polyamide resin lipoprotein solution (the N-BUTYL ACETATE solution of polyamide resin, NV=60%, big bamboo Ming Xin KCC system, trade(brand)name " PA-53 (B/100) ") 97 weight parts,
Hardening accelerator (tertiary amine, エ ア one プ ロ ダ Network Star ジ ヤ パ Application commercial firm system) 1.00 weight parts,
N-BUTYL ACETATE solvent (ダ イ セ Le Co., Ltd. system) 2.00 weight parts (adding up to 100.00 weight parts).
The modulation of＜coating 〉
Mix above-mentioned host 85.0 weight parts and above-mentioned stiffening agent 15.0 weight parts (adding up to 100 weight parts), the low smell solvent based coating composition (NV=73.0wt% of modulation, PVC (Pigment Volume Content, pigment volume concentration (PVC))=36.0%, toluene, xylene content=0% in the coating, content=0.0012% of the compound (C) of shared smell neutrality in the effective constituent in the coating).
In addition, the content of toluene and dimethylbenzene in the coating is to estimate according to the content of contained toluene and dimethylbenzene in the coating composition that is formed by host and stiffening agent mixing.
In addition, the content of the compound (C) of shared smell neutrality in the effective constituent in the coating, be to estimate according to the content of the compound (C) of smell neutrality contained in film (dry coating), filming is to mix the coating composition that forms by the coating sclerosis by host and stiffening agent to form.
＜application 〉
Inner face at 20 liters of (L) canescence cylinders, blow attached application epoxy resin ジ Application Network リ Star チ coating (trade(brand)name " EPICON ZINC SC B-2 " Chugoku Marine Paints, Ltd.'s system) as base paint, making dry film thickness is 25 μ m (thick), and slaking afterwards 10 minutes is when undercoat is unhardened, as coating materials, blow the above-mentioned low smell solvent based coating composition of attached application, making dry film thickness is 50 μ m (thick), leaves standstill after the slaking 30 minutes, 80 ℃ of heating 30 minutes, carry out forced drying.(total dry film thickness: 75 μ m)
Afterwards, cooled off 30 minutes, then, close the sealing of lid of canescence cylinder.
＜through the time odor intensity and the mensuration that discharges gas (dimethylbenzene gas) amount
(7 days, 1 month, 2 months, 3 months) carried out the mensuration through the canescence cylinder gas that inner face discharges of application afterwards after resulting canescence cylinder (trial target) through application left standstill the specified time, carried out the mensuration of odor intensity simultaneously.Carry out placing 1 hour with the state of opening canescence cylinder cap after eudiometry and the odor intensity mensuration, close lid again and form sealed state.
Each determination test all repeats to implement according to aforesaid operations.
The measuring method of＜smell 〉
Use bright physics and chemistry to learn " the Beichuan formula gas detector " of Industrial Co., Ltd's system, carry out discharging in the application canescence cylinder (trial target) mensuration (unit: ppm) of dimethylbenzene gas.
As a result, be 200ppm on the 7th, 70ppm after 1 month, 50ppm after 2 months, 25ppm after 3 months by the measured value of the xylene concentration of " Beichuan formula gas detector " gained.
In addition, according to the difference of determination object gaseous species, this detector uses different detector tubes, in this test, has used dimethylbenzene eudiometry detector tube.
The measured value of this dimethylbenzene gas represents that with the size of dimethylbenzene gas concentration this numerical value is big more, means that the amount of dimethylbenzene gas of release is many more.
In addition, odor intensity, the 7th day for " 1 " (feeling solvent odor), after 1 month for " 3 " (feeling to have solvent odor slightly), after 2 months for " 4 " (feeling scent of slightly), after 3 months for " 4 ".
Yi Merger is shown in table 2 as a result.
In addition, the judgement criteria of odor intensity is as follows.
The judgement criteria of＜odor intensity 〉
" 5 ": almost do not feel scent of.
" 4 ": feel scent of slightly.
" 3 ": feeling slightly has solvent odor.
