CN100528988C - Coating composition for forming coating film having gradient composition - Google Patents
Coating composition for forming coating film having gradient composition Download PDFInfo
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- CN100528988C CN100528988C CNB2005100697863A CN200510069786A CN100528988C CN 100528988 C CN100528988 C CN 100528988C CN B2005100697863 A CNB2005100697863 A CN B2005100697863A CN 200510069786 A CN200510069786 A CN 200510069786A CN 100528988 C CN100528988 C CN 100528988C
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00
- D06F39/12—Casings; Tubs
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F37/00—Details specific to washing machines covered by groups D06F21/00 - D06F25/00
- D06F37/02—Rotary receptacles, e.g. drums
- D06F37/04—Rotary receptacles, e.g. drums adapted for rotation or oscillation about a horizontal or inclined axis
- D06F37/10—Doors; Securing means therefor
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F37/00—Details specific to washing machines covered by groups D06F21/00 - D06F25/00
- D06F37/26—Casings; Tubs
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F37/00—Details specific to washing machines covered by groups D06F21/00 - D06F25/00
- D06F37/26—Casings; Tubs
- D06F37/28—Doors; Security means therefor
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00
- D06F39/12—Casings; Tubs
- D06F39/14—Doors or covers; Securing means therefor
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- E—FIXED CONSTRUCTIONS
- E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
- E05Y—INDEXING SCHEME RELATING TO HINGES OR OTHER SUSPENSION DEVICES FOR DOORS, WINDOWS OR WINGS AND DEVICES FOR MOVING WINGS INTO OPEN OR CLOSED POSITION, CHECKS FOR WINGS AND WING FITTINGS NOT OTHERWISE PROVIDED FOR, CONCERNED WITH THE FUNCTIONING OF THE WING
- E05Y2900/00—Application of doors, windows, wings or fittings thereof
- E05Y2900/30—Application of doors, windows, wings or fittings thereof for domestic appliances
- E05Y2900/312—Application of doors, windows, wings or fittings thereof for domestic appliances for washing machines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B40/00—Technologies aiming at improving the efficiency of home appliances, e.g. induction cooking or efficient technologies for refrigerators, freezers or dish washers
Abstract
The present invention provides a coating composition for forming coating film having a gradient composition. The coating composition comprises a resin A, a resin B, a compatibilizer C and a solvent D, where the solution consisting of the resin A, the resin B, the compatibilizer C and the solvent D is transparent; the difference in the surface tension between the resin A and the resin B is at least 3 dyn/cm; the compatibilizer C has a weight-average molecular weight of 100-100,000 and a surface tension between those of the resins A and B and a solubility parameter between those of the resins A and B, or a part compatible with the resin A and/or a part compatible with the resin B in the molecule; and the solvent D has a difference in the solubility parameter within a specific range from those of the resins A and B; and the compositional ratio of the resin A and the resin B in the dry coating film formed changes continuously from the film surface in the depth direction.
Description
Technical field
The present invention relates to a kind of coating composition that is used to form coating film having gradient composition.The present invention is used for coating, tackiness agent, film etc.
Background technology
Up to now, for adopting organic materials and the compo of inorganic materials, the mixed adhesive of different sorts polymkeric substance etc. to comprise the composition of multiple composition, can bring into play filming of each composition advantage effectively with formation and just carry out various researchs with different performance.
The applicant has also submitted the application of this respect to, for example as all outstanding cation electrodeposition coating of corrosion and weathering resistance, contain the film cation electrodeposition coating (for example patent documentation 1 etc.) of plasticity resin of Resins, epoxy with cationic electrodeposition and non-ionic types such as acrylic resin, vibrin.The cationic electrodeposition that use is formed by this cation electrodeposition coating is bathed and is carried out galvanic deposit and apply filming of obtaining and can make the non-ionic type plasticity resin of filming float on the position, upper strata because of oven dry and capillary difference, in addition, Resins, epoxy can be that lower floor's position genetic horizon separates at metal base surface, consequently the position, upper strata is mainly occupied by the non-ionic type plasticity resin of filming, and the lower floor position is mainly occupied the multilayer film that has concentration gradient like this by Resins, epoxy.
The applicant has also submitted such application to, filming of forming by powder coating, using acrylic resin powder coating and epoxy resin based powder coatings or vibrin on the surface-treated steel plate is that the mixture of powder coating carries out powder coated one time, heating makes the sclerosis of filming, and formation acrylic resin powder is filmed on the upper strata, the epoxy resin powder is filmed or vibrin is that powder is filmed the multilayer film of lower floor (for example patent documentation 2 etc.).
The applicant is in order to realize above-mentioned effect, and then in patent documentation 3, proposed to form corrosion and all good coating method of filming of weathering resistance by 1 coating step on the steel structure body surface by containing the main agents that comprises specific acrylic resin, Resins, epoxy and 2 liquid type Air drying type coating compositions of amine hardener.
