CN102911572B - Coating composition and coating film-forming methods - Google Patents

Coating composition and coating film-forming methods Download PDF

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CN102911572B
CN102911572B CN201210275187.7A CN201210275187A CN102911572B CN 102911572 B CN102911572 B CN 102911572B CN 201210275187 A CN201210275187 A CN 201210275187A CN 102911572 B CN102911572 B CN 102911572B
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hydroxyl
coating
coating composition
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CN102911572A (en
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花冈敏行
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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Abstract

The invention provides a kind of coating composition that can obtain all excellent film of scuff resistance, acid resistance and stain resistance excellence and then finished appearance and toolability.Described coating composition, contains: the acrylic resin of hydroxyl, with the polymerizable unsaturated monomer of specific hydroxyl and containing the polymerizable unsaturated monomer etc. of alicyclic alkyl for copolymerization component; Polyisocyanate compounds, is made up of the aliphatic diisocyanate of the amount structure with specific polymer component; And the silica dioxide granule that polysiloxane is modified, there is the primary particle size of specified range.

Description

Coating composition and coating film-forming methods
Technical field
The present invention relates to the coating composition obtaining the also excellent film of scuff resistance, acid resistance and stain resistance excellence and then finished appearance and toolability.
Background technology
Require that being coated in car body waits for that the film performance such as scuff resistance, acid resistance, stain resistance, finished appearance of the coating in coat is excellent.
At present, treat coat coating as above-mentioned, widely using trimeric cyanamide crosslinked is coating.Trimeric cyanamide is cross-linked to be coating be containing hydroxy-containing resin and the melamine resin as linking agent coating.But trimeric cyanamide is crosslinked is that coating has trimeric cyanamide cross-link bond to be easily hydrolyzed because of acid rain, the problem of the acid resistance difference of film.
The two-component type urethane crosslinks system coating composition that a kind of acrylic resin, hydroxyl oligomer ester and isocyanate prepolymer by hydroxyl is formed is disclosed in Japanese Unexamined Patent Publication 6-220397 publication.Because the urethane crosslinks key of this coating is difficult to hydrolysis, so the acid resistance of film is excellent.But the scuff resistance of film is insufficient.
A kind of organic solvent system thermosetting coating compositions is disclosed in Japanese Unexamined Patent Publication 2000-136332 publication, it is characterized in that, containing compositions of thermosetting resin and colloidal silica, wherein, the content of colloidal silica is, the resin solid content of every 100 these resin combinations of weight part, with solid ingredient gauge be 3 ~ lower than 10 weight parts.This coating utilizes the effect of colloidal silica and surface hardness uprises, so excellent scratch resistance, but during as linking agent use melamine resin, the acid resistance of film is insufficient, and in addition, toolability is insufficient.
In WO2006/28130 publication, disclose a kind of coating composition, contain to contain the hydroxy-containing resin and fatty family polyisocyanate compounds that the polymerizable unsaturated monomer of alicyclic alkyl, the polymerizable unsaturated monomer of hydroxyl etc. are copolymerization component.The scuff resistance of the film of this coating and acid resistance are excellent, but sometimes the stain resistance of film and resistance to toolability insufficient.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 6-220397 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2000-136332 publication
Patent documentation 3:WO2006/28130 publication
Summary of the invention
The object of this invention is to provide a kind of coating composition that can obtain all excellent film of scuff resistance, acid resistance and stain resistance excellence and then finished appearance and toolability.
The present inventor conducts in-depth research to solve above-mentioned problem, found that the coating composition of the silica dioxide granule that the acrylic resin, polyisocyanate compounds and the polysiloxane that utilize containing hydroxyl are modified, can achieve the above object, thus complete the present invention, wherein, the acrylic resin of described hydroxyl with hydroxyl polymerizable unsaturated monomer, containing the polymerizable unsaturated monomer etc. of specific alicyclic alkyl for copolymerization component, described polyisocyanate compounds is made up of the aliphatic diisocyanate comprising specific polymer component.
that is, the invention provides the coating composition shown in the following:
Item 1. coating compositions, it comprises:
The acrylic resin (A) of hydroxyl, it is the multipolymer of monomer component, and described monomer component comprises: the polymerizable unsaturated monomer (a) of the hydroxyl of 25 quality % to 50 quality %; 5 quality % to 30 quality % contain C 6-C 20the polymerizable unsaturated monomer (b) of alicyclic alkyl; And 20 other polymerizable unsaturated monomers (c) of quality % to 70 quality %;
Polyisocyanate compounds (B), it comprises aliphatic diisocyanate, based on the total amount of described polyisocyanate compounds, described polyisocyanate compounds (B) comprises other polymkeric substance comprising at least three kinds of monomers of the isocyanate trimer of 30 quality % to 70 quality %, the urea diketone dimer of 3 quality % to 30 quality % and 0 quality % to 67 quality %; And
The silica dioxide granule (C) that polysiloxane is modified, described in each, the average primary particle diameter of the silica dioxide granule (C) that polysiloxane is modified is 1nm to 40nm.
The coating composition of item 2. as described in item 1, wherein, described containing C 6-C 20the polymerizable unsaturated monomer (b) of alicyclic alkyl comprises at least one be selected from (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) t-butylcyclohexyl ester, (methyl) vinylformic acid ring ten diester, (methyl) isobornyl acrylate, (methyl) vinylformic acid diamantane ester and (methyl) vinylformic acid three ring ester in the last of the ten Heavenly stems.
The coating composition of item 3. as described in item 1 or 2, wherein, the weight-average molecular weight of the acrylic resin (A) of described hydroxyl is 5,000 to 30,000.
The coating composition of item 4. as described in any one of item 1 to 3, wherein, the silica dioxide granule (C) that described polysiloxane is modified comprises the polysiloxane of organic decoration separately as polysiloxane.
The coating composition of item 5. as described in any one of item 1 to 3, wherein, the silica dioxide granule (C) that described polysiloxane is modified comprises at least one in polydimethylsiloxane and polydiphenylsiloxane separately as polysiloxane.
The coating composition of item 6. as described in any one of item 1 to 5, wherein, the isocyanate groups in described polyisocyanate compounds (B) is 0.8 to 1.5 with the equivalence ratio (NCO/OH) of the hydroxyl in the acrylic resin (A) of described hydroxyl.
The coating composition of item 7. as described in any one of item 1 to 6, wherein, based on the acrylic resin (A) of described hydroxyl and the total amount of described polyisocyanate compounds (B), the ratio of mixture of the acrylic resin (A) of described hydroxyl is 55 quality % to 80 quality %, the ratio of mixture of described polyisocyanate compounds (B) is 20 quality % to 45 quality %, and the ratio of mixture of the silica dioxide granule (C) of described polysiloxane modification is 0.1 quality % to 10 quality %.
The coating composition of item 8. as described in any one of item 1 to 7, wherein, the second-order transition temperature (Tg) of the film formed by described coating composition is 70 ° of C to 110 ° of C.
In addition, the invention provides the article comprising the film obtained by coating aforementioned coating composition.
In addition, the invention provides the method forming multilayer film, it comprise use at least one deck pigmented basecoat coating and at least one deck Clearcoat coating in succession apply object to be coated, wherein said coating comprises and is used as the aforementioned coating composition of the Clearcoat coating for the superiors to apply.
Think coating composition of the present invention by containing polysiloxane modify silicon-dioxide and excellent scratch resistance, and acrylic resin has the clicyclic hydrocarbon structure of hard in a large number and becomes the film of high rigidity, so toolability and the also excellent film of stain resistance can be obtained.
Think that silicon-dioxide that polysiloxane is modified is different from the silica dioxide granule be not wrapped by with the general colloidal silica particle surface that is representative, that there is the particle by the coated structure of the organic layer of polysiloxane, so the space steric effect of the organic layer reactive functional groups that suppresses to remain in the surface of silica dioxide granule with as the acrylic resin of binder ingredients or polyisocyanate compounds, and then other silica dioxide granules, the reaction of reactive functional groups, so compared with when using the silica dioxide granule of unmodified, silica dioxide granule in the coating composition, stable in the film formed in addition, and be uniformly distributed in film.
Thus, the characteristic that silica dioxide granule has is imparted in the matrix structure of binder ingredients equably, thus the mechanical properties of film can be made by leaps and bounds to improve, therefore, it is possible to obtain the film of particularly excellent scratch resistance.
In addition, polyisocyanate compounds particularly as crosslinker component more has for low-molecular-weight urea diketone dimer component in the structure of the amount of polymer component, so the mobility of coating film after coating improves, the film that finished appearance is also excellent can be obtained.Because also in the lump containing isocyanate trimer, so solidified nature is also excellent, cross-linking density improves, thus the also excellent film of scuff resistance can be obtained.
And then crosslinking structure is the urethane crosslinks structure of the hydrolytic resistance excellence under acid effect, so the also excellent film of acid resistance can be obtained.
As mentioned above, utilize coating composition of the present invention, can obtain scuff resistance, acid resistance and stain resistance excellent and then, finished appearance and all excellent film of toolability.
Embodiment
Below describe coating composition of the present invention (hereinafter sometimes referred to " this coating ") and method of forming layered coating film in detail.
The feature of coating composition of the present invention is, contains: the acrylic resin (A) of hydroxyl, with the polymerizable unsaturated monomer of specific hydroxyl and containing the polymerizable unsaturated monomer etc. of alicyclic alkyl for copolymerization component; Polyisocyanate compounds (B), is made up of the aliphatic diisocyanate of the amount structure with specific polymer component; And the silica dioxide granule (C) that polysiloxane is modified, there is the primary particle size of specified range.
the acrylic resin (A) of hydroxyl
The acrylic resin (A) of hydroxyl makes by the polymerizable unsaturated monomer of (a) hydroxyl, (b) carbon atom quantity to be prepared by the monomer component copolymerization that the polymerizable unsaturated monomer of the alicyclic alkyl of 6 ~ 20 and (c) other polymerizable unsaturated monomers are formed by ordinary method.
The polymerizable unsaturated monomer (a) of hydroxyl is the compound respectively in 1 molecule with 1 hydroxyl and unsaturated link(age), and this hydroxyl works as main functional group of reacting with the polyisocyanate compounds (B) as linking agent.As this monomer, specifically preferably acrylic or methacrylic acid and carbonatoms are the monoesters compound of the dibasic alcohol of 2 ~ 10, such as, can enumerate (methyl) hydroxyalkyl acrylates such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxybutyl, (methyl) vinylformic acid 4-hydroxybutyl.And then, as this monomer, the ring opening polyaddition thing etc. of lactone such as above-mentioned (methyl) hydroxyalkyl acrylates and 6-caprolactone etc. can be enumerated.Specifically, such as can enumerate " PLACCEL FA-1 ", " PLACCEL FA-2 ", " PLACCEL FA-3 ", " PLACCEL FA-4 ", " PLACCEL FA-5 ", " PLACCEL FM1 ", " PLACCEL FM2 ", " PLACCEL FM3 ", " PLACCEL FM4 ", " PLACCELFM5 " (being DIACEL chemistry (strain) system above, trade(brand)name) etc.