" 2 ": feel scent of.
" 1 ": feeling has solvent odor.
" 0 ": discomfort is arranged.
＜film to the mensuration of the adaptation of base material, the scratch hardness of filming
(a) test method:
Basically carry out according to the test method of record in " JIS K 5600 ".
(b) making of test film
Test is with the manufacture method of application plate, remove use 1.6mm (thick) sandblast steel plate (JIS K 5410) as the base material, with above-mentioned " through the time odor intensity and release gas (dimethylbenzene gas) the mensuration of amount " situation identical, carry out application.
Promptly, on the plastics steel plate (JIS K 5410) of 1.6mm (thick), blow attached application epoxy resin ジ Application Network リ Star チ coating (trade(brand)name " EPICON ZINC SC B-2 " as base paint, Chugoku Marine Paints, Ltd.'s system), making dry film thickness is 25 μ m (thick), slaking afterwards 10 minutes, when undercoat is unhardened, as coating materials, blow the above-mentioned low smell solvent based coating composition of attached application, making dry film thickness is 50 μ m (thick), after the slaking 30 minutes, 80 ℃ of heating 30 minutes, carry out forced drying.(total dry film thickness: 75 μ m)
Afterwards, cooling is 30 minutes.
Then, respectively at following condition determination, measure tack, the scratch hardness of filming, resistance to liquid (resistance to chemical reagents), anti-neutral brine sprayability, the wet fastness of filming.
Its result is,
The tack of filming (with JIS K 5600-5-6, cross-section method tack test method(s) is as the criterion) is " having " (25 orders adhere to/25 orders in),
The scratch hardness of filming (with JIS K 5600-5-4, pencil method scratch hardness test method is as the criterion) is " 3H ",
Resistance to liquid (resistance to chemical reagents) (with JIS K 5600-6-1, resistance to liquid (general method) test method(s), topical application are as the criterion) is, to 10%H
2SO
4The aqueous solution, the 10%NaOH aqueous solution and 99.8% aqueous ethanolic solution are " 4 " (variable color is arranged slightly),
Anti-neutral brine sprayability (with JIS K 5600-7-1, anti-neutral brine spray testing method is as the criterion), general place is " 5 " (not changing), the crosscut position is " 4 " (albefaction, variable color take place slightly, get rusty),
Wet fastness (with JIS K 5600-7-2, wet fastness (dewfall method continuously)-rotary test method(s) is as the criterion) is " 4 " (albefaction, variable color take place slightly),
A And is shown in table 3 as a result.
＜the tack of filming 〉
With " JIS K 5600-5-6 ", the horizontal method tack test method(s) of stealing is as the criterion the driving fit stripping test of filming on the test film that is coated.
Judgement criteria is as follows.
" have ": 25 orders adhere in 25 orders.
" nothing ": below above-mentioned.
＜the scratch hardness of filming 〉
With " JIS K 5600-5-4 ", pencil method scratch hardness test is a standard, the pencil hardness test of the test film that is coated.Represent with the concentration mark of pencil with the pencil-lead hardness that cut films of will filming.
＜resistance to liquid (resistance to chemical reagents) 〉
With JIS K 5600-6-1, resistance to liquid (general method) test method(s), some volumetry are as the criterion, the resistance to chemical reagents test of the test film that is coated.
As experimental liquid, use 10%H
2SO
4The aqueous solution, the 10%NaOH aqueous solution and 99.8% aqueous ethanolic solution.Test period is 72 hours.
The judgement criteria of resistance to liquid is as follows.
" 5 ": do not change.
" 4 ": variable color is arranged slightly.
" 3 ": albefaction, variable color take place.
" 2 ": expansion, fold, cracking are arranged slightly.
" 1 ": expansion, fold, cracking are arranged.
＜anti-neutral brine sprayability 〉
With JIS K 5600-7-1, anti-neutral brine spray testing method is as the criterion, and carries out the resist coating film test for the brine spray that is coated test film.