[patent documentation 1] spy opens clear 62-174277 communique
[patent documentation 2] spy opens clear 54-105135 communique
[patent documentation 3] spy opens the 2002-167545 communique
But by filming that above-mentioned Air drying type coating composition forms, its interior structure of forming of filming by resin properties of using and the decision of organic solvent kind is not desirable sometimes.
Summary of the invention
The object of the present invention is to provide a kind of coating composition, it can give full play to the advantage of various resins in the mixed system of different resins, and change continuously along depth direction by the film surface by the composition ratio of components in the dry coating that makes formation, form coating film having gradient composition.
The present invention relates to a kind of coating composition that is used to form coating film having gradient composition, it is characterized in that this coating composition contains resin (A), resin (B), solubilizing agent (C) and solvent (D), only by resin (A), resin (B), the solution that solubilizing agent (C) and solvent (D) form is transparent, the difference of the surface tension of resin (A) and resin (B) is more than 3dyn/cm, the weight-average molecular weight of solubilizing agent (C) is 100～100,000, its have between the surface tension value of the surface tension value that is positioned at resin (A) and resin (B) surface tension value and, be positioned at the solubility parameter value between the solubility parameter value of the solubility parameter value of resin (A) and resin (B), the part that mixes that perhaps has the mix part and/or the resin (B) of resin (A) in its molecule, solvent (D) is that difference with resin (A) and resin (B) solubility parameter value separately is at the independent solvent (D-1) below 3.0, or contain and the difference of the solubility parameter value of resin (A) the solvent below 1.5 (i) and with the difference of the solubility parameter value of resin (B) at the solvent below 1.5 (ii) as the mixed solvent (D-2) of its at least a portion composition, the composition ratio of components of resin in the dry coating of formation (A) and resin (B) is changed along depth direction continuously by the film surface.The invention still further relates to and on substrate surface, be coated with this coating composition and form the coated article that coating film having gradient composition makes in the formation method of Air drying acquisition coating film having gradient composition with by this method.
According to the present invention, for mixed with resin system not of the same race with specific surface tension difference, by using the composition that forms transparent uniform solution by specific solubilizing agent and solvent, can form composition ratio of components in the dry coating by the film surface along depth direction continually varying coating film having gradient composition, thereby can give full play to the advantage of each resin.And then the composition ratio of the table the inside of filming can be controlled by solubility parameter value, the velocity of evaporation of solvent.The coating film having gradient composition of Xing Chenging can be brought into play different performance on film surface and substrate interface like this.
The mixed system of acrylic resin and Resins, epoxy can form by 1 coating step and can give full play to filming of corrosion and weathering resistance two aspect performances as under the situation of Air drying type coating, is suitable for the coating on steel structure body etc.
Composition of the present invention contains resin (A), resin (B), solubilizing agent (C) and solvent (D), and only the solution that is obtained by resin (A), resin (B), solubilizing agent (C) and solvent (D) is transparent homogeneous.
Here so-called " transparent " is meant according to the experiment of the JIS K54004.2 transparency, in the developmental tube that the water white transparency of 2 about 15 * 150mm and internal diameter and wall thickness equate, pour sample and sample (deionized water) respectively into to about 100mm, two pipes are placed side by side, under scattering daylight, see through from the side and observe, the transparency is poor unlike sample, does not also find the state of suspended substance, precipitation and liquid phase separation.
For to be generally used for forming the resin of filming, the difference of its surface tension must be more than 3dyn/cm, preferably in 10～40dyn/cm scope for above-mentioned resin (A) and resin (B).If therefore the difference of this surface tension, then has the low surface tension composition less than 3dyn/cm can not be not preferred fully to the film surface orientation.
Surface tension in this specification sheets is the various resins of coating on sheet glass, and it is 100% independent resin molding that drying obtains solids component, is determined at 20 ℃ of contact angles of these resin moldings down according to water-paraffin method etc., calculates.
Composition ratio of components in its dry coating of coating film having gradient composition that is formed by the present composition is continuous variation by the film surface along depth direction, does not have clear and definite interface between the heterogeneity in filming.And each composition can not separate on the direction of base material being parallel to, and has equally distributed structure.
When the surface tension of above-mentioned resin (A) is hanged down than the surface tension of resin (B), the film surface of the dry coating of approaching more formation, the composition ratio of components of resin (A) is high more, when the surface tension of resin (B) is hanged down than the surface tension of resin (A), the film surface of the dry coating of approaching more formation, the composition ratio of components of resin (B) is high more.
This alternation is formed the affirmation of structure can be by for example, and the coating film having gradient composition that the physics cutting-out forms on various base materials is determined at resin on each depth location of the alternation face that obtains and forms recently and carry out by FT-IR spectrography etc.And, can in resin (A) or resin (B), add fluorescent probe, use the luminescence distribution of confocal its fluorescent probe of observation such as laser microscope to carry out.