As the polymerizable unsaturated monomer (a) of hydroxyl, by making to relax as the polyisocyanate compounds of linking agent and the reactivity of acrylic resin (A), thus the finished appearance of the film obtained can be made to improve, the therefore preferred polymerizable unsaturated monomer (a1) containing having secondary hydroxyl.
As the polymerizable unsaturated monomer (a1) with secondary hydroxyl, the carbonatoms such as can enumerating the alkyl in the ester portion of the unsaturated monomers (a1) such as (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxybutyl, (methyl) vinylformic acid 3-hydroxybutyl is 2 ~ 8, is preferably the polymerizable unsaturated monomer with secondary hydroxyl of 2 ~ 4 and then preferably 2 ~ 3.Particularly preferably can use (methyl) vinylformic acid 2-hydroxy propyl ester.When the carbonatoms of this alkyl is more than 5, the finished appearance of film reduces sometimes, and in addition, the working life of coating composition reduces sometimes.They can be used alone or be two kinds or more.
There is the total amount of proportioning relative to monomer component of the polymerizable unsaturated monomer (a1) of secondary hydroxyl, be preferably 25 ~ 50 quality % and then be preferably 25 ~ 45 quality % and then be particularly preferably in the scope of 25 ~ 40 quality %.
In addition, never make the acid resistance of film reduce and improve scuff resistance aspect and consider, also preferably use and have the polymerizable unsaturated monomer (a2) of cyclohexyl ring and hydroxyl.Specifically can enumerate CHDMMA (Japan changes into society's system, 1,4 cyclohexane dimethanol mono acrylic ester) etc.
As unsaturated monomer (a2), and then also can use and such as make to there is (wait mole) reactant reaction of the polyester oligomer of hydroxy-cyclohexyl or hydroxymethylcyclohexyl and (methyl) acrylate of diisocyanate cpd and hydroxyl and the macromonomer etc. obtained at molecule two end.As above-mentioned polyester oligomer, such as, can enumerate " Off レ キ ソ レ ッ ズ 148, ", " Off レ キ ソ レ ッ ズ 188 " (being trade(brand)name, the U.S., King Industries society system) etc.
In addition, by with above-mentioned and have the polymerizable unsaturated monomer of cyclohexyl ring and hydroxyl (a2) for copolymerization component and obtain and have the acrylic resin of cyclohexyl ring and hydroxyl such as also by the acrylic resin that makes to have hydroxyl and the acid anhydrides (such as hexahydrophthalic anhydride) with cyclohexyl ring, addition reaction can occur and then made by acid/epoxy reaction and have the compound of epoxy group(ing) and hydroxyl (such as Racemic glycidol etc.) and the carboxylic acid generation addition reaction generated by this addition reaction and obtain the method for terminal hydroxyl etc. and obtain.
The proportioning of the polymerizable unsaturated monomer (a) of hydroxyl is preferably 25 ~ 50 quality % relative to the total amount of monomer component, is particularly preferably 25 ~ 45 quality % and then is particularly preferably in the scope of 25 ~ 40 quality %.
When the proportioning of the polymerizable unsaturated monomer (a) of hydroxyl is lower than 25 quality %, sometimes cured coating film crosslinked insufficient, scuff resistance is insufficient.On the other hand, during more than 50 quality %, reduce with the intermiscibility of the monomer component (unsaturated monomer (b) or unsaturated monomer (c)) beyond unsaturated monomer (a), copolyreaction, and then the acrylic resin of the hydroxyl obtained (A) reduces with the intermiscibility of other components (silica dioxide granule (C) that polyisocyanate compounds (B) or polysiloxane are modified), thus the finished appearance of the film obtained reduces sometimes.
Should illustrate, in this specification sheets, " (methyl) acrylate " refers to " acrylate or methacrylic ester ".
Polymerizable unsaturated monomer (b) containing alicyclic alkyl is the polymerizable unsaturated monomer of the alicyclic alkyl being 6 ~ 20 containing carbonatoms.
By with unsaturated monomer (b) for copolymerization component, the second-order transition temperature of the acrylic resin (A) of hydroxyl is made to increase, polarity reduces, so the stain resistance of film, the effect of water tolerance raising that the finished appearance that can obtain being obtained by film coated surface smoothing improves and obtains.
Be the typical example of the alicyclic alkyl of 6 ~ 20 as carbonatoms, cyclohexyl, ring octyl group, cyclo-dodecyl, isobornyl, adamantyl, tristane base etc. can be enumerated.
As the concrete example of the polymerizable unsaturated monomer (b) containing alicyclic alkyl, such as can enumerate (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl (such as (methyl) vinylformic acid 4-methylcyclohexyl methyl esters), (methyl) acrylic acid ethyl cyclohexylmethyl (such as (methyl) vinylformic acid 4-ethylcyclohexyl methyl esters), (methyl) methoxyethyl cyclohexylmethyl (such as (methyl) vinylformic acid 4-methoxycyclohexyl methyl esters), (methyl) t-butylcyclohexyl ester, (methyl) vinylformic acid ring octyl group ester, (methyl) acrylate base esters such as (methyl) vinylformic acid ring ten diester, (methyl) isobornyl acrylate, (methyl) vinylformic acid three ring ester in the last of the ten Heavenly stems, (methyl) vinylformic acid diamantane ester, (methyl) vinylformic acid 3, the polymerizable unsaturated monomer containing bridge alicyclic alkyl such as 5-dimethyladamantane ester, (methyl) vinylformic acid 3-Fourth Ring ten diester, as preference, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate etc. can be enumerated.
Proportioning containing the polymerizable unsaturated monomer (b) of alicyclic alkyl is preferably 5 ~ 30 quality % relative to the total amount of monomer component, is particularly preferably 10 ~ 30 quality % and then is particularly preferably in the scope of 10 ~ 25 quality %.
During containing the proportioning of the polymerizable unsaturated monomer (b) of alicyclic alkyl lower than 5 quality %, the hardness of cured coating film is insufficient sometimes, stain resistance is insufficient.On the other hand, during more than 30 quality %, sometimes cured coating film much higher hard and the finished appearance of film is reduced.
Other polymerizable unsaturated monomers (c) are the polymerizable unsaturated monomers (a) of above-mentioned hydroxyl and have the compound of 1 unsaturated link(age) containing in 1 molecule beyond the polymerizable unsaturated monomer (b) of alicyclic alkyl, and its concrete example is set forth in following (1) ~ (8).
(1) containing the polymerizable unsaturated monomer of acidic group: the compound in 1 molecule with more than 1 acidic group and 1 unsaturated link(age), such as, the carboxylic polymerizable unsaturated monomers such as (methyl) vinylformic acid, butenoic acid, methylene-succinic acid, toxilic acid and Maleic Acid, Anhydrous can be enumerated; Vinyl sulfonic acid, (methyl) sulfoethyl acrylate etc. are containing sulfonic polymerizable unsaturated monomer; The acid phosphoric acid ester system polymerizable unsaturated monomers etc. such as 2-(methyl) acryloxyacetic acid phosphoric acid ester, 2-(methyl) acryloxy propionic phosphoric acid ester, 2-(methyl) acryloxy-3-chloropropionic acid phosphoric acid ester, 2-methaciylyloxyethylphenyl phosphoric acid.They can use a kind or use in combination of two or more.The above-mentioned polymerizable unsaturated monomer containing acidic group also can work as internal activator when (A) component and linking agent (B) component generation crosslinking reaction, and its usage quantity preferably uses based on the total amount of the monomer component of the acrylic resin (A) of formation hydroxyl in the scope of 0 ~ 5 quality %, particularly 0.1 ~ 3 quality %.
(2) acrylic or methacrylic acid and carbonatoms are the monoesters compound of the monohydroxy-alcohol of 1 ~ 20: such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butylacrylate, (methyl) i-butyl base ester, (methyl) acrylate tert-buthyl, (methyl) 2-EHA, (methyl) isooctyl acrylate ester, the different tetradecyl ester of (methyl) vinylformic acid, vinylformic acid isooctadecane base ester (Osaka Organic Chemical Industry society system, trade(brand)name), (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) octadecyl acrylate, (methyl) vinylformic acid tetrahydro furfuryl ester etc.
In addition, in above-claimed cpd, the carbonatoms with branched structure can be preferably used to be the polymerizable unsaturated monomer (c2-1) of the alkyl of more than 8 from the viewpoint of improving the scuff resistance of film.By with polymerizable unsaturated monomer (c2-1) for be formed monomer component, in the acrylic resin obtained (A), part imports soft structures, in addition, the polarity of resin reduces, and improves so can obtain the film scuff resistance brought by imparting flexibility and improves effect by the surface smoothing finishability brought.In addition, because have branched structure, so the second-order transition temperature of film can be suppressed to reduce, so be also favourable from the viewpoint of acid resistance raising with the polymerizable unsaturated monomer of the alkyl with the carbonatoms with straight-chain being more than 8 compared with when being formed component.
As having the concrete example that the carbonatoms having branched structure is the polymerizable unsaturated monomer of the alkyl of more than 8, in above-claimed cpd, such as, can enumerate 2-EHA, (methyl) isooctyl acrylate ester, the different tetradecyl ester of (methyl) vinylformic acid, vinylformic acid isooctadecane base ester (Osaka Organic Chemical Industry society system, trade(brand)name).
During with polymerizable unsaturated monomer (c2-1) for being formed component, its proportioning is preferably 3 ~ 40 quality % relative to the total amount of monomer component, is particularly preferably in the scope of 10 ~ 30 quality %.
(3) containing the polymerizable unsaturated monomer of alkoxysilyl: such as vinyltrimethoxy silane, vinyltriethoxysilane, acryloyl-oxyethyl Trimethoxy silane, methacryloxyethyl Trimethoxy silane, acryloxypropyl Trimethoxy silane, methacryloxypropyl trimethoxy silane, acryloxypropyl triethoxyl silane, methacryloxypropyl, vinyl three ('beta '-methoxy oxyethyl group) silane etc.Wherein, as the preferred polymerizable unsaturated monomer containing alkoxysilyl, vinyltrimethoxy silane, γ-acryloxypropyl Trimethoxy silane, γ-methacryloxypropyl trimethoxy silane etc. can be enumerated.
