CN1524889A - Multipolymer containing fluorine for paint, combination for paint and paint - Google Patents
Multipolymer containing fluorine for paint, combination for paint and paint Download PDFInfo
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- CN1524889A CN1524889A CNA2004100082154A CN200410008215A CN1524889A CN 1524889 A CN1524889 A CN 1524889A CN A2004100082154 A CNA2004100082154 A CN A2004100082154A CN 200410008215 A CN200410008215 A CN 200410008215A CN 1524889 A CN1524889 A CN 1524889A
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- fluorinated copolymer
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- fluoroolefin
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/0015—Sports garments other than provided for in groups A41D13/0007 - A41D13/088
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
- A41D13/0512—Neck or shoulders area
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D29/00—Uniforms; Parts or accessories of uniforms
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D2600/00—Uses of garments specially adapted for specific purposes
- A41D2600/10—Uses of garments specially adapted for specific purposes for sport activities
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Physical Education & Sports Medicine (AREA)
- Otolaryngology (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The weak solvent-soluble fluorine-containing copolymer is a copolymer of a fluoroolefin and a double bond-containing monomer capable of copolymerizing with the fluoroolefin, wherein the content of fluorine derived from the fluoroolefin is 10 wt% or more, and the double bond-containing monomer contains 10-30 mol% of a hydroxyl group and 20-80 mol% of a branched C3 or more alkyl group.
Description
Technical field
The coating that the present invention relates to dissolve in Weak solvent with fluorinated copolymer, contain coating composition and the coating of this coating with fluorinated copolymer.
Background technology
In the past, as forming the good coating resin of filming of weathering resistance, known had a fluorine resin.The coating that contains this fluorine resin uses as etch-proof outer protective membrane, or is the outer protective membrane use of base material as cement.
But, this coating is owing to contain so-called strong solvents such as toluene, dimethylbenzene, if so synthetic resins mixed coating, chlorinated rubber that this coating directly is coated in through yearly fluctuation are on the old coating film of coating and other lacquer etc., then exist and the problem that contraction or expansion maybe can not obtain good adhesive property occurs.
On the other hand, adopt in use solidifying agent in recent years and contain the binary liquid shape coating that the solution with the crosslinkable resin of this solidifying agent mixes.Because binary liquid shape coating is by the three-dimensional eyed structure of being cross-linked to form of resin and solidifying agent, so can obtain hardness height, good the filming of stain resistance.As this binary liquid shape coating, known have used the isocyanate-based solidifying agent and have as with the coating of the resin of the hydroxyl at the crosslinking reaction position of this solidifying agent, the content of the hydroxyl in the resin (hydroxyl value) is many more, the hardness that gained is filmed is high more.
But, be used for the resin of binary liquid shape coating owing to have hydroxyl, so polarity is higher, be not soluble in Weak solvent.Therefore, in binary liquid shape coating, use the strong strong solvent of solvency power usually.As mentioned above, existence can destroy the problem of old coating film etc. when old coating film etc. is repaired.
At this problem, developed the Weak solvent type coating of the Weak solvent a little less than using solvency power than strong solvent.For example, Japanese patent laid-open 8-32847 number (patent documentation 1) proposed to comprise the coating composition that dissolves in as the fluorinated copolymer of the mineral turpentine solvent of Weak solvent.
But fluorinated copolymer used in the patent documentation 1 improves hydroxyl value in order to be used for binary liquid shape coating, and the solvability to Weak solvent just descends like this, the application difficulty, and very difficult acquisition has filming of sufficient intensity.
Therefore, the purpose of this invention is to provide and to form the high coating fluorinated copolymer of filming, dissolve in Weak solvent of hardness, contain the coating composition and the coating of this coating with fluorinated copolymer.
Summary of the invention
The present inventor conscientiously studies the back to foregoing problems and finds, monomer as fluorinated copolymer, use fluoroolefin and can with the monomer that contains two keys of fluoroolefin copolymerization, contain the hydroxyl that comprises 10～30 moles of % in the monomer of two keys, and contain the branched-chain alkyl of carbonatoms more than 3 of 20～80 moles of %, so can address the above problem, and finish the present invention based on this.