On the test film that is coated, use point of a knife cut wound (crosscut) on filming of the instrument of regulation in " JIS K 5600-5-6:4.1.1 ", reach the blank of test film deeply, form the diagonal lines of two intersections, test period is 1000 hours.
The evaluation of filming is carried out according to following standard, and the general place of filming and crosscut position be coated with membrane stage evaluation.
The judgement criteria of anti-neutral brine sprayability is as follows.
" 5 ": do not change.
" 4 ": albefaction, variable color are arranged slightly, get rusty.
" 3 ": get rusty, expand, peel off.
" 2 ": small area gets rusty, expands, peels off.
" 1 ": big area is got rusty, expands, is peeled off.
＜wet fastness 〉
With " JIS K 5600-7-2 ", (dewfall method continuously)-rotary test method(s) is a standard to wet fastness, the anti-moisture test of filming, and test period is 800 hours.
Judgement criteria is as follows.
" 5 ": do not change.
" 4 ": albefaction, variable color are arranged slightly.
" 3 ": peel off.
" 2 ": small area gets rusty, expands, peels off.
" 1 ": big area is got rusty, expands, is peeled off.
[embodiment 2～4, comparative example 1～2]
Except that the combined group of coating composition among the embodiment 1 is become to do respectively to modulate coating composition similarly to Example 1 the variation as shown in table 1, carry out the test identical with embodiment 1.
Mixing is formed, measurement result is shown in table 1～3.
Table 1
| Raw-material kind | The main composition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | |
| Host | Epoxy resin solution (BA) | The N-BUTYL ACETATE solution of BPA Resins, epoxy | 30.00 | 30.00 | 30.00 | 30.00 | - | 30.00 |
| Epoxy resin solution (XA) | The xylene solution of BPA Resins, epoxy | - | - | - | - | 30.00 | - | |
| Smell neutrality compound group (C) | (*1) | 0.01 | 0.03 | 0.05 | 0.09 | - | - | |
| Sagging dose of resistance falls in anti-Shen | Polyethylene wax | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | |
| Hinder sagging dose (inorganic system) | Wilkinite, hectorite, aluminum stearate | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | |
| Tinting pigment (in vain) | Titanium dioxide (rutile-type, Detitanium-ore-type) | 18.00 | 18.00 | 18.00 | 18.00 | 18.00 | 18.00 | |
| Filler pigment 1 | Barium sulfate | 8.00 | 8.00 | 8.00 | 8.00 | 8.00 | 8.00 | |
| Filler pigment 2 | Talcum | 18.00 | 18.00 | 18.00 | 18.00 | 18.00 | 18.00 | |
| Filler pigment 3 | Silica powder | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | 7.00 | |
| Organic solvent (TX) | Toluene, dimethylbenzene | - | - | - | - | 8.00 | - | |
| N-BUTYL ACETATE (BA) | N-BUTYL ACETATE | 7.99 | 7.97 | 7.95 | 7.91 | 0.00 | 8.00 | |
| Organic solvent (except that TX) | MEK, MIBK, isopropylcarbinol, IPA, propyl carbinol, turps, ethyl cellosolve, ethylene glycol butyl ether, | 5.80 | 5.80 | 5.80 | 5.80 | 5.80 | 5.80 | |
| Additive | Defoamer, leveler | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | |
| Add up to (weight part) | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | ||
| Stiffening agent | Polyamide resin lipoprotein solution (BA) | 97.00 | 97.00 | 97.00 | 97.00 | - | 97.00 | |
| Polyamide resin lipoprotein solution (XA) | - | - | - | - | 97.00 | - | ||
| Hardening accelerator | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | ||