By with containing the polymerizable unsaturated monomer of alkoxysilyl for being formed component, except the cross-link bond of hydroxyl and isocyanate group, the cross-link bond formed by the reaction of the mutual condensation reaction of alkoxysilyl and alkoxysilyl and hydroxyl can also be generated.Thus, from the viewpoint of the cross-linking density raising of the film obtained, the effect that scuff resistance, acid resistance and stain resistance improve can be obtained.
During with the polymerizable unsaturated monomer containing alkoxysilyl for being formed component, its proportioning is preferably 1 ~ 20 quality % relative to the total amount of monomer component, is particularly preferably in the scope of 1 ~ 10 quality %.
(4) fragrant family polymerizable unsaturated monomer: such as vinylbenzene, alpha-methyl styrene, Vinyl toluene etc.
By with fragrant family polymerizable unsaturated monomer for being formed component, the Tg of the resin obtained rises, in addition, the hydrophobicity film of high refractive index can be obtained, thus can obtain improve that the finished appearance brought improves by the gloss of film, effect that water tolerance and acid resistance improve.Therefore, as other polymerizable unsaturated monomers (c), preferably comprise the fragrant family polymerizable unsaturated monomer such as above-mentioned vinylbenzene (4).
During with fragrant family polymerizable unsaturated monomer for being formed component, its proportioning is preferably 3 ~ 50 quality % relative to the total amount of monomer component, is particularly preferably in the scope of 5 ~ 40 quality %.
(5) containing the polymerizable unsaturated monomer of glycidyl: the compound respectively in 1 molecule with 1 glycidyl and unsaturated link(age), be specifically glycidyl acrylate, methyl propenoic acid glycidyl base ester etc.
(6) nitrogenous polymerizable unsaturated monomer: such as acrylamide, Methacrylamide, DMAA, N, N-dimethyl propyl acrylamide, N-butoxy methyl acrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, diacetone acrylamide, N, N-dimethyl aminoethyl (methyl) acrylate, vinyl pyridine, vinyl imidazole etc.
(7) other vinyl compounds: such as vinyl-acetic ester, vinyl propionate base ester, vinylchlorid, VEOVA 9, VEOVA 10 (Japan EpoxyResin) etc. as versatic acid vinyl ester.
(8) containing the nitrile based compound of unsaturated link(age): such as vinyl cyanide, methacrylonitrile etc.
Other polymerizable unsaturated monomers (c) above-mentioned can use one kind or two or more.
The monomer mixture copolymerization be made up of above-mentioned polymerizable unsaturated monomer (a), (b) and (c) can be obtained the acrylic resin (A) of hydroxyl.
Copolymerization process for above-mentioned monomer mixture copolymerization being obtained the acrylic resin (A) of hydroxyl is not particularly limited, known copolymerization process itself can be used, wherein can be preferably used in organic solvent, carry out the solution polymerization process that is polymerized under the existence of polymerization starter.
As the organic solvent used during above-mentioned solution polymerization process, such as, can enumerate the aromatic series series solvents such as toluene, dimethylbenzene, SWASOLVE1000 (COSMO oil society system, trade(brand)name, high point petroleum series solvent); The ester series solvents such as ethyl acetate, 3-methoxybutyl acetic ester, ethylene glycol monoethyl ether acetate, methyl proxitol acetate; The ketone series solvents such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone, propionic acid propyl diester, propionic acid butyl ester, propionic acid ethoxyethyl group ester etc.
Above-mentioned organic solvent can use a kind or use in combination of two or more, and preferably uses high boiling ester series solvent, ketone series solvent from the viewpoint of the solvability of acrylic resin.In addition, and then also can use by appropriately combined high boiling aromatic series series solvent.
The polymerization starter that can use during acrylic resin (A) copolymerization as hydroxyl; such as can enumerate 2; 2 '-Diisopropyl azodicarboxylate, benzoyl peroxide, ditertiary butyl peroxide, two t-amyl peroxy compounds, tert-butyl hydroperoxide octanoate, 2, the radical polymerization initiator that 2 '-azo two (2-methylbutyronitrile) etc. itself are known.
From the viewpoint of having scuff resistance and water tolerance concurrently, the hydroxyl value of the acrylic resin (A) of hydroxyl is preferably 120 ~ 200mgKOH/g and then is preferably 130 ~ 200mgKOH/g and then is particularly preferably in the scope of 140 ~ 200mgKOH/g.
The weight-average molecular weight of the acrylic resin of hydroxyl is preferably in the scope of 5000 ~ 30000, and then is preferably 5000 ~ 20000 and then be particularly preferably in the scope of 10000 ~ 20000.By making weight-average molecular weight be more than 5000, the film performances such as acid resistance can being suppressed to reduce, in addition, by being less than 30000, the finished appearance reduced with film smoothness can be suppressed to reduce, so preferably.
Should illustrate, in this specification sheets, weight-average molecular weight is the value calculated for benchmark with the molecular weight of polystyrene standard by the chromatogram by gel permeation chromatography.Gel permeation chromatography uses " HLC8120GPC " (Dong Caoshe system).As post, use " TSKgel G-4000HXL ", " TSKgel G-3000HXL ", such 4 of " TSKgel G-2500HXL ", " TSKgel G-2000HXL " (being eastern Cao (strain) society system, trade(brand)name), in moving phase: tetrahydrofuran (THF), mensuration temperature: 40 DEG C, flow velocity: 1cc/ divides, detector: carry out under the condition of RI.
The second-order transition temperature of the acrylic resin (A) of hydroxyl is preferably-30 DEG C ~ 30 DEG C, is particularly preferably in the scope of-20 DEG C ~ 20 DEG C.If second-order transition temperature is lower than-30 DEG C, then hardness of film is insufficient sometimes, and in addition, if more than 30 DEG C, then the painting face smoothness of film and resistance to Fractured reduce sometimes.
In addition, the acrylic resin that so-called urethane is modified also is comprised in the acrylic resin (A) of hydroxyl.
The acrylic resin (A) of hydroxyl can be used alone or be two kinds or more.
In coating composition of the present invention, as matrix resin, also can as required also with the resin beyond the acrylic resin (A) of hydroxyl.Therefore, in coating composition of the present invention, also comprise contain hydroxyl as matrix resin acrylic resin (A) beyond the coating composition of resin.Specifically, such as can enumerate vibrin, polyether resin, urethane resin etc., as preference, hydroxyl group containing polyester resin and hydroxyl urethane resin can be enumerated.
Hydroxyl group containing polyester resin can be utilized well-established law, be prepared by the esterification of such as polyprotonic acid and polyvalent alcohol.This polyprotonic acid is the compound in 1 molecule with more than 2 carboxyls, such as, can enumerate phthalic acid, m-phthalic acid, terephthalic acid, succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, tetrahydrophthalic acid, hexahydrophthalic acid, toxilic acid, fumaric acid, methylene-succinic acid, trimellitic acid, Pyromellitic Acid and their acid anhydrides etc., in addition, this polyvalent alcohol is the compound in 1 molecule with more than 2 hydroxyls, such as, can enumerate ethylene glycol, propylene glycol, 1,3-PD, BDO, 1,5-PD, 1,6-hexylene glycol, 2,2-diethyl-1,3-PD, neopentyl glycol, 1,9-nonanediol, Isosorbide-5-Nitrae-cyclohexanediol, hydroxyl trimethylacetic acid DOPCP, 2-butyl-2-ethyl-1,3-PD, 3-methyl isophthalic acid, 5-pentanediol, 2,2,4-neopentyl glycol, the glycolss such as hydrogenation biphenol A, and TriMethylolPropane(TMP), trimethylolethane, glycerol, the polyol component more than ternarys such as tetramethylolmethane, and, 2,2-dimethylol propionic acid, the acid of 2,2-dihydroxymethyl butane, the acid of 2,2-dihydroxymethyl pentane, the acid of 2,2-dihydroxymethyl hexane, the hydroxycarboxylic acids etc. such as 2,2-dihydroxymethyl octanesulfonic acid.
In addition, also can make the mono-epoxy compounds such as the alpha-olefin such as propylene oxide and butylene oxide ring epoxide, CarduraE10 (glycidyl esters of Japan Epoxy Resin society system, trade(brand)name, synthesis height chain saturated fatty acid) etc. and acid-respons and above-claimed cpd is imported vibrin.
When carboxyl is imported vibrin, such as, also can hydroxyl polyester carry out half-esterification by acid anhydrides is added to and import.
The hydroxyl value of hydroxyl group containing polyester resin is preferably in the scope of 100 ~ 200mgKOH/g, and then is preferably in the scope of 120 ~ 180mgKOH/g.The weight-average molecular weight of hydroxyl group containing polyester resin is preferably in the scope of 2500 ~ 40000, and then is preferably in the scope of 5000 ~ 30000.
As hydroxyl urethane resin, the hydroxyl urethane resin by making polyvalent alcohol and polymeric polyisocyanate react and obtain can be enumerated.
As polyvalent alcohol, such as, as low-molecular-weight polyvalent alcohol, the trivalent alcohols etc. such as the dibasic alcohol such as ethylene glycol, glycol ether, propylene glycol, butyleneglycol, hexamethylene glycol, TriMethylolPropane(TMP), glycerol, tetramethylolmethane can be enumerated.As the polyvalent alcohol of high molecular, polyether glycol, polyester polyol, acrylic polyol, epoxy polyol etc. can be enumerated.As polyether glycol, macrogol, polypropylene glycol, polytetramethylene glycol etc. can be enumerated.As polyester polyol, above-mentioned dibasic alcohol, dipropylene glycol, 1 can be enumerated, the lactone such as polycondensate, the polycaprolactone opening polymerization polymer polyvalent alcohol, polycarbonate diol etc. of the diprotic acid such as alcohol and hexanodioic acid, nonane diacid, sebacic acid such as 4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol.In addition, the carboxylic polyvalent alcohol such as 2,2-dimethylol propionic acid, 2,2-dihydroxymethyl butane acid can such as also be used.