Promptly, the invention provides the coating fluorinated copolymer that dissolves in Weak solvent, the feature of this multipolymer is, it be fluoroolefin and can with the monomeric multipolymer of two keys of containing of fluoroolefin copolymerization, based on the fluorine content of fluoroolefin more than 10 quality %, contain in the monomer of two keys and comprise the hydroxyl of 10～30 moles of %, and contain the branched-chain alkyl of carbonatoms more than 3 of 20～80 moles of %.
The present invention also provides and has contained the coating composition of aforementioned coating with fluorinated copolymer and Weak solvent.
The present invention further provides the coating that contains aforementioned coating composition and solidifying agent.
Embodiment
Below, the present invention is described in detail.
(coating fluorinated copolymer)
Coating fluorinated copolymer of the present invention be fluoroolefin and can with the monomeric multipolymer of two keys of containing of fluoroolefin copolymerization, based on the fluorine content of fluoroolefin more than 10 quality %, contain the hydroxyl that comprises 10～30 moles of % in the monomer of two keys, and containing the branched-chain alkyl of carbonatoms more than 3 of 20～80 moles of %, this multipolymer dissolves in Weak solvent.
The fluorine adduct number of fluoroolefin better is more than 2, more preferably 3～4.If the fluorine adduct number is more than 2, then weathering resistance is abundant, so fine.
Fluoroolefin can exemplify tetrafluoroethylene, trifluorochloroethylene, vinylidene fluoride, R 1216 etc., and good especially is tetrafluoroethylene and trifluorochloroethylene.
Contain two keys monomer can with the fluoroolefin copolymerization, preferably use the vinyl monomer beyond the fluoroolefin.This vinyl monomer is for having with CH
2The compound of the carbon-to-carbon double bond that=CH-represents.This vinyl monomer comprise have the straight chain shape, the alkyl vinyl ether of chain or cyclic alkyl, alkyl vinyl acetate etc.
The monomer that contains two keys among the present invention comprises these two kinds of the monomer that possesses two keys (hereinafter referred to as the monomer that contains hydroxyl) that contains hydroxyl and the monomer that possesses two keys (hereinafter referred to as the monomer that contains branched-chain alkyl) that contain the branched-chain alkyl of carbonatoms more than 3.The monomer that contains hydroxyl also can contain the branched-chain alkyl of carbonatoms more than 3, and the monomer that contains branched-chain alkyl also can contain hydroxyl.
The hydroxyl that contains 10～30 moles of % in the monomer that contains two keys of the present invention.
If the monomeric content that contains hydroxyl then in order to obtain higher the filming of hardness, is preferably in the hydroxyl that imports q.s in the fluorinated copolymer at 10 moles more than the %.
In addition, if the monomeric content that contains hydroxyl then preferably can be kept as the enough solvability of coating time spent in Weak solvent at 30 moles below the %.
There is no particular limitation to the monomeric carbonatoms that contains hydroxyl, is preferably 2～10, and more preferably 2～6, good especially is 2～4.
The monomer that contains hydroxyl can exemplify hydroxyalkyl vinyl ethers such as 4-hydroxybutyl vinyl ether (HBVE), 2-hydroxyethyl vinyl ether (HEVE), cyclohexanedimethanol one vinyl ether, hydroxyalkyl allyl ether series such as hydroxyethyl allyl ethers, cyclohexanedimethanol one allyl ethers, (methyl) Hydroxyethyl Acrylate etc. (methyl) vinylformic acid hydroxyalkyl acrylate class etc.Because the copolymerization weathering resistance of filming good, that form is good, so be preferably the hydroxyalkyl vinyl ethers.Wherein,, be preferably the hydroxyalkyl vinyl ether of carbonatoms 2～4, be more preferably HEVE owing to the favorable solubility in Weak solvent.
Not clear to the reason of using the favorable solubility of HEVE in Weak solvent, may be because carbonatoms is less, the hydroxyl of the side chain in the fluorinated copolymer is present near the main chain, so that other side chain forms is sterically hindered, is not vulnerable to the cause of the influence of Weak solvent.
This monomer that contains hydroxyl can a kind uses separately, also can be used in combination more than 2 kinds.
The branched-chain alkyl of carbonatoms more than 3 that comprises 20～80 moles of % in the monomer that contains two keys of the present invention.