| Dimethylbenzene, toluene | - | - | - | - | 2.00 | - | ||
| N-BUTYL ACETATE (BA) | 2.00 | 2.00 | 2.00 | 2.00 | - | 2.00 | ||
| Add up to (weight part) | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | ||
| Host/stiffening agent (weight proportion) | 85/15 | 85/15 | 85/15 | 85/15 | 85/15 | 85/15 | ||
| Dimethylbenzene and content of toluene (%) in the blend compositions of host and stiffening agent | 0.00 | 0.00 | 0.00 | 0.00 | 15.00 | 0.00 | ||
| The content (%) of odor neutralizer in the effective constituent of the blend compositions of host and stiffening agent (filming) | 0.012 | 0.036 | 0.061 | 0.110 | 0.000 | 0.000 |
The composition of smell neutrality compound group (C) (* 1) etc.:
(1): caproic acid-2-propylene ester (CH
3(CH
2)
4COOCH
2CH=CH
2), (2): enanthic acid-2-propylene ester (C
6H
13COOCH
2CH=CH
2), (3): sad-2-propylene ester (C
7H
15COOCH
2CH=CH
2), (4): acetic acid-4-(1, the 1-methylethyl) cyclohexyl [general name: the acetate p-tertiary butyl-cyclohexyl ester], (5): 5-heptyl dihydro-2 (3H)-furanone (Shanghai カ サ go one ユ ニ オ Application corporate system, trade(brand)name: " neutralizing agent 350120-1 ")
Dimethylbenzene gas concentration (ppm)/odor intensity that table 2[measures by gastic reactotube]
| Host/stiffening agent (weight ratio of mixture) | Duration of test | ||||
| 7 days | 1 month | 2 months | 3 months | ||
| Embodiment 1 | 85/15 | 200/1(*1) | 70/3 | 50/4 | 25/4 |
| Embodiment 2 | 85/15 | 300/2 | 80/4 | 60/4 | 10/5 |
| Embodiment 3 | 85/15 | 200/2 | 70/2 | 50/4 | 15/5 |
| Embodiment 4 | 85/15 | 300/2 | 80/2 | 70/4 | 20/4 |
| Comparative example 1 | 85/15 | (＞1000)/0 | 800/1 | 400/1 | 300/3 |
| Comparative example 2 | 85/15 | 250/1 | 100/1 | 50/3 | 30/3 |
(
*1) 200/1=dimethylbenzene gas concentration 200ppm/ odor intensity " 1 "
The evaluation of the tack that table 3[films, scratch hardness, resistance to liquid, anti-neutral salt water-based, wet fastness]
| Host/stiffening agent (weight proportion) | Tack | Scratch hardness | Resistance to liquid | Anti-neutral brine sprayability | Wet fastness | ||||
| 10％ H 2SO 4aq | 10％ NaOHaq | 99.8% ethanol | General place | The crosscut position | |||||
| Embodiment 1 | 85/15 | Have | 3H | 4 | 4 | 4 | 5 | 4 | 4 |
| Embodiment 2 | 85/15 | Have | 3H | 4 | 4 | 4 | 5 | 4 | 4 |
| Embodiment 3 | 85/15 | Have | 3H | 4 | 4 | 4 | 5 | 4 | 4 |
| Embodiment 4 | 85/15 | Have | 3H | 4 | 4 | 4 | 5 | 4 | 4 |
| Comparative example 1 | 85/15 | Have | 3H | 4 | 4 | 4 | 5 | 4 | 4 |
| Comparative example 2 | 85/15 | Have | 3H | 4 | 4 | 4 | 5 | 4 | 4 |
The possibility that industry is utilized
As above-mentioned, the inside surface coating of the suitable container as transporting cargo of the low odor solvent-based coating composition that the present invention relates to, building construction thing etc. is with uses such as coating, can significantly reduce, be suppressed at the coating smell that occurs behind the dried coating film, and the person's that can improve the coating decoration safety and sanitation condition, even have in addition in inside surface coating has the container of this coating and place, carry, preserve goods, coating smell also difficulty is attached on the goods, the advantage that commodity price can not reduce. This coating can be coated with in the various formed bodies such as being contained in container, building, structure, and any situation all has above-mentioned effect.