As the polymeric polyisocyanate with above-mentioned polyol reaction, such as, can enumerate the aliphatic polymeric isocyanate compounds such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, lysinediisocyanate, and the biuret type affixture of above-mentioned polymeric polyisocyanate, isocyanic ester cycloaddition thing, isophorone diisocyanate, 4,4 '-methylene-bis (cyclohexyl isocyanate), methylcyclohexane-2,4-(2,6-) vulcabond, 1,3-(Isosorbide-5-Nitrae)-two (isocyanatomethyl) hexanaphthene, Isosorbide-5-Nitrae-cyclohexyl diisocyanate, 1, the alicyclic diisocyanate compounds such as 3-pentamethylene vulcabond, 1,2-cyclohexyl diisocyanate, and the biuret type affixture of above-mentioned polymeric polyisocyanate, isocyanic ester cycloaddition thing, xylylene diisocyanate, between xylylene diisocyanate, tetramethyl-xylylene diisocyanate, first phenylene diisocyanate, 4, 4 '-diphenylmethanediisocyanate, 1, 5-naphthalene diisocyanate, 1, 4-naphthalene diisocyanate, 4, 4 '-toluidine diisocyanate, 4, 4 '-diphenyl ether diisocyanate, (or to) phenylene diisocyanate, 4, 4 '-biphenylene vulcabond, 3, 3 '-dimethyl-4, 4 '-biphenylene vulcabond, two (4-isocyanatophenyl) sulfone, the aromatic diisocyanate compounds such as isopropylidene two (4-phenyl isocyanate), and the biuret type affixture of above-mentioned polymeric polyisocyanate, isocyanic ester cycloaddition thing, triphenyl methane-4,4 ', 4 "-triisocyanate, 1,3,5-triisocyanate base benzene, 2,4,6-triisocyanate base toluene, 4,4 '-dimethyl diphenylmethane-2,2 ', 5,5 '-tetraisocyanate etc. have the polyisocyanate compounds of more than 3 isocyanate group in 1 molecule, and the biuret type affixture of above-mentioned polymeric polyisocyanate, isocyanic ester cycloaddition thing, Deng.
The hydroxyl value of hydroxyl urethane resin is preferably in the scope of 80 ~ 200mgKOH/g, and then is preferably in the scope of 100 ~ 180mgKOH/g.The weight-average molecular weight of hydroxyl urethane resin is preferably in the scope of 2500 ~ 40000, and then is preferably in the scope of 5000 ~ 30000.The second-order transition temperature of hydroxyl urethane resin is preferably-40 DEG C ~ 85 DEG C and then be preferably in the scope of-30 DEG C ~ 80 DEG C.
And during with resin (being more specifically vibrin, polyether resin, urethane resin etc.) beyond the acrylic resin (A) of above-mentioned hydroxyl, the resin-phase beyond the acrylic resin (A) of this hydroxyl is preferably below 100 quality % for the solid ingredient total amount of the acrylic resin (A) of hydroxyl, is more preferably in the scope of 10 ~ 50 quality %.
polyisocyanate compounds (B)
The polyisocyanate compounds (B) of coating composition of the present invention is made up of aliphatic diisocyanate, and aliphatic diisocyanate refers to the diisocyanate cpd in the structure of diisocyanate cpd with aliphatic alkyl chain.The carbonatoms of aliphatic alkyl chain is preferably 4 ~ 30, be particularly preferably 4 ~ 20 and then be particularly preferably 4 ~ 10.In the present invention, polyisocyanate compounds (B) comprises isocyanate trimer and urea diketone dimer.Aliphatic diisocyanate can also containing polymers more than other tripolymers.In the present invention, " polyisocyanate compounds (B) is made up of aliphatic diisocyanate " represents that polyisocyanate compounds (B) is that raw material generates with aliphatic diisocyanate, more specifically, such as represent that polyisocyanate compounds (B) is obtained by the multimerization of aliphatic diisocyanate (Dimerized, tripolymer etc.).
As aliphatic diisocyanate, specifically such as can enumerate trimethylene diisocyanate, tetramethylene-1,4-vulcabond, pentamethylene-1,5-vulcabond, 1, hexamethylene-diisocyanate, 1,2-trimethylene diisocyanate, 1,2-tetramethylene diisocyanate, 2,3-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate, 2,2,4-trimethylammoniums-hexa-methylene-1,6-vulcabond, 2,6-cyanato methyl capronates, lysinediisocyanate etc.Wherein, from the viewpoint of the easiness that scuff resistance, industry are bought, particularly preferably use hexamethylene diisocyanate (hereinafter referred to as HMDI).
Isocyanate trimer as one of the formation component of polyisocyanate compounds refers to polymeric polyisocyanate that be made up of 3 molecule diisocyanate monomers, that have isocyanate group.
In polyisocyanate compounds, the content of isocyanate trimer is benchmark with the total amount of polyisocyanate compounds (B) is 30 ~ 70 quality %, be preferably 40 ~ 70 quality % and then be preferably 50 ~ 70 quality %.If lower than 30 quality %, then the viscosity of polyisocyanate compounds (composition) increases sometimes, and bridging property reduces.In addition, if more than 70 quality %, then this viscosity increases, so finished appearance reduces sometimes.
When deriving the polymeric polyisocyanate containing isocyanate group by diisocyanate monomer, isocyanation esterification catalyzer usually can be used to carry out.As concrete isocyanation esterification catalyzer, such as generally preferred have alkaline catalyzer, there is (1) tetramethyl-ammonium, the oxyhydroxide of the tetra-allkylammoniums such as tetraethyl ammonium or such as acetic acid, the organic monoacid salt such as capric acid, (2) trimethylammonium hydroxypropyl ammonium, trimethylammonium hydroxyethyl ammonium, triethyl hydroxypropyl ammonium, the oxyhydroxide of hydroxyalkyl ammonium or the such as acetic acid such as triethyl hydroxyethyl ammonium, the organic monoacid salt such as capric acid, (3) acetic acid, caproic acid, sad, the such as tin of the alkyl carboxylic acids such as tetradecanoic acid, zinc, plumbous, sodium, the metal-salts such as potassium, (4) sodium, the metal alkoxides such as potassium, (5) hexamethyldisilazane etc. are containing the compound of amino silyl, (6) Mannich bases, (7) the also use etc. of tertiary amines and epoxy compounds.
In above-claimed cpd, from the viewpoint of the selectivity (isocyanation esterification) of reaction, particularly preferably (1), (2), (3).Sometimes generation urea diketone is there is, generates the side reactions such as the polymeric polyisocyanate of biuret-containing base in the compound containing amino silyl according to its working conditions.
Above-mentioned catalyzer can be used and obtain the polymeric polyisocyanate containing isocyanate group.The polymeric polyisocyanate containing isocyanate group obtained, except tripolymer, also comprises the polymer such as pentamer, heptamer.Transformation efficiency (mass ratio of the polymeric polyisocyanate generated by isocyanation esterification reaction) for obtaining the isocyanation esterification reaction of the isocyanate trimer concentration range of afore mentioned rules is preferably less than 20% and then preferably less than 15%.If more than 20%, then be sometimes difficult to obtain as constitutive requirements afore mentioned rules, isocyanate trimer concentration, the finished appearance of the film sometimes obtained is insufficient.
In the reaction of above-mentioned isocyanation esterification, sometimes generate polymeric polyisocyanate etc. containing uretdion containing the polymeric polyisocyanate beyond the polymeric polyisocyanate of isocyanate group simultaneously.The urea diketone dimer relative concentration generated by isocyanation esterification reaction, in the polymeric polyisocyanate generated by isocyanation esterification reaction, is preferably below 2 quality %, is more preferably below 1 quality %.
As polyisocyanate compounds one of formation component, urea diketone dimer refers to polymeric polyisocyanate that be made up of 2 molecule diisocyanate monomers, that have uretdion.
In polyisocyanate compounds, the dimeric content of urea diketone is benchmark from the viewpoint of the solidified nature of coating composition and the finished appearance of film that obtains with the total amount of polyisocyanate compounds (B) is 3 ~ 30 quality %, be preferably 5 ~ 25 quality % and then be preferably 8 ~ 20 quality %.If lower than 3 quality %, then the viscosity of polyisocyanate compounds (composition) increases sometimes, and the finished appearance of the film obtained reduces.In addition, if more than 30 quality %, then the solidified nature of coating composition reduces sometimes.
Urea diketone dimer can use the diketonate catalyzer of urea to obtain.As the diketonate catalyzer of urea, specifically such as have as tertiary phosphine, the cycloalkyl phosphines etc. such as trialkyl phosphine, three (dimethylamino) phosphine etc. three (dialkyl amido) phosphine, cyclohexyl di-n-hexyl phosphine such as tri-n-butyl phosphine, tri-n-octyl phosphine.Above-claimed cpd also can be obtained by allophanatization catalyzer.In addition, the great majority in above-claimed cpd also promote isocyanation esterification reaction simultaneously, also generate the polymeric polyisocyanate containing isocyanate group except containing the polymeric polyisocyanate of uretdion.
In addition, also can not use above-mentioned catalyzer and be obtained by heating.The yield of polymeric polyisocyanate containing uretdion obtained by heating is low, as being inefficent for the means obtained containing the polymeric polyisocyanate of uretdion.
But, distinguished that not use catalyzer, the diisocyanate monomer amount free when storing containing the polymeric polyisocyanate of uretdion that obtain by means of only heating very low.
Once thought that uretdion easily decomposed because of heating, so storage causes from the diisocyanate monomer that dissociates containing the polymeric polyisocyanate of uretdion.
Consider above-mentioned reason, as the polymeric polyisocyanate containing uretdion of one of the formation component of polyisocyanate compounds preferably by adding hot preparation.
In polyisocyanate compounds, preferably not biuret-containing type polymeric polyisocyanate.
Aforesaid isocyanation esterification reaction, the diketonate reaction of urea can successively be carried out respectively, also can carry out side by side.Preferably first carry out isocyanation esterification reaction, then carry out the diketonate reaction of urea, isocyanation esterification reaction use catalyzer, the diketonate reaction of urea are undertaken simplifying preparation section, so preferably by heating.
After above-mentioned reaction completes, unreacted diisocyanate monomer is removed by thin film evaporation still, extraction etc.
Preferably not containing unreacted diisocyanate monomer in polyisocyanate compounds, residual diisocyanate monomer concentration is preferably below 1 quality %, and then is preferably below 0.5 quality %.
The aliphatic diisocyanate of polyisocyanate compounds (B) is formed except isocyanate trimer and urea diketone dimer in the present invention, can also containing polymers more than other tripolymers.
As polymers more than other tripolymers, be not particularly limited, known polymer itself can be widely used, such as, can enumerate urea diketone tripolymer etc.
Polyisocyanate compounds (B) can be used alone or uses in combination of two or more.
In polyisocyanate compounds, viscosity when 25 DEG C is preferably 100 ~ 3000mPas and then is preferably 200 ~ 2000mPas and then is preferably 200 ~ 1000mPas.If lower than 100mPas, then the solidified nature of coating composition of the present invention reduces sometimes.In addition, if more than 3000mPas, then the finished appearance of the film sometimes obtained reduces.
In polyisocyanate compounds (B), with the total amount of polyisocyanate compounds for benchmark, the content of isocyanate trimer is 30 ~ 70 quality %, is preferably 40 ~ 70 quality % and then is preferably 50 ~ 70 quality %, the dimeric content of urea diketone is 3 ~ 30 quality %, is preferably 5 ~ 25 quality % and then is preferably 8 ~ 20 quality %, and polymeric content more than other tripolymers is 0 ~ 67 quality %, is preferably 5 ~ 55 quality % and then is preferably in the scope of 10 ~ 42 quality %.