And from forming the angle of transparent uniform solution and coating film having gradient composition, resin (A) is 0.2～4.0 with the difference expectation of the solubility parameter value of resin (B), preferably in 0.3～2.5 scope.
Resin dissolves parameter value in this specification sheets mainly on average condenses energy by constituent parts functional group and molecular volume decides, and is the index of expression dissolving power, can use the Fedors formula to calculate.For example see by R.F.Fedors at Polymer Engineering andScience about the detailed content of Fedors formula, 14, (2), and 1974, in p.147 giving a report.
The angle of the advantage of each resin from the performance coating film having gradient composition, the ratio of mixture of resin (A) and resin (B) counts 10/90～90/10 with the solids component weight ratio, preferably in 30/70～70/30 scope.
Above-mentioned resin (A), resin (B) are present known resin, for example acrylic resin, Resins, epoxy, vibrin, urethane resin, polyamide resin, polyolefin resin etc., can be therefrom aptly the close resin of the condition of stating of selector use.The molecular weight of these resins is not particularly limited, as long as can film forming, and can be according to selected aptly the getting final product such as the physical properties of filming of expectation.
When the surface tension of above-mentioned resin (A) is hanged down than the surface tension of resin (B), from alternation component film shaping aspect, it is 20～45dyn/cm that the surface tension of resin (A) is selected in expectation respectively, the surface tension of resin (B) such resin in 30～50dyn/cm scope, for example the resin that can select aptly to meet these conditions from the above-mentioned resin that illustrates for example uses.Each resin of above-mentioned example can use any one resin (A), resin (B) according to synthesis material that uses and performance number etc.
Particularly resin (A) is an acrylic resin, when resin (B) is Resins, epoxy, angle from the shaping of alternation component film, the surface tension of acrylic resin is in 20～45dyn/cm scope, the surface tension of Resins, epoxy is in 30～50dyn/cm scope, the difference of surface both tension force preferably is fit in 10～30dyn/cm scope more than 10dyn/cm.And, from the solution that forms transparent homogeneous and the angle of coating film having gradient composition, the solubility parameter value of acrylic resin is in 8.0～10.0 scopes, Resins, epoxy solubility parameter value is in 9.0～12.0 scopes, the difference of both solubility parameter values is 0.2～3.0, preferably expects in 0.3～2.0 scope.And then set out with the solution that forms transparent homogeneous and the angle of coating film having gradient composition, the ratio of mixture of aforesaid propylene acid resin and Resins, epoxy counts 10/90～90/10 with the solids component weight ratio, and is preferred 30/70～70/30th, suitable.
Usually can use the monomer mixture radical polymerization that will contain (methyl) acrylate, for example acrylic copolymer that in the presence of radical polymerization initiator, in organic solvent, obtains as the aforesaid propylene acid resin by solution polymerization." (methyl) vinylformic acid " meaning is " acrylic or methacrylic acid " in this specification sheets.
As above-mentioned (methyl) acrylate, for example can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, vinylformic acid 2-ethylhexyl fat, (methyl) vinylformic acid n-octyl, (methyl) lauryl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid isobornyl fat, (methyl) vinylformic acid tridecane ester, (methyl) vinylformic acid C1～24 alkyl esters such as (methyl) stearyl acrylate ester; The polymerizability unsaturated monomer of hydroxyls such as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, polyethyleneglycol (methyl) acrylate; Vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride etc. contain carboxyl polymerizability unsaturated monomer; (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-epoxy group(ing) cyclohexyl methyl ester etc. contains the epoxy-based polymerization unsaturated monomer; (methyl) vinylformic acid N, N dimethylamine base ethyl ester, (methyl) vinylformic acid N, N dimethylamine base ethyl ester, (methyl) vinylformic acid N, (methyl) acrylic-amino alkyl esters such as N dimethylamine base propyl ester; Acrylamide, Methacrylamide, N, N dimethylamine base ethyl (methyl) acrylamide, N, N dimethylamine base ethyl (methyl) acrylamide, N, (methyl) acrylamide or derivatives thereofs such as N dimethylamine base propyl group (methyl) acrylamide, N hydroxymethyl acrylamide, N hydroxymethyl acrylamide methyl ether, N hydroxymethyl acrylamide butyl ether; Vinyl cyanide, methacrylonitrile etc., these materials can use a kind or make up more than 2 kinds and to use.