Because containing the monomer content of branched-chain alkyl is 20～80 moles of %, even adopt the monomer that contains hydroxyl of above-mentioned amount, also can guarantee the solvability in Weak solvent.By using this monomer that contains branched-chain alkyl can guarantee that the deliquescent reason in Weak solvent is not clear, may be similar to the molecular structure of Weak solvent because contain the monomeric molecular structure of branched-chain alkyl, the cause that intermiscibility is higher.
As long as the carbonatoms that contains the branched-chain alkyl in the monomer of branched-chain alkyl is not particularly limited it more than 3, is preferably 4～15, and more preferably 4～10.
The monomer that contains branched-chain alkyl can exemplify vinyl ethers, allyl ether series or (methyl) ethyl propenoate class that contains branched-chain alkyl.Can exemplify sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl, 2-ethylhexyl, 2-methyl hexyl etc. as branched-chain alkyl.Consider well that from copolymerization the monomer that contains branched-chain alkyl can exemplify 2-ethylhexyl vinyl ether (2-EHVE), tert-Butyl vinyl ether vinyl ethers such as (t-BuVE), wherein that good especially is 2-EHVE.
This monomer that contains branched-chain alkyl can a kind uses separately, also can be used in combination more than 2 kinds.
Under the prerequisite that does not influence effect of the present invention, other beyond the monomer that the monomer that contains two keys of the present invention also comprises the monomer that contains hydroxyl, contain branched-chain alkyl contains the monomer of two keys.
The monomer that contains two keys as other is preferably the monomer that contains alkyl.This alkyl comprises straight chain shape, chain or cyclic alkyl.The carbonatoms of this alkyl is preferably 2～8, and more preferably 2～6.
Particularly adopt comprise cyclic alkyl contain the monomer of two keys the time, the second-order transition temperature of fluorinated copolymer (Tg) rises, the hardness of filming also can further improve, and is very desirable.
This monomer that contains two keys that comprises cyclic alkyl can exemplify cyclic alkyl vinyl ethers such as cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 3,3,5-3-methyl cyclohexanol ester etc. (methyl) vinylformic acid cyclic alkyl ester class etc.
This other the monomer that contains two keys can a kind uses separately, also can be used in combination more than 2 kinds.
In the monomeric total amount that contains two keys, other the monomeric ratio that contains two keys is preferably 0～70 mole of %, more preferably 30～60 moles of %.
In the fluorinated copolymer be based on the polymerized unit of fluoroolefin with based on the ratio of the monomeric polymerized unit that contains two keys, polymerized unit based on fluoroolefin is preferably 30～70 moles of %, 40～60 moles of % more preferably, be preferably 70～30 moles of % based on the monomeric polymerized unit that contains two keys, more preferably 60～40 moles of %.If at 70 moles below the %, then the solvability of fluorinated copolymer in Weak solvent is abundant based on the ratio of the polymerized unit of fluoroolefin, if, then can obtain sufficient weathering resistance, so very desirable at 30 moles more than the %.
Coating fluorinated copolymer of the present invention is that comprise the monomer that contains hydroxyl at fluoroolefin with the regulation ratio and contain branched-chain alkyl monomeric contains in the monomeric mixture of two keys, in the presence of the polymerisation medium or not, make polymerization initiating accident sequence effects such as polymerization starter or ionization ray carry out copolyreaction and make.
Fluoroolefin in the copolyreaction and the monomeric usage ratio that contains two keys preferably with above-mentioned fluorinated copolymer in based on the polymerized unit of fluoroolefin and identical based on the ratio of the monomeric polymerized unit that contains pair keys.
But ketones such as polymerisation medium exemplified by methyl ethyl ketone, hexone, ester such as ethyl acetate, n-butyl acetate class, aromatic solvents such as dimethylbenzene and toluene, aliphatic solvents such as pimelinketone, solvent oil, mineral turpentine, petroleum naphtha, the 3-ethoxyl ethyl propionate, methyl amyl ketone, tert.-butyl acetate, 4-chlorobenzene and trifluoromethylbenzene, the benzo trifluoromethylbenzene, monochlorotoluene, 3,4-dichloro benzo trifluoromethylbenzene etc.