In addition, in above-mentioned polyisocyanate compounds, also can use as the closure polyisocyanate compounds of the compound that free isocyanate group blocking agent is obtained.
Encapsulant is the material free isocyanate group closed.Closure polyisocyanate compounds by being heated to such as more than 100 DEG C, being preferably more than 130 DEG C, can make isocyanate group regenerate, easily reacts with hydroxyl.As this encapsulant, such as, can enumerate the phenol systems such as phenol, cresols, xylenol, nitrophenols, ethylphenol, xenol, butylphenol, isopropyl-phenol, nonylphenol, octyl phenol, methyl hydroxybenzoate; The lactan systems such as ε-caprolactam, δ-Valerolactim, butyrolactam, azetidinone; The fatty alcohol systems such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, dodecyl alcohol; The ether systems such as ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, carbiphene, propylene glycol monomethyl ether, methoxyl group methyl alcohol; Phenylcarbinol; Oxyacetic acid; The ethyl glycolates such as methyl glycolate, ethyl glycollate, butyl glycolate; The lactates such as lactic acid, methyl lactate, ethyl lactate, n-Butyl lactate; The alcohol systems such as methylolurea, melamine methylol, diacetone alcohol, vinylformic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester; The oxime systems such as formyl amidoxime, acetyl amidoxime, acetoxime, methyl ethyl ketone oxime, diacetyl monooxime, diphenylketoxime, hexanaphthene oxime; Dimethyl malonate, diethyl malonate, methyl aceto acetate, methyl acetoacetate, Acetyl Acetone isoreactivity methylene base system; The mercaptan system such as butanethiol, tert-butyl mercaptan, hexyl mercaptans, tertiary lauryl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol; Acetyl replaces the sour acid amides systems such as methoxy propanamine, N-ethanoyl Ortho Toluidine, acrylamide, Methacrylamide, ethanamide, stearylamide, benzamide for propylamine, acetyl; The imide series such as succinimide, phthalic imidine, maleimide; The amine systems such as diphenylamine, phenyl naphthyl amines, xylidine, N-phenyl xylidine, carbazole, aniline, ALPHA-NAPHTHYL AMINE, butylamine, dibutylamine, butyl phenyl amine; The imidazoles systems such as imidazoles, 2-ethyl imidazol(e); The pyrazoles systems such as 3，5-dimethylpyrazole; The urea systems such as urea, thiocarbamide, ethylidene-urea, ethylene thiourea, diphenyl urea; The carbamate systems such as N-phenylcarbamic acid phenylester; Second embraces the imines such as imines, tetrahydroform system; The encapsulants such as the sulphite such as S-WAT, potassium sulfite system.
When carrying out closure (encapsulant is reacted), solvent can be added as required and carry out.As the solvent used in closure reaction, can use and reactive solvent is not had to isocyanate group, such as, can enumerate acetone, methyl ethyl ketone and so on ketone, ethyl acetate and so on ester class, the kind solvent of N-Methyl pyrrolidone (NMP).
In addition, as required, also can be used together beyond the polyisocyanate compounds (B) be such as made up of above-mentioned aliphatic polymeric isocyanate, aliphatic polymeric isocyanate, alicyclic polymeric isocyanate, aromatic-aliphatic polymeric polyisocyanate, aromatic poly-isocyanate and above-mentioned polymeric polyisocyanate derivative etc.Therefore, coating composition of the present invention also can comprise beyond the polyisocyanate compounds (B) that is made up of above-mentioned aliphatic polymeric isocyanate, aliphatic polymeric isocyanate, alicyclic polymeric isocyanate, aromatic-aliphatic polymeric polyisocyanate, aromatic poly-isocyanate and above-mentioned polymeric polyisocyanate derivative etc.
As the aliphatic polymeric isocyanate beyond the polyisocyanate compounds be made up of aliphatic polymeric isocyanate (B), such as can enumerate lysine ester triisocyanate, 1,4,8-triisocyanate base octane, 1,6,11-triisocyanate base undecane, 1,8-diisocyanate based-4-isocyanatomethyl octane, 1,3,6-triisocyanate base hexane, 2, the aliphatics triisocyanates etc. such as 5,7-trimethylammonium-1,8-diisocyanate based-5-isocyanatomethyl octane.
As alicyclic polymeric isocyanate, such as can enumerate 1, 3-cyclopentene diisocyanate, 1, 4-cyclohexyl diisocyanate, 1, 3-cyclohexyl diisocyanate, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexylisocyanate (common name: isophorone diisocyanate), 4, 4 '-methylene-bis (cyclohexyl isocyanate), methyl-2, 4-cyclohexyl diisocyanate, methyl-2, 6-cyclohexyl diisocyanate, 1, 3-or 1, two (isocyanatomethyl) hexanaphthenes (common name: hydrogenated xylylene vulcabond) of 4-or its mixture, the alicyclic diisocyanates such as norbornene alkyl diisocyanate, such as 1, 3, 5-triisocyanate butylcyclohexane, 1, 3, 5-trimethylammonium isocyanic ester butylcyclohexane, 2-(3-isocyanate group propyl group)-2, 5-bis-(isocyanatomethyl)-dicyclo (2.2.1) heptane, 2-(3-isocyanate group propyl group)-2, 6-bis-(isocyanatomethyl)-dicyclo (2.2.1) heptane, 3-(3-isocyanate group propyl group)-2, 5-bis-(isocyanatomethyl)-dicyclo (2.2.1) heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanate group propyl group)-dicyclo (2.2.1) heptane, 6-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanate group propyl group)-dicyclo (2.2.1) heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanate group propyl group)-dicyclo (2.2.1)-heptane, the alicyclic triisocyanates etc. such as 6-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanate group propyl group)-dicyclo (2.2.1) heptane.
As aromatic-aliphatic polymeric polyisocyanate, such as can enumerate 1,3-or 1,4-xylylene diisocyanate or its mixture, ω, ω '-diisocyanate based-1,4-diethylbenzene, 1,3-or 1, the two araliphatic diisocyanate, such as 1 such as (1-isocyanate group-1-methylethyl) benzene (common name: tetramethyl-xylylene diisocyanate) or its mixture of 4-, the aromatic-aliphatic triisocyanates etc. such as 3,5-triisocyanate ylmethyl benzene.
As aromatic poly-isocyanate, such as can enumerate a phenylene diisocyanate, to phenylene diisocyanate, 4, 4 '-diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, 2, 4 '-or 4, 4 '-diphenylmethanediisocyanate or its mixture, 2, 4-or 2, 6-first phenylene diisocyanate or its mixture, 4, 4 '-toluidine diisocyanate, 4, the aromatic diisocyanates such as 4 '-diphenyl ether diisocyanate, such as triphenyl methane-4, 4 ', 4 ' "-triisocyanate, 1, 3, 5-triisocyanate base benzene, 2, 4, the aromatic tri-isocyanates such as 6-triisocyanate base toluene, such as 4, 4 '-ditan-2, 2 ', 5, the aromatic series tetraisocyanates etc. such as 5 '-tetraisocyanate.
In addition, as the derivative of polymeric polyisocyanate, such as, can enumerate the dimer of above-mentioned polyisocyanate compounds, tripolymer, biuret, allophanate, carbodiimide, urea diketone, ketal imines, isocyanic ester, oxadiazine triketone, polymethylene polyphenyl base polymeric polyisocyanate (rough MDI, polymeric MDI) and rough TDI etc.
The above-mentioned polyisocyanate compounds that can carry out as required using can be used alone, and in addition, also may be two kinds or more.
the silica dioxide granule (C) that polysiloxane is modified
The silica dioxide granule (C) that polysiloxane is modified is the silica dioxide granule with the structure that particle surface is modified by polysiloxane chain.
As silica dioxide granule, such as, can use powder silicon-dioxide, colloidal silica.In addition, silica dioxide granule can use the particle of the arbitrary shape in spherical, hollow form, vesicular, bar-shaped, tabular, threadiness and indefinite shape etc., wherein preferably spherical particle.
In addition, as silica dioxide granule, preferably use the colloidal silica obtained in water or organic solvent by silica particle Granular composite.When using colloidal silica, preferably use with the state of dispersion liquid.As the dispersion liquid of colloidal silica, preferably its medium is organic solvent.As this organic solvent, methyl alcohol, Virahol, ethylene glycol, butanols, ethylene glycol list propyl ether, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, dimethylbenzene, dimethyl formamide etc. can be enumerated.In addition, also can use by above-mentioned solvent two or more and with and the mixed solvent that obtain or by water miscible organic solvent and water and use and the mixed solvent that obtains.In above-mentioned organic solvent, carry out easiness, particular methanol, Virahol, methyl ethyl ketone, dimethylbenzene from the viewpoint of the modification reaction to silica particles.
As the method that silica particles is modified with polysiloxane chain, such as, can enumerate: use the organoalkoxysilane with polysiloxane chain to be carried out the method for modifying by the dealcoholization of the silanol with silica particles; The organoalkoxysilane with polysiloxane chain is hydrolyzed in the presence of water and after producing silanol group, is carried out the method for modifying by the dehydration condensation between this silanol group and silanol group of silica particles; The method etc. of modifying is carried out by the dehydration condensation had between the alcohol of polysiloxane chain and the silanol group of silica particles.
In addition, as the additive method that silica particles is modified with polysiloxane chain, can enumerate: make the organoalkoxysilane with reactive group (be commonly referred to as silane coupling agent, hereinafter referred to as " compound (C1) ") occur to dewater or after dealcoholization condensation reaction, enable the method that the compound (C2) with functional group and the polysiloxane chain forming chemical bond with above-mentioned reaction-ity group reaction reacts at silica particles by method similar to the above; And then make compound (C1) and there is the reaction-ity group reaction had with compound (C1) and the compound (C2) of the functional group and polysiloxane chain that can form chemical bond reacts in advance, after obtaining having the alkoxysilane compound containing trialkylsilyl group in molecular structure of polysiloxane chain, make the method etc. of this compound and silica dioxide granule reaction.
As the reactive group that above-claimed cpd (C1) has, such as, can enumerate epoxy group(ing), amino, sulfydryl, isocyanate group etc.In addition, as the concrete example of compound (C1), such as can enumerate the compound that 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl group triethoxyl silane etc. have epoxy group(ing); N-2-(amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, N-2-(amino-ethyl)-APTES, 3-TSL 8330, APTES etc. have amino compound; 3-mercaptopropyi methyl dimethoxysilane, 3-mercaptopropyi Trimethoxy silane etc. have the compound of sulfydryl; 3-isocyanate group propyl-triethoxysilicane etc. has the compound etc. of isocyanate group.