As can with other polymerizability unsaturated monomers of above-mentioned (methyl) acrylic ester copolymer, that can enumerate has vinyl acetate between to for plastic, vinylchlorid, vinylbenzene, Vinyl toluene, an alpha-methyl styrene; Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxy propyl-triethoxysilicane etc. contain the unsaturated monomer of alkoxysilyl; (methyl) perfluoroalkyl acrylate classes such as (methyl) vinylformic acid perfluoro butyl ethyl ester, (methyl) vinylformic acid perfluoro capryl ethyl ester; Use CF
2=CF
2, CHF=CF
2, CH
2=CF
2Deng general formula CX
2=X
2(in the formula, X represents identical or different H, Cl, Br, F, alkyl or haloalkyl.But have at least 1 F in the formula) expression fluoroolefins; 2-(2 '-hydroxyl-5 '-methacryloxyethyl phenyl)-2H-benzotriazole, 4-(methyl) acryloxy-1,2,2,6, ultraviolet-absorbing such as 6-pentamethyl-piperidines or UV stable polymerizability unsaturated monomer etc., these materials can use a kind or make up more than 2 kinds and use.
Organic solvent when synthesizing as the aforesaid propylene acid resin is not particularly limited, that can enumerate has aromatic series hydrocarbon system organic solvents such as toluene, dimethylbenzene, ketone such as methylethylketone, mibk is organic solvent, esters such as N-BUTYL ACETATE are organic solvent, alcohol such as Virahol are organic solvent, petroleum spirit, normal hexane, octane, 2,2, the aliphatic hydrocarbon that 2-trimethylpentane, octane-iso, positive nonane, hexanaphthene, methylcyclohexane are such etc.These solvents are used singly or in combination can.The synthetic acrylic resin can directly use the organic solvent when synthetic, also can be by behind these organic solvents of volatilization such as drying under reduced pressure, and be dissolved in again in the desired organic solvent and use.
Polymerization starter is not particularly limited, can use Diisopropyl azodicarboxylate, 2,2-azo two (2-methylbutyronitrile), 2,2-azo two (2-methyl propionitrile), 2,2-azo two (2, the 4-methyl pentane nitrile) azo series initiators such as, superoxide such as benzoyl peroxide, tert-butyl hydroperoxide octanoate, diisobutyl superoxide, two (2-ethylhexyl peroxidation trimethylacetic acid ester), decanoyl peroxide.
The weight-average molecular weight of the acrylic resin that as above obtains is 1,000～150,000, preferred 2000～120,000.So-called weight-average molecular weight is to be the value that benchmark converts according to the molecular weight of gel permeation chromatography with the polystyrene molecular weight in this specification sheets.
Above-mentioned Resins, epoxy can be enumerated bisphenol A type epoxy resin, bisphenol f type epoxy resin, dihydroxyphenyl propane D type Resins, epoxy, bisphenol-A epoxy resin, cycloaliphatic epoxy resin, with these used for epoxy resin alkylphenols or/and the alkylphenol of the introducing epoxy group(ing) that fatty acid modified modified epoxy that obtains or alkyl bis-phenol or alkylphenol phenolic varnish type resin and epichlorohydrin reaction make or alkylphenol phenolic varnish type resin etc.
What the weight-average molecular weight of Resins, epoxy was fit to is in about scope of 200～about 3000, preferably in about scope of 300～about 1000.
Solubilizing agent of the present invention (C) is blended for the intermiscibility that improves resin (A) and resin (B), has the part that mixes of the mix part and/or the resin (B) of resin (A) usually in its molecule.By this solubilizing agent (C), when resin (A) and resin (B) can prevent layer separating of resin (A) and resin (B) during system for non-mixing, thereby can realize that obtaining alternation by two kinds of components forms structure.
The weight-average molecular weight of solubilizing agent of the present invention (C) is 100～100,000, it has the surface tension value between the surface tension value of the surface tension value that is positioned at resin (A) and resin (B), and be positioned at solubility parameter value between the solubility parameter value of the solubility parameter value of resin (A) and resin (B), perhaps have the part that mixes of the mix part and/or the resin (B) of resin (A) in its molecule.The words that exceed this scope, the solution that is formed by resin (A), resin (B), solubilizing agent (C) and solvent (D) can not keep transparent homogeneous, when making is filmed, can produce and film inequality or produce the unaccommodated situation of the instability that becomes in the storage etc., therefore not preferred.
, then can be ad lib in known resin and compound, select aptly to use as long as show above-mentioned effect as solubilizing agent (C), also can use a kind or make up more than 2 kinds and use.
Resin (A) is an acrylic resin, resin (B) is under the situation of Resins, epoxy, above-mentioned solubilizing agent (C) then has no particular limits as long as satisfy above-mentioned condition, particularly suitable is that its weight-average molecular weight is 300～100,000, has the surface tension value between the surface tension value of the surface tension value of acrylic resin and Resins, epoxy, and the solubility parameter value between the solubility parameter value of the solubility parameter value of acrylic resin and Resins, epoxy, perhaps weight-average molecular weight is 300～100,000, have the part that mixes of the mix part and/or the Resins, epoxy of acrylic resin in the molecule.That specifically can enumerate has, in acrylic resin copolymerization contain carboxyl the polymerizability unsaturated monomer, with Resins, epoxy in contained epoxy group(ing) at least partly or entirely react (methyl) acrylate that graft polymerization in the acrylic modified epoxy resin that makes, the Resins, epoxy or copolymerization aforesaid propylene acid resin enumerate in illustrating or other polymerizability unsaturated monomers etc. and the acrylic modified epoxy resin, the weight-average molecular weight that make are 300～2,000 Resins, epoxy etc.