Polymerization starter can exemplify 2; 2 '-Diisopropyl azodicarboxylate; 2; 2 '-azo bicyclohexane carbonic acid nitrile (2; 2 '-azobiscyclohexanecarbonatenitrile); 2; 2 '-azo two (2; the 4-methyl pentane nitrile); 2; 2 '-azo two azo series initiators such as (2-methyl isopropyl cyanides); peroxidation ketones such as cyclohexanone peroxide; hydroperoxide type such as t-butyl hydroperoxide; diacyl peroxide classes such as benzoyl peroxide; dialkyl peroxide classes such as di-t-butyl peroxide; 2, ketal peroxide classes such as 2-two (t-butylperoxy) butane; alkyl peroxyesters such as t-butylperoxy pivarate; superoxide series initiators such as percarbonic acid salts such as di-isopropyl peroxy dicarbonate salt etc.
In this fluorinated copolymer, based on the fluorine content of fluoroolefin corresponding to the total mass of fluorinated copolymer more than 10 quality %, be preferably 20～30 quality %.If fluorine content is more than 10 quality %, the weathering resistance of then filming is abundant, and is very desirable.
In addition, this fluorinated copolymer contain as with the hydroxyl of the reactive moieties of solidifying agent.Hydroxyl value in the fluorinated copolymer (hereinafter referred to as OHV) is scaled the chemical reaction equivalent of potassium hydroxide, form to divide corresponding to fluorinated copolymer total solid and be preferably 40～55mgKOH/g, more preferably 45～55mgKOH/g.
If OHV more than 40mgKOH/g, then can obtain higher the filming of hardness, if OHV below 55mgKOH/g, then coating has sufficient solvability with fluorinated copolymer in Weak solvent, so very desirable.
Fluorinated copolymer be primary standard with the polystyrene, the number-average molecular weight (Mn) of utilizing gel permeation chromatography (GPC) to measure is preferably 5000～7500.If Mn is more than 5000, then weathering resistance is good, if Mn below 7500, so the favorable solubility in Weak solvent then is very desirable.
In addition, the second-order transition temperature of fluorinated copolymer (hereinafter referred to as Tg) better is more than 25 ℃, more preferably 30～40 ℃.If Tg then can obtain filming of high rigidity more than 25 ℃, so very desirable.
Coating of the present invention is with preferably also containing carboxyl in the fluorinated copolymer.By containing carboxyl, can improve the pigment-dispersing when using as coating.The content of the carboxyl in the fluorinated copolymer (acid number (hereinafter referred to as AV)) is converted into the chemical reaction equivalent of potassium hydroxide, form to divide corresponding to fluorinated copolymer total solid and be preferably 1～5mgKOH/g, more preferably 2～5mgKOH/g.
After this carboxyl for example can and contain the monomeric polyreaction of two keys at above-mentioned fluoroolefin, the reaction by the hydroxyl in the fluorinated copolymer and polycarboxylic acid or its acid anhydrides imported.In addition, also can import by the monomeric direct polymerization that contains two keys that comprises carboxyl.
(coating composition)
Contain coating of the present invention in the coating composition of the present invention with fluorinated copolymer and Weak solvent.
Weak solvent is the 3rd a kind of organic solvent in the organic solvent classification of the Japanese law of labour safety and health, comprises following 1)～3) in any.1) is gasoline, coal-tar naphtha (comprising solvent oil), sherwood oil, petroleum naphtha, sherwood oil, turps, mineral turpentine (comprising mineral thinner, solvent oil, rosin and mineral turpentine), 2) be only by 1) mixture formed, 3) be 1) and 1) mixture of in addition material, 1) content surpass 5 quality %.
Coating composition of the present invention has used above-mentioned the 3rd kind of organic solvent as Weak solvent, and the content that is equivalent to the 2nd kind of organic solvent of strong solvent is no more than 5 quality % of all solvents.
Consider more than room temperature that from flash point Weak solvent is mineral turpentine preferably.
In the coating composition of the present invention except coating of the present invention with fluorinated copolymer and the Weak solvent, in order to improve the drying property of filming, also can contain CAB (cellulose acetobutyrate), NC (soluble cotton) etc., in order to improve gloss, hardness, the execution of coating of filming, also can contain coating resins such as polymkeric substance that vinylformic acid or its ester form, polyester.