Claims (14)
1. low smell solvent based coating composition is characterized in that, contains (A) and is selected from least a kind coating resin in Resins, epoxy, urethane resin and the acrylic resin,
(B) low smell organic solvent,
(C) be selected from carbonatoms more than 8 ester and/or at least a kind compound in the lactone, and contain the stiffening agent of (D) coating resin (A) usefulness according to necessity,
And, do not contain dimethylbenzene and toluene in fact as organic solvent.
2. low smell solvent based coating composition as claimed in claim 1, its feature are that also low smell organic solvent (B) is for being selected from least a kind in N-BUTYL ACETATE, vinyl acetic monomer, cellosolve acetate, ethyl cellosolve, the ethylene glycol butyl ether.
3. low smell solvent based coating composition as claimed in claim 1 or 2, its feature also be, be selected from carbonatoms more than 8 ester and/or lactone at least a kind compound (C) for being selected from caproic acid-2-propylene ester (CH
3(CH
2)
4COOCH
2CH=CH
2), enanthic acid-2-propylene ester (C
6H
13COOCH
2CH=CH
2), sad-2-propylene ester (C
7H
15COOCH
2CH=CH
2), acetic acid-4-(1, the 1-dimethyl ethyl) cyclohexyl:
, 5-heptyl dihydro-2 (3H)-furanone:
In any compound more than a kind.
4. as each described low smell solvent based coating composition in the claim 1～3, its feature also is, contains the low smell organic solvent (B) of 5～30 weight % in the coating composition.
5. as each described low smell solvent based coating composition in the claim 1～4, its feature also is, in coating composition, be selected from carbonatoms more than 8 ester and/or lactone at least a kind the content range of compound (C) be 0.01～1.0 weight %.
6. as each described low smell solvent based coating composition in the claim 1～5, its feature is that also the host of urethane resin is at least a kind of resin that is selected from polyester polyol, acrylic polyol and polythiol.
7. as each described low smell solvent based coating composition in the claim 1～6, its feature also is, the stiffening agent of used for epoxy resin (D-1) is the stiffening agent that is made of polymeric amide or its modifier, the stiffening agent that urethane resin is used (D-2) is at least a compound that is selected from hexamethylene diisocyanate (HDI), '-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI).
8. the paint for container composition is characterized in that, is formed by each described low smell solvent based coating composition in the claim 1～7.
9. the inner coating composition of freight container is characterized in that, is formed by each described low smell solvent based coating composition in the claim 1～7.
10. freight container bottom coating composition is characterized in that, is formed by each described low smell solvent based coating composition in the claim 1～7.
11. freight container sealing ply coating composition is characterized in that, is formed by each described low smell solvent based coating composition in the claim 1～7.
12. buildings or structure coating composition is characterized in that, are formed by each described low smell solvent based coating composition in the claim 1～7.
13. low smell is filmed, and it is characterized in that, is formed by each described coating composition in the claim 1～12.
14. be attached with freight container, buildings or the structure of low smell Tu film, it is characterized in that, be formed with the described low smell of claim 13 at the inner surface of freight container, buildings or structure and film.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2003/008111 WO2005000979A1 (en) | 2003-06-26 | 2003-06-26 | Lowly odorous solvent-based coating composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105369175A Division CN102010644A (en) | 2003-06-26 | 2003-06-26 | Low-odor solvent-based coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1788059A true CN1788059A (en) | 2006-06-14 |
Family