The combined amount of above-mentioned solubilizing agent (C) is 5～100 weight parts with respect to total solids composition 100 weight parts of resin (A) and resin (B), preferably in the scope of 5～50 weight parts (solids component), this is fit to from the solution that forms transparent homogeneous and the angle of coating film having gradient composition.
Solvent of the present invention (D) is that difference with above-mentioned resin (A) and resin (B) solubility parameter value separately is below 3.0, preferred independent solvent (D-1) below 1.5, perhaps contain difference with the solubility parameter value of resin (A) below 1.5, preferably the solvent below 1.1 (i) and with the difference of the solubility parameter value of resin (B) below 1.5, preferably at the solvent below 1.1 (ii) as the mixed solvent (D-2) of at least a portion in its composition.The difference of solubility parameter value is not in above-mentioned scope the time, the solution that resin (A), resin (B), solubilizing agent (C) and solvent (D) form can not keep transparent homogeneous, having formation and can produce unfavorable situations such as the instability that becomes in the inequality of filming, the storage when filming, is not preferred.
And the angle that is shaped from coating film having gradient composition, the ratio rate of evaporation of above-mentioned solvent (D-1) is desirably in below 500, preferably 50～300, and then the angle that is shaped from coating film having gradient composition, solvent (i) in the solvent (D-2) and solvent ratio rate of evaporation (ii) is desirably in below 500, preferably 50～300.And then the difference of solvent (i) and solvent ratio rate of evaporation (ii) is desirably in more than 1 preferred 2～300.
Here the ratio rate of evaporation of solvent (D) is with the vaporator rate of the N-BUTYL ACETATE relative rate as 100 o'clock, the meaning be than rate of evaporation greater than 100 o'clock, the evaporite ratio N-BUTYL ACETATE is fast, less than 100 o'clock than N-BUTYL ACETATE slow evaporation.
The combined amount of solvent (D) more than 40 weight parts, is preferably used 40～350 weight parts for total solids component 100 weight parts of resin (A) and resin (B).The amount of solvent (D) is not in above-mentioned scope the time, and the system of dissolving resin (A) and resin (B) is difficult to keep transparent homogeneous, thereby does not expect.Contain solvent (i) in the mixed solvent (D-2) in addition and solvent total amount (ii) is desirably in more than the 50 weight %, more than the preferred 70 weight %.
Above-mentioned resin (A) is an acrylic resin, resin (B) is under the situation of Resins, epoxy, as what independent solvent (D-1) can be enumerated toluene arranged, aromatic series hydrocarbon system organic solvents such as dimethylbenzene, methylethylketone, ketone such as mibk are organic solvent, esters such as N-BUTYL ACETATE are organic solvent, alcohol such as Virahol are organic solvent, propylene glycol monomethyl ether, glycol ethers such as propylene glycol monobutyl ether are organic solvent, normal hexane, octane, 2,2, the 2-trimethylpentane, octane-iso, positive nonane, hexanaphthene, the organic solvents such as aliphatic hydrocarbon that methylcyclohexane is such, the solvent (i) that uses in the mixed solvent (D-2) can be enumerated toluene, aromatic series hydrocarbon system organic solvents such as dimethylbenzene, ketone such as mibk are organic solvent, esters such as N-BUTYL ACETATE are organic solvent, alcohol such as Virahol are organic solvent, propylene glycol monomethyl ether, glycol ethers such as propylene glycol monobutyl ether are organic solvent, normal hexane, octane, 2,2, the 2-trimethylpentane, octane-iso, positive nonane, hexanaphthene, the organic solvents such as aliphatic hydrocarbon that methylcyclohexane is such, solvent (ii) can be enumerated toluene, aromatic series hydrocarbon system organic solvents such as dimethylbenzene, methylethylketone, ketone such as mibk are organic solvent, esters such as N-BUTYL ACETATE are organic solvent, alcohol such as Virahol are organic solvent, propylene glycol monomethyl ether, glycol ethers such as propylene glycol monobutyl ether are organic solvent, normal hexane, octane, 2,2, the 2-trimethylpentane, octane-iso, positive nonane, hexanaphthene, the organic solvents such as aliphatic hydrocarbon that methylcyclohexane is such.Can in these materials, suit to select to use.