The reactive group that the functional group that above-claimed cpd (C2) has has according to compound (C1) is selected.When the reactive group that compound (C1) has is epoxy group(ing), the functional group that above-claimed cpd (C2) has is preferably carboxyl.In addition, the reactive group that compound (C1) has is for time amino, and the functional group that above-claimed cpd (C2) has is preferably epoxy group(ing).And then, when the reactive group that compound (C1) has is sulfydryl, the functional group that above-claimed cpd (C2) has is preferably isocyanate group, when the reactive group that compound (C1) has is isocyanate group, the functional group that above-claimed cpd (C2) has is preferably hydroxyl or sulfydryl.In addition, above-claimed cpd (C2) preferably has functional group at the one-side ends of polysiloxane chain.
Because reaction is easily so particularly preferably when the functional group that in aforesaid combination, the reactive group that compound (C1) has is isocyanate group, above-claimed cpd (C2) has is hydroxyl.
As the compound of the formation polysiloxane chain that above-claimed cpd (C2) has, polydimethyl oxirane, poly-phenylbenzene oxirane etc. can be enumerated.In addition, be bonded in organic group on the Siliciumatom of above-mentioned polysiloxane can all identical also can be different.
When the functional group that the reactive group that above-claimed cpd (C1) has is isocyanate group, above-claimed cpd (C2) has is hydroxyl, the usage quantity of above-claimed cpd (C1) with 1 mole of above-claimed cpd (C2) for benchmark, be preferably 0.5 ~ 1.1, never compound (C1) aspect of remained unreacted is considered, is particularly preferably 0.9 ~ 1.0 mole.
In addition, in above-mentioned situation, the reaction of compound (C1) and compound (C2) can be carried out under solvent-free, also can use solvent, but becomes good from the viewpoint of the mobility of reaction solution and preferably use solvent.As solvent, such as, can enumerate the ester series solvents such as ethyl acetate, butylacetate, propylene glycol monomethyl ether; The ether series solvents such as Di Iso Propyl Ether, glycol dimethyl ether, diethylene glycol dimethyl ether; The halogen such as methylene dichloride, ethylene dichloride series solvent; The aromatic series such as toluene, dimethylbenzene series solvent; The ketone series solvents such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone; The aprotic polar solvent such as dimethyl formamide, dimethyl sulfoxide (DMSO) etc.In above-mentioned solvent, preferred ester series solvent, ketone series solvent, ether series solvent.
In addition, in order to promote the reaction of above-claimed cpd (C1) and compound (C2), preferably react under the existence of polyurethane-reinforcement catalyzer.As polyurethane-reinforcement catalyzer, such as, can enumerate the amine catalysts such as pyridine, pyrroles, triethylamine, diethylamide, dibutylamine; The phosphine catalyst such as triphenylphosphine, triethyl phosphine; The organo-tin compounds such as dibutyltindilaurylmercaptide cinnamic acid salt, tin octylate trilauryl salt, tin octylate diacetin, dibutyltin diacetate, stannous octoate; The organometallic compounds etc. such as zinc octoate.In addition, because and carry out smoothly, so preferably with polyurethane-reinforcement reaction when organo-tin compound and amine.
As the modifier for obtaining the silica dioxide granule that polysiloxane is modified, preferredization compound can enumerate the compound (polysiloxane) with polysiloxane chain that following general formula represents.
(R 1 xR 2 3-xSiR 3) yR 5(1)
In above-mentioned general formula, x=0 ~ 2, particularly 0, y=1 ~ 10, preferably 2 ~ 5, R 1to be carbonatoms be, and 1 ~ 18, particularly carbonatoms are the monovalent organic group of 1 ~ 3, r 2 be by hydroxyl or carbonatoms be 1 ~ 6 particularly carbonatoms be 1 ~ 2 straight-chain, particularly chlorine or carbonatoms are 1 ~ 4, preferably carbon is former for the alkoxyl group of chain or ring-type, halogen atom subnumber is the hydrolization group of carboxylic acid group's formation of 2, r 3 be by oxygen or preferred carbonatoms the straight-chain of 1 ~ 8 or the alkylidene group of side chain, alkylene ether, alkylen thioether, be preferably epoxy alkylidene group polyethers, the alkylene of ethane, propylene oxide or butylene oxide ring or the mixture based on them base polyethers, alkylene polyesters or also there is polyurethane-base and/or urea groups except ester group and/or ether the divalence that forms of organic fatty race, aromatic series or araliphatic groups (araliphatic group) organic group, and R 5be by having the number-average molecular weight of number-average molecular weight 300 ~ 5000, the carbonatoms of the alkyl substituent of Siliciumatom be 1 ~ 8 the organic group that forms of poly-diakyl oxirane.
by the above-mentioned compound (polysiloxane) with polysiloxane chainthe silica dioxide granule modified is coated by this compound (modifier), the functionality response gene remaining in the surface of silica dioxide granule inhibits the reactivity with other functional groups because of sterically hindered, so silica dioxide granule in the coating composition, in addition also extremely stable in the film formed, and to be evenly distributed in film.This compound (modifier) is by the surface of covalent bonding at silica dioxide granule.
In addition, this compound (modifier) has more than at least 1 or 2 fixed base of reacting with surface and the polysiloxane of silica dioxide granule.
And then, there is the end that this binding affinity fixed base is introduced into this polysiloxane, and be also present in a side chain of this polysiloxane.
in the compound (polysiloxane) that what above-mentioned general formula (1) represented have polysiloxane chain, as so preferred compound, the compound that following general formula (2) represents can be enumerated.
R 1 xR 2 3-xSi－R 3－R 4(2)
Herein, R 4be by number-average molecular weight be 300 ~ 5000, the monovalent organic group that forms of the alkyl substituent of the Siliciumatom poly-diakyl oxirane with the carbonatoms of 1 ~ 8.
The compound (modifier) that above-mentioned formula (2) represents is head base, the bonding temporary location (R of the responding property of surface had silica dioxide granule 3) and poly-diakyl oxirane (R 4) compound of straight chain structure of terminal group.
This compound via at least 1, be preferably more than 2, be more preferably 3 covalent linkage by the surface of covalent bonding at silica dioxide granule.And then, this compound comprise can not and silica dioxide granule surface reaction and be the interval component (poly-diakyl oxirane (R of inertia to (A) component and (B) component 4)).
Relative to the polysiloxane chain modification amount of silica particle solids constituent mass, relative to the solid ingredient total amount of silica dioxide granule, being preferably 0.1 ~ 80 quality %, from the viewpoint of film coated surface being modified efficiently, being preferably 0.1 ~ 40 quality %.
The primary particle size of the silica dioxide granule (C) that polysiloxane is modified is preferably 1 ~ 100nm, is more preferably 1 ~ 50nm, and then is more preferably 1 ~ 40nm.
Should illustrate, in the present invention, above-mentioned primary particle size refers to that the accumulation size distribution of being started at by small particle size side in the size-grade distribution of volume reference is the particle diameter (D of 50% 50).
The size-grade distribution of volume reference is by laser diffraction/scattering method.In the present invention, the size-grade distribution of the volume reference of the silica dioxide granule (C) that polysiloxane is modified uses laser diffraction/diffuse transmission type particle size distribution device " MICROTRAC NT3300 " (trade(brand)name, Ji Zhuan society system) to measure.Now, sample concentration adjusts by the regulation transmitance scope reached set by device.
In coating composition of the present invention, from the viewpoint of the solidified nature, scuff resistance etc. of film, the equivalence ratio (NCO/OH) of the hydroxyl in the acrylic resin (A) of the isocyanate group in polyisocyanate compounds (B) and hydroxyl is preferably 0.8 ~ 1.5 and then be preferably 0.8 ~ 1.2 and then be particularly preferably in the scope of 0.80 ~ 1.15.
In coating composition of the present invention, the amount of the silica dioxide granule (C) that the acrylic resin (A) of hydroxyl, polyisocyanate compounds (B) and polysiloxane are modified is advisable with following ranges, that is: with the total amount of (A) component and (B) component for benchmark as non-volatile contentthe acrylic resin (A) of hydroxyl is 55 ~ 80 quality %, is preferably 60 ~ 75 quality %, polyisocyanate compounds (B) is 20 ~ 45 quality %, is preferably 25 ~ 40 quality %, and the silica dioxide granule (C) that polysiloxane is modified is 0.1 ~ 10 quality %, is preferably 0.2 ~ 5 quality % and then is preferably in the scope of 0.3 ~ 3 quality %.
From the viewpoint of obtaining the excellent and then finished appearance of scuff resistance, acid resistance and stain resistance and the also excellent film of toolability, the second-order transition temperature (Tg) of the film formed by coating composition of the present invention is preferably 70 ~ 110 DEG C and then preferably in the scope of 70 ~ 100 DEG C.
Should illustrate, in the present invention, the second-order transition temperature (Tg) of film is the value obtained by Measurement of Dynamic Viscoelasticity.
Dynamic viscoelastic be determined at the condition of heat-up rate 3 DEG C/min, temperature range 20 ~ 200 DEG C, frequency 11Hz under carry out.The temperature when second-order transition temperature (Tg DEG C) of film is the value display maximum value of tan δ in this mensuration.As Measurement of Dynamic Viscoelasticity device, use FTRheospectra DVE-V4 (Rheology society system, trade(brand)name, Measurement of Dynamic Viscoelasticity device).
other components
The coating composition of this coating to be the silicon-dioxide (C) modified with the acrylic resin of hydroxyl (A), polyisocyanate compounds (B) and polysiloxane be necessary component, usually containing organic solvent, and then the additive for coatings that usually can use in the field of coating containing other curing catalysts, pigment, pigment dispersing agent, flow agent, rheology control agent, UV light absorber, photostabilizer, softening agent etc. as required.
As above-mentioned curing catalysts, such as, can enumerate organo-metallic catalyst, the tertiary amines etc. such as stannous octoate, dibutyl tin two (2-ethylhexoate), dioctyl tin two (2-ethylhexoate), dioctyl tin diacetin, dibutyltindilaurylmercaptide cinnamic acid salt, Dibutyltin oxide, dioctyl tin oxide, 2-ethyl hexane lead plumbate.
Can be used alone above-claimed cpd as curing catalysts or and use two or more.The amount of curing catalysts is different according to its kind, relative to the solid ingredient total amount of (A) component, (B) component and (C) component, is generally 0 ~ 5 quality %, is preferably about 0.1 ~ 4 quality %.
As pigment, can be not particularly limited to use, such as, can enumerate titanium oxide, zinc oxide, carbon black, cadmium red, chrome vermillion, chrome yellow, chromic oxide, Prussian blue, the tinting pigment such as cobalt blue, azo pigment, phthalocyanine pigment, quinoline Azone pigment, isoindoline pigment, intellectual circle's series pigments, perylene dye; The filler pigments such as talcum, clay, kaolin, barium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon-dioxide, aluminum oxide are white; By metallic pigment etc. such as the mica powder of aluminium powder form, mica powder, titanium-oxide-coated.