ID=33549041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA038266903A Pending CN1788059A (en) | 2003-06-26 | 2003-06-26 | Lowly odorous solvent-based coating composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4451390B2 (en) |
| CN (1) | CN1788059A (en) |
| WO (1) | WO2005000979A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105008471A (en) * | 2013-03-08 | 2015-10-28 | 中国涂料株式会社 | Anti-corrosion paint composition, anti-corrosion coating, and method for preventing corrosion of base material |
| CN108570260A (en) * | 2018-05-25 | 2018-09-25 | 安徽猛牛彩印包装有限公司 | A kind of printing ink with high adhesion force performance |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014005862A1 (en) * | 2012-07-06 | 2014-01-09 | Basf Se | Use of aqueous hybrid binders and alkyd systems for coating agents |
| CN105492550B (en) | 2013-08-23 | 2018-09-25 | 中国涂料株式会社 | The anti-corrosion method of anticorrosive coating composition, anticorrosion film and base material |
| CN106318172A (en) * | 2015-07-09 | 2017-01-11 | 黄光耀 | Solvent-borne coating and main agents, hardening agent and preparation method and coating method of coating |
| JP6766207B2 (en) * | 2019-03-22 | 2020-10-07 | 大日本塗料株式会社 | Paint composition |
| RU2734689C1 (en) * | 2020-03-04 | 2020-10-22 | Общество с ограниченной ответственностью "НТС-Лидер" | Polyurethane composition for protective coating of internal surface of oil and gas equipment |
| WO2023182060A1 (en) * | 2022-03-25 | 2023-09-28 | 日本ゼオン株式会社 | Vinyl chloride resin composition, vinyl chloride resin molded article, and laminate |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63284271A (en) * | 1987-05-16 | 1988-11-21 | Yukio Kawanishi | Fragrance emitting paint |
| JPH06200208A (en) * | 1993-01-06 | 1994-07-19 | Rasa Koei Kk | Deodorant-containing epoxy resin lining material |
| JPH0790050A (en) * | 1993-09-14 | 1995-04-04 | New Japan Chem Co Ltd | Epoxy resin and its production |
| JP3442170B2 (en) * | 1994-12-02 | 2003-09-02 | 旭化成株式会社 | Film-forming aid for acrylic aqueous dispersion and method for producing the same |
| JP3323072B2 (en) * | 1996-08-22 | 2002-09-09 | アイシン化工株式会社 | Epoxy resin composition |
| EP0950652B1 (en) * | 1998-04-13 | 2002-07-03 | Kuraray Co., Ltd. | Cis-configurational unsaturated ester, process for producing the same, and fragrance composition containing the same |
| ATE367845T1 (en) * | 1998-06-15 | 2007-08-15 | Procter & Gamble | FRAGRANCE COMPOSITIONS |
| JP2000226357A (en) * | 1998-12-04 | 2000-08-15 | Kuraray Co Ltd | Cis-form unsaturated ester, its production and perfume composition including the same |
| EP1239890B1 (en) * | 1999-12-13 | 2004-11-10 | Symrise GmbH & Co. KG | Odor neutralizers |
| JP2002294139A (en) * | 2001-04-02 | 2002-10-09 | Toyo Ink Mfg Co Ltd | Coating composition and its coated product |
| JP2003147386A (en) * | 2001-11-09 | 2003-05-21 | Soda Aromatic Co Ltd | Fragrance composition and fragrant cosmetic comprising the same |
-
2003
- 2003-06-26 CN CNA038266903A patent/CN1788059A/en active Pending
- 2003-06-26 JP JP2005503215A patent/JP4451390B2/en not_active Expired - Fee Related
- 2003-06-26 WO PCT/JP2003/008111 patent/WO2005000979A1/en active Application Filing
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105008471A (en) * | 2013-03-08 | 2015-10-28 | 中国涂料株式会社 | Anti-corrosion paint composition, anti-corrosion coating, and method for preventing corrosion of base material |
| TWI561593B (en) * | 2013-03-08 | 2016-12-11 | Chugoku Marine Paints | Anti-corrosive coating composition, anti-corrosive coating film and anti-corrosive method of base member |
| CN105008471B (en) * | 2013-03-08 | 2017-08-15 | 中国涂料株式会社 | The anti-corrosion method of anticorrosive coating composition, anticorrosion film and base material |
| CN108570260A (en) * | 2018-05-25 | 2018-09-25 | 安徽猛牛彩印包装有限公司 | A kind of printing ink with high adhesion force performance |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005000979A1 (en) | 2005-01-06 |
| JPWO2005000979A1 (en) | 2006-08-03 |
| JP4451390B2 (en) | 2010-04-14 |
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