In the coating composition of the present invention, coating of the present invention better is to account for more than the 20 quality % of total solid formation branch contained in the coating composition with fluorinated copolymer, is more preferably more than 30 quality %, preferably more than 40 quality %.
In the coating composition of the present invention, the contained solid branch that forms preferably can all be dissolved in the Weak solvent, but some insoluble parts also can be arranged.
Weak solvent amount in the coating composition can consider that the solvability of fluorinated copolymer, the suitable viscosity when carrying out application as coating and coating process etc. make decision.
The favorable solubility of fluorinated copolymer of the present invention in Weak solvent is so contained Weak solvent amount can be 10～30 quality % in the coating composition.
Coating composition of the present invention can be used as binary liquid shape coating, mixes with solidifying agent before use.
(coating)
Contain coating composition of the present invention and solidifying agent in the coating of the present invention.
This solidifying agent better be with fluorinated copolymer in the crosslinkable solidifying agent of hydroxyl, for example, the isocyanate-based solidifying agent of isocyanate-based solidifying agent, blockization, trimeric cyanamide are coating solidifying agent such as solidifying agent.
The isocyanate-based solidifying agent can exemplify no xanthochromic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate.
The isocyanate-based solidifying agent of blockization can exemplify the isocyanate group of isocyanate curing agent by the solidifying agent of blockizations such as hexanolactam, isophorone, β-diketone.
Trimeric cyanamide is that solidifying agent can exemplify butylation trimeric cyanamide etc. and utilizes the trimeric cyanamide of lower alcohol etherificate, epoxide modified trimeric cyanamide etc.
The content of the solidifying agent in the coating comprises the resinous principle of the fluorinated copolymer in the coating composition corresponding to 100 mass parts, is preferably 1～100 mass parts, more preferably 1～50 mass parts.
If solvent resistance and hardness that the content of solidifying agent more than 1 mass parts, is then filmed are enough, if the content of solidifying agent below 100 mass parts, then processibility and shock-resistance are good, so very desirable.
The functional additive that preferably also contains other in the coating of the present invention as required.Other functional additive comprises silane coupling agent, UV light absorber, curing catalyst, photostabilizer and the delusterant etc. of tinting pigment, dyestuff, raising coating adhesion.
Tinting pigment, dyestuff can exemplify mineral dyes such as the good carbon black of weathering resistance, titanium oxide, and phthalocyanine blue, phthalocyanine green, quinoline a word used for translation ketone are red, flavanthrone, isoindoline-1-ketone are pigment dyestuff and dyestuffs such as Huang.
Silane coupling agent can exemplify the 3-aminopropyltriethoxywerene werene, the 3-TSL 8330, N-2-(amino-ethyl)-3-TSL 8330, the urea groups propyl-triethoxysilicane, vinyltriethoxysilane, vinyltrimethoxy silane, 3-metacryloxy propyl trimethoxy silicane, 3-metacryloxy propyl-triethoxysilicane, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, the 3-glycidoxypropyltrime,hoxysilane, 3-sulfydryl propyl trimethoxy silicane, 3-isocyanic ester propyl-triethoxysilicane, Union carbide A-162, methyltrimethoxy silane etc.
It is UV light absorber that UV light absorber can exemplify benzophenone series, benzotriazole system, triazine system, cyanoacrylate.
Curing catalyst can exemplify dibutyl tin dilaurate that is used for the isocyanate-based solidifying agent etc., and being used for trimeric cyanamide is the acid curing catalysts such as tosic acid of solidifying agent.
It is photostabilizer etc. that photostabilizer can exemplify ヒ Application ダ-De amine, ァ デ カ ス プ LA62, ァ デ カ ス プ LA67 are (above by ァ デ カ ァ-ガ ス KCC system, trade(brand)name), チ ヌ PVC Application 292, チ ヌ PVC Application 144, チ ヌ PVC Application 123, チ ヌ PVC Application 440 (above) etc. by チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ Co., Ltd. system, trade(brand)name.
Delusterant can exemplify super-fine powder synthetic silica etc., uses under the situation of delusterant, can form to have graceful inferior gloss, remove good the filming of luster effect.
The functional additive mixing of coating composition of the present invention, solidifying agent, interpolation as required just can be made coating of the present invention.