In the composition of the present invention, can comprise as required contain with above-mentioned resin (A) and/or resin (B) in contained functional group have the stiffening agent (E) of reactive functional group.The alternation by above-mentioned resin (A) and resin (B) gained that this stiffening agent (E) preferably can not hinder in the filming of formation is formed structure.Resin (A) is that acrylic resin, resin (B) are during for Resins, epoxy; Resins, epoxy affixture, ketoimine thing, polymeric amide amine, aromatic amine, aliphatics or the ester ring type mannich compound etc. that can use aliphatics for example or alicyclic polyamine, this polyamine are as stiffening agent (E), and it can be used alone or in combination of two or more kinds.The usage quantity of stiffening agent (E) is not preferably hindering alternation to form suitable selection use in the scope of structure.
In the composition of the present invention, can further not hinder alternation to form additives such as suitable hybrid pigment, UV light absorber, photostabilizer, hardening catalyst, tackifier, anti-sagging agent, flow agent, defoamer, dispersion agent, organic solvent in the scope of structure as required.
In the inventive method, can on substrate surface, be coated with the coating composition that obtains by aforesaid way, thus the dry coating film having gradient composition that forms.The drying conditions of the inventive method is not particularly limited, and from the angle of easy formation coating film having gradient composition, the Air drying condition is particularly preferred.Here so-called Air drying is near main drying room temperature, the drying under the drying conditions of external heat source not.
The coated surface that the substrate surface that glass, ceramic based material, metal based material, other various inorganic based materials, paper, timber, plastics etc. are arranged, its surface treatment face and then the coating thereon that can enumerate as substrate surface makes etc.Object lesson has the plastics film face, carries out the steel plate face of surface preparation or zinc-plated, old coating film face etc. as required.
Coating method as above-mentioned coating composition can use method commonly used such as brushing, roller coating, spraying, flow coat, various spreader coatings.From the angle of alternation and film properties, the expectation of the thickness of the coating film having gradient composition of formation is in the scope of 5～200 μ m, preferably in the scope of 10～120 μ m.
Description of drawings
Fig. 1 represents to form (content) by the acrylic resin along the depth direction that filming of obtaining of embodiment 1 measured by the FT-IR optical spectroscopy.
Embodiment
The present invention will be described in more detail below to enumerate embodiment.In addition, " part " and " % " does not have all expressions " weight part " and " weight % " of other explanations.
According to mixing ratio of components mixing acrylic resin (A-1) as shown in table 1, Resins, epoxy (B-1), solubilizing agent (C-1) and solvent (D-1), (D-2), make coating composition.The combined amount of acrylic resin, Resins, epoxy and solubilizing agent is the solids component amount in the table 1.
The coating composition applicator with gapping interval 250 μ m on sheet glass that obtains is coated with,, makes the experiment coated plate in room temperature (about 20 ℃) following dry 1 week.
Embodiment 2～4, comparative example 1～2
Except form according to the mixing of table 1 mix, making each coating composition, and make and respectively test coated plate with embodiment 1 identical step.
Each coating composition and its test coated plate to above-mentioned acquisition carry out following evaluation experimental.The result is shown in Table 1 in the lump.In addition, each composition is described as follows in the table 1.
Acrylic resin (A-1): by the multipolymer that following monomer is formed, weight-average molecular weight is 120,000, and surface tension is 33.1dyn/cm, and the solubility parameter value is 9.8.In addition, methacrylic acid 9-anthryl methyl esters adds in the acrylic resin as fluorescent probe, to observe its luminescence distribution under confocal some laser microscope.
40 parts of vinylbenzene
120 parts of Propenoic acid, 2-methyl, isobutyl esters
30 parts of isobutyl acrylate
10 parts of glycidyl methacrylate
0.5 part of methacrylic acid 9-anthryl methyl esters
Resins, epoxy (B-1): " Epikote 1001 ": Japan Epoxy Resins Co., Ltd. makes, trade(brand)name, bisphenol A type epoxy resin, epoxy equivalent (weight) 473, weight-average molecular weight 2800.Surface tension is 46.9dyn/cm, and the solubility parameter value is 11.5.
Solubilizing agent (C-1): the p-tert-butylphenol affixture of bisphenol A type epoxy resin, weight-average molecular weight 880.Surface tension is 44.8dyn/cm, and the solubility parameter value is 11.2.
Solubilizing agent (C-2): " Epikote 828EL ": Japan Epoxy Resins Co., Ltd. makes, trade(brand)name, bisphenol A type epoxy resin, epoxy equivalent (weight) 187, weight-average molecular weight 460.Surface tension is 30.8dyn/cm, and the solubility parameter value is 10.1.
Solubilizing agent (C-3): make by following steps.106 parts of petroleum spirits of heating and 86 parts " Epikote 828EL " dripped the mixture of following vinyl monomer and polymerization starter to 140 ℃ in 3 hours in nitrogen gas stream, dripped the back aging 2 hours.Add 0.04 part of tetraethylammonium bromide then, reacted about 2 hours,, obtain acrylic modified epoxy resin (C-3) when resinous acid value adds 31 parts of petroleum spirits during for 0.3mgKOH/g.The nonvolatile component of this resin solution is 65%, and epoxy equivalent (weight) is 652.The surface tension of acrylic modified epoxy resin (C-3) is 32.5dyn/cm, and the solubility parameter value is 8.9, and weight-average molecular weight is 50,000.