Above-mentioned pigment can be used alone or uses two or more.The content of pigment is different according to its kind, relative to the solid ingredient total amount of (A) component, (B) component and (C) component, is generally 0 ~ 200 quality %, is preferably about 1 ~ 100 quality %.
In addition, the content of tinting pigment is different according to its kind, relative to the solid ingredient total amount of (A) component, (B) component and (C) component, is generally 0 ~ 150 quality %, is preferably about 1 ~ 100 quality %.
As UV light absorber, current known material can be used, such as, can enumerate the UV light absorber such as benzotriazole system absorption agent, triazine system absorption agent, Whitfield's ointment system absorption agent, benzophenone series absorption agent.
As UV light absorber content in the coating composition, from the viewpoint of weathering resistance, yellowing resistance, usually relative to resin solid content total amount, be preferably in the scope of 0 ~ 10 quality %, particularly 0.2 ~ 5 quality % and then particularly 0.3 ~ 2 quality %.
As photostabilizer, current known material can be used, such as, can enumerate hindered amine system photostabilizer.
As photostabilizer content in the coating composition, from the viewpoint of weathering resistance, yellowing resistance, usually relative to resin solid content total amount, be preferably in the scope of 0 ~ 10 quality %, particularly 0.2 ~ 5 quality % and then particularly 0.3 ~ 2 quality %.
Coating composition of the present invention is not when the isocyanate group of the polyisocyanate compounds as (B) component is closed, from the viewpoint of storage stability, the two-component type coating that the silicon-dioxide (C) that the acrylic resin (A) of preferred hydroxyl and polysiloxane are modified is separated with polyisocyanate compounds (B), is preferably mixed into the two to exercise and uses before being about to use.
the coating method of coating composition
Treat coat as what be suitable for this coating, be not particularly limited, such as preferred metal bases such as steel plate, aluminium sheet, aluminium alloy plate such as cold-rolled steel sheet, steel plate galvanized, galvanized alloy steel plate, stainless-steel sheet, tin plate; Various plastic materials etc.In addition, can be formed by this metal base or plastic material, the car body of various vehicles such as automobile, cart, freight container etc.
in addition, as treating coat, can implement the metallic surface of above-mentioned metal base, car body object after the surface treatments such as phosphatizing, chromic salt process, composite oxides process.Enter and, as treating coat, can be form various galvanic deposit on above-mentioned metal base, car body etc. object after the primary coat cloth film of coating etc. and/or middle coating film.
As the coating method of this coating, be not particularly limited, such as, can pass through the coating methods such as aerial spraying, hydraulic spraying, rotary-atomizing coating, curtain painting coating and form wet type film.In above-mentioned coating method, electrostatic applying can be carried out as required.Wherein, particularly preferably aerial spraying.The glue spread of this coating is preferably the amount of solidification thickness about 10 ~ 50 μm usually.
In addition, when carrying out the coating of aerial spraying, hydraulic spraying and rotary-atomizing, preferably with an organic solvent the viscosity of equal solvent to this coating suitably adjusts in advance, in the range of viscosities its viscosity being in be applicable to carry out above-mentioned coating, that is, be in the range of viscosities of about 15 ~ 60 seconds usually when 20 DEG C in Ford cup #No.4 viscometer.
The solidification of the wet type film obtained treating coat top to apply this coating is undertaken by heating, heats and is undertaken by known heater means, the drying ovens such as such as applicable hotblast stove, electric furnace, infrared rays induced heat stove.Heating temperature is 60 ~ 180 DEG C, be preferably in the scope of 90 ~ 150 DEG C is suitable.Heat-up time is not particularly limited, and is preferably in the scope of 15 ~ 30 minutes.
This coating can obtain all excellent film of scuff resistance, acid resistance and stain resistance excellence and then finished appearance and toolability, makes top painting Clearcoat coating so can be suitable for.This coating can be particularly useful as automotive coating.
method of forming layered coating film
Be coated with this coating and can enumerate a kind of method of forming layered coating film as the method for forming layered coating film of top painting Clearcoat coating, treating coat applies in turn at least 1 layer of painted bottom-coating and at least 1 layer of Clearcoat coating and forming the method for multilayer film, it is characterized in that, the Clearcoat coating as the superiors applies coating composition of the present invention.
Specifically, treating such as after implementing electrodeposition coating and/or middle painting coating coat applies solvent-borne type or aqueous basecoat coating, in order to not make this curing of coating but promote being vaporized of the solvent in bottom-coating as required, such as, after carrying out about 3 ~ 30 minutes preheat at 40 ~ 90 DEG C, after the primary coat film that this is uncured carries out the coating of this coating as Clearcoat coating, the method for forming layered coating film of 2 coatings, 1 roasting mode that primary coat is solidified together with Clear coating.
In addition, the top that the top being also applicable to 3 coating 2 roasting modes or 3 coatings, 1 roasting mode is coated with in coating is coated with Clearcoat coating.
As the bottom-coating of above-mentioned use, current known common thermohardening type bottom-coating can be used, specifically, such as can acrylic resin, vibrin, Synolac, aminoresin, polyisocyanate compounds, block gather by the matrix resins such as urethane resin system the reactive functional groups that the solidifying agent such as isocyanate compound and matrix resin contain appropriately combined and the coating obtained.
In addition, as bottom-coating, from the viewpoint of environmental problem, resource-saving etc., the high solid-state version coating that the usage quantity of preferred organic solvent is few, and then water-borne coatings or powder coating can be used.
In method of forming layered coating film, during coating more than 2 layers Clear coatings, except this coating, as Clearcoat coating, the thermohardening type Clearcoat coatings such as current known vinylformic acid/melamine resin system can be used.
Embodiment
Below, enumerate embodiment and comparative example, further illustrate the present invention.But the present invention is not limited to following embodiment.Should illustrate, below " part " and " % " be quality criteria, in addition, the thickness of film is all based on cured coating film.
the preparation example of the acrylic resin of hydroxyl
Preparation example 1 ~ 15
In the four-hole boiling flask possessing whipping appts, thermometer, prolong, nitrogen inlet, drop into ethoxyethyl propionate 31 parts, under nitrogen ventilation, be warming up to 155 DEG C.After reaching 155 DEG C, stop logical nitrogen, dripped the monomer mixture of the composition and ratio be made up of the monomer shown in following table 1 and polymerization starter with 4 hours.Then, pass into nitrogen at 155 DEG C and make its slaking after 2 hours, be cooled to 100 DEG C, with butylacetate 32.5 parts (only preparation example 10 is 7.5 parts) dilution, thus obtain acrylic resin (A-1) ~ (A-15) of the hydroxyl of solid ingredient 60%.The quality solid concentration of component (%) of the acrylic resin of the hydroxyl obtained and resin character value are shown in following table 1.
Second-order transition temperature (DEG C) in table 1 is calculated by following formula.
1/Tg(K)＝(W1/T1)＋(W2/T2)＋……
Tg(℃)＝Tg(K)－273
In various, the monomer massfraction separately used in W1, W2, expression copolymerization, the Tg (K) of the homopolymer of T1, T2, each monomer of expression.Should illustrate, T1, T2, be the value obtained by PolymerHandbook (Second Edition, J.BrandUpE.H.ImmergUt compile).
Should illustrate, the second-order transition temperature in above-mentioned document as monomer component with the acrylic resin of the hydroxyl of the monomer not having to record (data) is the value measured by Seiko electronic industry DSC220U (differential scanning type calorimeter).Be determined as follows and carry out: sample 50mg is taken in special planchet by specified amount, after 3 hours, in rare gas element, be warming up to 150 DEG C with the speed of 10 DEG C/min from-50 DEG C in 130 DEG C of dryings, read the temperature of the flex point of the calorimetric change curve obtained.
Should illustrate, acrylic resin (A-13) ~ (A-15) of hydroxyl is comparative example resin.
Table 1
the preparation of coating composition
Embodiment 1 ~ 17 and comparative example 1 ~ 8
Use the starting material recorded in the acrylic resin of the hydroxyl obtained in above-mentioned preparation example 1 ~ 15 and aftermentioned table 2, use paddle type stirrer to carry out stirring by the proportioning shown in aftermentioned table 2 and mix, implementing coating, obtain each coating composition.Should illustrate, the proportioning of the coating composition shown in table 2 is the solid ingredient mass ratio of each component.
(* 1) in table 2 ~ (* 12) have following implication respectively.
(* 1) polyisocyanate compounds A:Sumidur N-3300 lives to change Bayer urethane (strain) society system.The polyisocyanate compounds be made up of hexamethylene diisocyanate, polymeric ratio of component are: polymers 47% more than isocyanate trimer 53%, other tripolymers.Solid ingredient 100%, NCO containing ratio 21.8%.
(* 2) polyisocyanate compounds B:Duranate TLA-100 Asahi Chemical Industry CHEMICALS (strain) society system.The polyisocyanate compounds be made up of hexamethylene diisocyanate, polymeric ratio of component are: polymers 25% more than isocyanate trimer 63%, urea diketone dimer 12%, other tripolymers.Solid ingredient 100%, NCO containing ratio 21.8%.
The mixture of the 1:1 (mass ratio) of (* 3) polyisocyanate compounds C:Duranate TLA-100 (Asahi Chemical Industry CHEMICALS (strain) society system) and Desmodur N-3400 (living to change Bayer urethane (strain) society system).The polyisocyanate compounds be made up of hexamethylene diisocyanate, polymeric ratio of component are: polymers 30% more than isocyanate trimer 45%, urea diketone dimer 25%, other tripolymers.Solid ingredient 100%, NCO containing ratio 21.8%.
(* 4) polyisocyanate compounds D:Desmodur N-3400 lives to change Bayer urethane (strain) society system.The polyisocyanate compounds be made up of hexamethylene diisocyanate, polymeric ratio of component are: polymers 36% more than isocyanate trimer 27%, urea diketone dimer 37%, other tripolymers.Solid ingredient 100%, NCO containing ratio 21.8%.
(* 5) Takenate D160N: Wu Tian pharmaceutical industries society system, trade(brand)name, the adducts of hexamethylene diisocyanate and TriMethylolPropane(TMP), solid ingredient 75%, NCO is containing dose rate 12.6%.
(* 6) NANOBYK-3650:BYK society system, trade(brand)name, straight chained alkyl is modified polydimethyl oxirane and is modified silica dioxide granule dispersion liquid, low polarity, median size 20nm, solid ingredient concentration 31% (silica dioxide granule concentration 25%).
(* 7) NANOBYK-3651:BYK society system, trade(brand)name, branched-chain alkyl is modified polydimethyl oxirane and is modified silica dioxide granule dispersion liquid, high polarity, median size 20nm, solid ingredient concentration 34%.(silica dioxide granule concentration 20%).