Order by merging is not particularly limited, can be pre-mixed coating composition of the present invention and additive, sneak into solidifying agent then therein, also can mix coating composition of the present invention and solidifying agent, mixed additive then, they also can mix simultaneously.
Arbitrary method such as the method that adopts coating of the present invention to carry out application comprises spraying, the spraying of calming the anger, brushing, pickling process, cylinder coating, flow coat.
The material of the article that are coated comprises inorganicss such as concrete, natural stone, glass, metals such as iron, stainless steel, aluminium, copper, brass, titanium, organism such as plastics, rubber, tackiness agent and timber.Be specially adapted to form the application on the surface of filming.In addition, be applicable to the application of FRP as organic/inorganic composite material, resin reinforcing concrete, fiber strengthening concrete etc.
The article that are coated comprise transportation means such as automobile, electric car, aircraft, bridge member, native art member such as iron tower, industrial machinery materials such as water-proof material film, groove, pipe, material of construction such as skin, door, window member, monument, pillar, road members such as the central decoupled band of road, guardrail, sound-proof wall, signal equipment material, electric and electronic unit etc.
Below, for the present invention will be described in detail, exemplify embodiment (example 1,7～10 is embodiment, and example 2～6,11～15 is a comparative example).The present invention is not limited in these examples.
(manufacturing of fluorinated copolymer A)
Drop into monomer mixture, the dimethylbenzene of 670g, the ethanol of 189g and the salt of wormwood of 9.5g that contains two keys in the autoclave of stainless steel stirrer having of internal volume 2000mL, remove the molten oxygen of depositing with nitrogen, the composition of this monomer mixture is the 2-ethylhexyl vinyl ether (2-EHVE) of the cyclohexyl vinyl ether of 263g (CHVE), 182g and the hydroxybutyl vinyl ether (HBVE) of 107g.
Then, import the trifluorochloroethylene (CTFE) of 505g in autoclave, slowly heat up, after temperature reached 65 ℃, with 50% xylene solution that imported the t-butylperoxy pivarate of 7.0g in 7 hours in autoclave, restir is stopped reaction after 15 hours.
Xylene solution while the fluorinated copolymer that evaporates gained carries out solvent exchange with mineral turpentine, after nonvolatile component reaches 60 quality %, adds the Tetra hydro Phthalic anhydride of the hydrogenation of 5.8g, add the triethylamine of 0.05g again after, flask is slowly heated up.After the interior temperature of flask reaches 70 ℃, this temperature was kept 2 hours, obtain number-average molecular weight (Mn) and be 7300, hydroxyl value is that 47mgKOH/g, acid number are that 2mgKOH/g, Tg are the mineral turpentine solution (nonvolatile component is 60 quality %) of 30 ℃ fluorinated copolymer A.
(manufacturing of fluorinated copolymer B)
Except that the HBVE of 2-EHVE, the 195g of CHVE, the 184g of the monomeric 170g of consisting of that contains two keys, other preparation manipulation is identical with the manufacturing of fluorinated copolymer A, makes Mn and be 7200, hydroxyl value is that 88mgKOH/g, acid number are that 2mgKOH/g, Tg are the mineral turpentine solution (nonvolatile component is 60 quality %) of 22 ℃ fluorinated copolymer B.
Contain HBVE in the monomer of two keys among the fluorinated copolymer B and surpass this point of 30 moles of % and be not inconsistent, and the hydroxyl value of fluorinated copolymer B surpasses 55mgKOH/g with the present invention.
(manufacturing of fluorinated copolymer C)
Except that the HBVE of 2-EHVE, the 109g of CHVE, the 66g of the monomeric 365g of consisting of that contains two keys, other preparation manipulation is identical with the manufacturing of fluorinated copolymer A, makes Mn and be 6800, hydroxyl value is that 48mgKOH/g, acid number are that 2mgKOH/g, Tg are the mineral turpentine solution (nonvolatile component is 60 quality %) of 37 ℃ fluorinated copolymer C.
This point of fluorinated copolymer C 20 moles of % of 2-EHVE less than in the monomer that contains two keys is not inconsistent with the present invention.
(manufacturing of fluorinated copolymer D)
Except that the HBVE of 2-EHVE, the 82g of the monomeric 507g of consisting of that contains two keys, other preparation manipulation is identical with the manufacturing of fluorinated copolymer A, makes Mn and be 7500, hydroxyl value is that 36mgKOH/g, acid number are that 2mgKOH/g, Tg are the mineral turpentine solution (nonvolatile component is 60 quality %) of 6 ℃ fluorinated copolymer D.