40 parts of vinylbenzene
120 parts of Propenoic acid, 2-methyl, isobutyl esters
30 parts of isobutyl acrylate
10 parts of glycidyl methacrylate
0.5 part of methacrylic acid 9-anthryl methyl esters
16 parts of tert-butyl hydroperoxide-2-ethylhexanoate
Solvent (D-1): mibk, solubility parameter value 8.6 is than rate of evaporation 165
Solvent (D-2): propylene glycol monomethyl ether, solubility parameter value 10.4 is than rate of evaporation 71
Stiffening agent (E-1): γ-An Jibingjisanyiyangjiguiwan.
(evaluation experimental)
(* 1) solution state: observe the solution of each coating composition, have or not muddiness evaluation with range estimation.
Transparent homogeneous: there is not muddiness in the mixing solutions, homogeneous, this state at least at room temperature kept for 1 week
Muddy: mixing solutions is uniform muddiness, is separated into 2 layers through for some time.
(* 2) are coated with membrane stage: visual observations is filmed and is had or not muddiness.
Transparent: the transparent homogeneous of filming
Muddy: filming is uniform muddiness
(* 3) alternation: use FT-IR device " FT/IR-420 " (Japanese beam split company make), measure film coated surface and substrate interface and the film acrylic resin of middle prescribed depth position and the composition ratio of components of Resins, epoxy according to the ATR method, thereby estimate respectively to test and be coated with the film component alternation on the coated plate, and use confocal some laser microscope " LSM-410 " (Carl Zeiss Japan manufacturing), observe luminous intensity by the fluorescent probe in the acrylic resin on the section of filming and confirm, estimate with following standard.In Fig. 1, illustrate respectively among the embodiment 1 and form (content) figure along the acrylic resin of the depth direction of filming.
A: all have the successive tapered structure from the film surface to substrate interface
B: have tapered structure at the film near surface
C: do not have tapered structure entirely
(* 4) corrosion: to except with the steel plate of petroleum ether degreasing as the base material and the coated plate that obtains of above-mentioned same procedure, the otch that cuts out wide 1mm is to arrive the bottom, carry out 100 hours brine spray experiment according to JIS K54009.1 after, the state that observation is filmed is estimated according to following standard.
Zero: not unusual
△: get rusty a little
*: obviously get rusty
Table 1
Claims (9)
1, a kind of coating composition that is used to form coating film having gradient composition, it is characterized in that this coating composition contains the resin that surface tension is 20～45dyn/cm (A), surface tension is the resin (B) of 30～50dyn/cm, solubilizing agent (C) and solvent (D), the difference of the surface tension of resin (A) and resin (B) is more than 3dyn/cm, the difference of the solubility parameter value of resin (A) and resin (B) is in 0.2～4.0 scope, the ratio of mixture of its resin (A) and resin (B) counts 10/90～90/10 with the solids component weight ratio, the weight-average molecular weight of solubilizing agent (C) is 100～100,000, it has the surface tension value between the surface tension value of the surface tension value that is positioned at resin (A) and resin (B), be positioned at the solubility parameter value between the solubility parameter value of the solubility parameter value of resin (A) and resin (B), the part that mixes that perhaps has the mix part and/or the resin (B) of resin (A) in its molecule, the combined amount of solubilizing agent (C) for total solids component 100 weight parts of resin (A) and resin (B) in 5～100 weight part scopes, solvent (D) is that difference with resin (A) and resin (B) solubility parameter value separately is at the independent solvent (D-1) below 3.0, or contain and the difference of the solubility parameter value of resin (A) the solvent below 1.5 (i) and with the difference of the solubility parameter value of resin (B) at the solvent below 1.5 (ii) as the mixed solvent (D-2) of its at least a portion composition, its combined amount for total solids component 100 weight parts of resin (A) and resin (B) in the scope of 40～350 weight parts, solvent (i) in the mixed solvent (D-2) and solvent total amount (ii) are more than the 50 weight %, the ratio rate of evaporation of solvent (D-1) is 50～300, solvent (i) in the solvent (D-2) and solvent ratio rate of evaporation (ii) is 50～300, the difference of solvent (i) and solvent ratio rate of evaporation (ii) is 2～300, only by resin (A), resin (B), the solution that solubilizing agent (C) and solvent (D) form is transparent, and the composition ratio of components of resin in the dry coating of formation (A) and resin (B) is changed along depth direction continuously by the film surface.
2, as the coating composition of claim 1 record, wherein the surface tension of resin (A) is lower than the surface tension of resin (B), and the closer to the dry coating surface that forms, the composition ratio of components of resin (A) is high more.