(* 8) NANOBYK-3652:BYK society system, trade(brand)name, straight chained alkyl is modified polydimethyl oxirane and is modified silica dioxide granule dispersion liquid, Semi-polarity, median size 20nm, solid ingredient concentration 31% (silica dioxide granule concentration 25%).
(* 9) NANOBYK-3610:BYK society system, trade(brand)name, alumina particle dispersion liquid modified by alkyl modified polysiloxane, low polarity, median size 20nm, solid ingredient concentration 37% (alumina particle concentration 30%).
(* 10) Snowtex XBA-ST: Nissan Chemical Ind Ltd's system, trade(brand)name, carry out by oxirane key the colloidal silica (not there is polysiloxane structure) that polymer quantizes and be suspended in dispersion liquid in organic solvent (dimethylbenzene/butanols), on its surface, there is hydroxyl, shape is spherical, and particle diameter is 10 ~ 20nm.Solid ingredient concentration 30%.
(* 11) UV1164:Ciba-geigy society system, UV light absorber.
(* 12) HALS292:Ciba-geigy society system, hindered amine as light stabilizer.
It is the viscosity of 25 seconds that each coating composition No.1 ~ 25 obtained in above-described embodiment 1 ~ 17 and comparative example 1 ~ 8 are added when butylacetate uses Ford cup #No.4 to be adjusted to 20 DEG C.
the making of test board
Use the material after the viscosity adjustment of above-mentioned each coating composition No.1 ~ 25 obtained in embodiment 1 ~ 17 and comparative example 1 ~ 8, make test board as described below respectively.
The inertia steel plate implementing zinc phosphate and change into the thickness 0.8mm of process is 20 μm of electrodeposition coating ELECRON GT-10 (Northwest coating society system, trade(brand)name, thermosetting epoxy resin cation electrocoating paints) by thickness, within 30 minutes, it is made to solidify 170 DEG C of heating, thereon by thickness 35 μm of aerial spraying Amilac TP-65-2 (in Northwest coating society system, trade(brand)name, polyester/melamine resin system automobile coating), be heating and curing 30 minutes at 140 DEG C.By thickness 15 μm coating water-based metal primary coat WBC713T#202 (Northwest coating society system, vinylformic acid/melamine resin system vapour Vehicular top is coated with bottom-coating, blackly tints) on this film, after room temperature places 5 minutes, after carrying out preheating for 10 minutes at 80 DEG C, this uncured film is pressed each coating composition after preparation in thickness 35 μm coating above-described embodiment and comparative example, viscosity adjustment, after room temperature places 10 minutes, within 20 minutes, make this two film solidify together 140 DEG C of heating and obtain test board.The each test board obtained is implemented the test of following film performance after normal temperature leaves standstill 7.
performance test results
Scuff resistance: with the water-fast adhesive tape sticking test board of NICHIBAN society system on automobile top-cap, 15 carwash are carried out with car washer under the condition of 20 DEG C, then, 20 degree of specular reflectances (20 ° of gloss numbers) of determination test plate, evaluate according to the gloss retention (%) relative to 20 ° of gloss numbers before test.This gloss retention higher expression scuff resistance is better.Car washer uses YASUI industry society's system " PO20FWRC ".
Acid resistance: drip 0.4cc40% sulfuric acid on the film of each test board, the hot plate being heated to 60 DEG C heated after 15 minutes, is washed by test board.Use surface roughness meter (the accurate society in Tokyo system, surfaceness form measuring instrument " SURFCOM570A ") under the condition of cutting (cutoff) 0.8mm (sweep velocity 0.3mm/sec, multiplying power 5000 times), measure sulfuric acid drip the etch depth (μm) at position and carry out acid proof evaluation.Etch depth less expression acid resistance is better.
Finished appearance (gloss): 20 degree of specular reflectances (20 ° of gloss numbers) of determination test plate are evaluated.As standard, if the value of 20 ° of gloss numbers is more than 86, then finished appearance (gloss) is good.
Toolability: after becoming 20 ° of gloss numbers (G1) below 0.5 sand papering (grinding) of test board #2000, after coming and going grinding 100 times, measures 20 ° of gloss numbers (G2) with the flannelette of band compound with the loading of 500g.The evaluation of toolability is carried out according to the value of Δ G (G2-G1).The value of Δ G is larger, and toolability (grinding toolability) is better.
Stain resistance: after each test coated plate is carried out 600 h run in sunshine weather meter (SUGA trier society system, promotion weathering test machine), on each test coated plate, make the pollution substance be made up of the mixture of earth, carbon black, mineral oil and clay be attached on flannelette, the coated face of coated plate is respectively tested in wiping lightly.By its 20 DEG C, leave standstill 24 hours in the thermostatic constant wet chamber of 75%RH after, painting face flowing water is cleaned, by the luminance difference (Δ L) of the coated plate dustiness by following benchmark evaluation film.Δ L value is less, and stain resistance is better.Δ L following formula is obtained:
Δ L=(the L value before stain resistance test)-(the L value after stain resistance test)
L value uses CR-200 (colour-difference meter of camera society) to measure.
◎：ΔL＜0.2、○：0.2≤ΔL＜1、△：1≤ΔL＜2、×：2≤ΔL。
In addition, in the test of stain resistance, use by the following test board obtained, similarly each test board is left standstill at normal temperature the test that 7 implement stain resistance afterwards, that is: be 20 μm of electrodeposition coating ELECRON GT-10 (Northwest coating society systems by thickness on the inertia steel plate implementing zinc phosphate and change into the thickness 0.8mm of process, trade(brand)name, thermosetting epoxy resin cation electrocoating paint), within 30 minutes, it is made to solidify 170 DEG C of heating, press thickness 35 μm of aerial spraying Amilac TP-65-2 (Northwest coating society system thereon, trade(brand)name, coating in polyester/melamine resin system automobile, tint in vain), within 30 minutes, curing of coating is made 140 DEG C of heating, then prepare by thickness 35 μm coating above-described embodiment and comparative example, carry out each coating composition after viscosity adjustment, after room temperature places 10 minutes, within 20 minutes, it is made to solidify 140 DEG C of heating.
Comprehensive evaluation: coating in the field of the coating of car body etc. belonging to the present invention, wishes scuff resistance, acid resistance and stain resistance excellence and finished appearance and toolability excellence.Therefore, comprehensive evaluation is carried out by following benchmark:
◎: the gloss retention (%) in scuff resistance test is more than 85, etch depth (μm) in acid resisting test is less than 0.6,20 ° of gloss numbers in finished appearance test (gloss) are more than 85, Δ G in toolability test is more than 45, and stain resistance is ◎;
Zero: the gloss retention (%) in scuff resistance test is more than 85, etch depth (μm) in acid resisting test is less than 0.6,20 ° of gloss numbers in finished appearance test (gloss) are more than 85, Δ G in toolability test is more than 45, and stain resistance is zero;
△: the gloss retention (%) in scuff resistance test is more than 85, etch depth (μm) in acid resisting test is less than 0.6,20 ° of gloss numbers in finished appearance test (gloss) are more than 85, Δ G in toolability test is more than 45, and stain resistance is △;
×: scuff resistance test in gloss retention (%) lower than the etch depth (μm) in 85 or acid resisting test be greater than 0.6 or finished appearance test (gloss) in 20 ° of gloss numbers lower than 85 toolability test in Δ G lower than 45 or stain resistance for ×; Above-mentioned performance test results is shown in table 2 in the lump.
Table 2
Table 3

Claims (10)

1. coating composition, it comprises:
The acrylic resin (A) of hydroxyl, it is the multipolymer of monomer component, and described monomer component comprises:
The polymerizable unsaturated monomer (a) of the hydroxyl of 25 quality % to 50 quality %;
5 quality % to 30 quality % contain C 6-C 20the polymerizable unsaturated monomer (b) of alicyclic alkyl; And
The other polymerizable unsaturated monomer (c) of 20 quality % to 70 quality %;
Polyisocyanate compounds (B), it comprises aliphatic diisocyanate, based on the total amount of described polyisocyanate compounds, described polyisocyanate compounds (B) comprises other polymkeric substance comprising at least three kinds of monomers of the isocyanate trimer of 30 quality % to 70 quality %, the urea diketone dimer of 3 quality % to 30 quality % and 0 quality % to 67 quality %; And
The silica dioxide granule (C) that polysiloxane is modified, described in each, the average primary particle diameter of the silica dioxide granule (C) that polysiloxane is modified is 1nm to 40nm.
2. coating composition as claimed in claim 1, wherein said containing C 6-C 20the polymerizable unsaturated monomer (b) of alicyclic alkyl comprises at least one be selected from (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) t-butylcyclohexyl ester, (methyl) vinylformic acid ring ten diester, (methyl) isobornyl acrylate, (methyl) vinylformic acid diamantane ester and (methyl) vinylformic acid three ring ester in the last of the ten Heavenly stems.
3. coating composition as claimed in claim 1 or 2, the weight-average molecular weight of the acrylic resin (A) of wherein said hydroxyl is 5,000 to 30,000.
4. coating composition as claimed in claim 1 or 2, the silica dioxide granule (C) that wherein said polysiloxane is modified comprises the polysiloxane of organic decoration separately as polysiloxane.
5. coating composition as claimed in claim 1 or 2, the silica dioxide granule (C) that wherein said polysiloxane is modified comprises at least one in polydimethylsiloxane and polydiphenylsiloxane separately as polysiloxane.
6. coating composition as claimed in claim 1 or 2, the isocyanate groups wherein in described polyisocyanate compounds (B) is 0.8 to 1.5 with the equivalence ratio (NCO/OH) of the hydroxyl in the acrylic resin (A) of described hydroxyl.
7. coating composition as claimed in claim 1 or 2, wherein based on the acrylic resin (A) of described hydroxyl and the total amount of described polyisocyanate compounds (B), the ratio of mixture of the acrylic resin (A) of described hydroxyl is 55 quality % to 80 quality %, the ratio of mixture of described polyisocyanate compounds (B) is 20 quality % to 45 quality %, and the ratio of mixture of the silica dioxide granule (C) of described polysiloxane modification is 0.1 quality % to 10 quality %.
8. coating composition as claimed in claim 1 or 2, the second-order transition temperature (Tg) of the film wherein formed by described coating composition is 70 DEG C to 110 DEG C.
9. article, it comprises the film obtained by the coating composition in coating claim 1 to 8 described in arbitrary claim.
10. form the method for multilayer film, it comprise use at least one deck pigmented basecoat coating material and at least one deck clearcoat coating material in succession apply object to be coated, wherein said coating comprises and is used as the coating composition in the claim 1 to 8 for the clearcoat coating material of the superiors described in arbitrary claim to apply.
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