3, as the coating composition of claim 1 or 2 records, wherein resin (A) is an acrylic resin, and resin (B) is a Resins, epoxy.
4, the coating composition of putting down in writing as claim 3, wherein the surface tension of acrylic resin is 20～45dyn/cm, the surface tension of Resins, epoxy is 30～50dyn/cm, the difference of both surface tension is 3～20dyn/cm, the solubility parameter value of acrylic resin is 8.0～10.0, the solubility parameter value of Resins, epoxy is 9.0～12.0, and the difference of both solubility parameter values is 0.2～3.0.
5, as the coating composition of claim 3 record, wherein the weight-average molecular weight of solubilizing agent (C) is 300～100,000, has acrylic resin part and/or the Resins, epoxy part that mixes that mixes in the molecule.
6, the coating composition of putting down in writing as claim 3, wherein the weight-average molecular weight of solubilizing agent (C) is 300～100,000, its have between the surface tension value of the surface tension value of acrylic resin and Resins, epoxy surface tension value and, the solubility parameter value between the solubility parameter value of the solubility parameter value of acrylic resin and Resins, epoxy.
7, as the coating composition of claim 1 record, said composition contains stiffening agent (E), and this stiffening agent contains with contained functional group in resin (A) and/or resin (B) and has reactive functional group.
8, the formation method that the coating composition with any one record in the claim 1～7 is applied on the substrate surface, drying forms coating film having gradient composition at normal temperatures.
9, a kind of coated article that makes with the method formation coating film having gradient composition of claim 8 record.
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| JP200431157 | 2004-02-06 | ||
| JP2004031157 | 2004-02-06 | ||
| JP200525202 | 2005-02-01 | ||
| JP2005025202A JP4822392B2 (en) | 2004-02-06 | 2005-02-01 | Coating composition for forming a gradient composition coating film |
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| CN1814681A CN1814681A (en) | 2006-08-09 |
| CN100528988C true CN100528988C (en) | 2009-08-19 |
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| JP (1) | JP4822392B2 (en) |
| KR (1) | KR100649070B1 (en) |
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| KR101615404B1 (en) | 2010-04-05 | 2016-04-25 | 가부시키가이샤 제이올레드 | Organic display device and method for manufacturing the same |
| JP5533221B2 (en) * | 2010-05-12 | 2014-06-25 | 横浜ゴム株式会社 | Primer composition for sealing material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105689A (en) * | 1994-09-05 | 1995-07-26 | 辽宁省印刷技术研究所 | Metal paint resisting flushing and high-temp. boiling |
| CN1181775A (en) * | 1995-04-21 | 1998-05-13 | 松下电工株式会社 | Coating resin compsn. |
| CN1469911A (en) * | 2000-10-20 | 2004-01-21 | ������������ʽ���� | Water-based coating composition for can inner surfaces |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0699652B2 (en) * | 1986-01-28 | 1994-12-07 | 関西ペイント株式会社 | Cationic electrodeposition coating composition for forming multilayer film |
| JP2860779B2 (en) * | 1995-06-01 | 1999-02-24 | 大日本印刷株式会社 | Composition for coating |
| JP4000573B2 (en) * | 1996-10-07 | 2007-10-31 | 日本ペイント株式会社 | Cationic electrodeposition coating composition having excellent repellency resistance |
| JP4118356B2 (en) * | 1996-12-12 | 2008-07-16 | 日本ペイント株式会社 | Antifouling paint composition |
| JP4736144B2 (en) * | 1997-04-16 | 2011-07-27 | 日本ペイント株式会社 | High corrosion resistance, high weather resistance, cationic electrodeposition coating composition |
| JP4697996B2 (en) * | 1999-04-13 | 2011-06-08 | 三井化学株式会社 | Thermosetting powder coating composition |
| JP4201923B2 (en) * | 1999-06-08 | 2008-12-24 | 日本ペイント株式会社 | Multi-layer electrodeposition coating film and method for forming multilayer coating film including the coating film |
| JP2003328192A (en) * | 2002-03-08 | 2003-11-19 | Kansai Paint Co Ltd | Multilayer electrodeposition coating film forming method and coated product |
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- 2005-02-01 JP JP2005025202A patent/JP4822392B2/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105689A (en) * | 1994-09-05 | 1995-07-26 | 辽宁省印刷技术研究所 | Metal paint resisting flushing and high-temp. boiling |
| CN1181775A (en) * | 1995-04-21 | 1998-05-13 | 松下电工株式会社 | Coating resin compsn. |
| CN1469911A (en) * | 2000-10-20 | 2004-01-21 | ������������ʽ���� | Water-based coating composition for can inner surfaces |
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| JP4822392B2 (en) | 2011-11-24 |
| KR20060041724A (en) | 2006-05-12 |
| CN1814681A (en) | 2006-08-09 |
| JP2005248172A (en) | 2005-09-15 |
| KR100649070B1 (en) | 2006-11-27 |
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