Containing 2-EHVE in the monomer of two keys among the fluorinated copolymer D surpasses this point of 80 moles of % and is not inconsistent with the present invention.
(manufacturing of fluorinated copolymer E)
Except that the HBVE of 2-EHVE, the 87g of CHVE, the 194g of the monomeric 272g of consisting of that contains two keys, other preparation manipulation is identical with the manufacturing of fluorinated copolymer A, makes Mn and be 7400, hydroxyl value is that 38mgKOH/g, acid number are that 2mgKOH/g, Tg are the mineral turpentine solution (nonvolatile component is 60 quality %) of 24 ℃ fluorinated copolymer E.
This point of 10 moles of % of HBVE less than that contains among the fluorinated copolymer E in the monomer of two keys is not inconsistent with the present invention.In addition, the not enough 40mgKOH/g of the hydroxyl value of fluorinated copolymer E.
(manufacturing of fluorinated copolymer F)
Except that the HBVE of the n-octyl vinyl ether (NOVE) of CHVE, the 182g of the monomeric 263g of consisting of that contains two keys, 107g, other preparation manipulation is identical with the manufacturing of fluorinated copolymer A, makes Mn and be 7500, hydroxyl value is that 47mgKOH/g, acid number are that 2mgKOH/g, Tg are the mineral turpentine solution (nonvolatile component is 60 quality %) of 28 ℃ fluorinated copolymer F.
Not comprising this point of monomer that contains branched-chain alkyl among the fluorinated copolymer F is not inconsistent with the present invention.
(manufacturing of fluorinated copolymer G)
Except that the HEVE of 2-EHVE, the 99g of CHVE, the 262g of the monomeric 235g of consisting of that contains two keys, other preparation manipulation is identical with the manufacturing of fluorinated copolymer A, make Mn and be 6700, hydroxyl value is that 45mgKOH/g, acid number are that 2mgKOH/g, Tg are the mineral turpentine solution (nonvolatile component 60%, nonvolatile component 70%) of 26 ℃ fluorinated copolymer G.
(example 1～7)
With the mineral turpentine (nonvolatile component 60 quality %) of the fluorinated copolymer A～G of gained as 1, with the mineral turpentine dilution until gonorrhoea occurring, but try to achieve dilution ratio (dilutions of mineral turpentine).
Table 1 is depicted as the monomer of fluorinated copolymer A～G and forms (mole %), hydroxyl value, acid number, Mn and mineral turpentine dilution property.Even fluorinated copolymer A, D, G do not see appearance fully from turbid yet when having diluted 10 times, so their mineral turpentine dilution property is more than 10 times.
Table 1
| Example | ????1 | ???2 | ????3 | ????4 | ????5 | ???6 | ????7 |
| Fluorinated copolymer | ????A | ???B | ????C | ????D | ????E | ???F | ????G |
| ????CTFE | ????50 | ???50 | ????50 | ????50 | ????50 | ???50 | ????50 |
| ????CHVE | ????25 | ???16 | ????34 | ????- | ????26 | ???25 | ????20 |
| ????2EHVE | ????14 | ???14 | ????5 | ????41 | ????15 | ???- | ????18 |
| ????HBVE | ????11 | ???20 | ????11 | ????9 | ????9 | ???11 | ????- |
| ????HEVE | ????- | ???- | ????- | ????- | ????- | ???- | ????12 |
| ????NOVE | ????- | ???- | ????- | ????- | ????- | ???14 | ????- |
| Hydroxyl value | ????47 | ???88 | ????48 | ????36 | ????38 | ???47 | ????45 |
| Acid number | ????2 | ???2 | ????2 | ????2 | ????2 | ???2 | ????2 |
| ????Mn | ????7300 | ???7200 | ????6800 | ????7500 | ????7400 | ???7500 | ????6700 |
| Mineral turpentine dilution property | More than 10 times | 1.5 doubly | 3 times | More than 10 times | 10 times | 3.5 doubly | More than 10 times |
(example 8～15)
In the mineral turpentine solution (nonvolatile component 60 quality %) of the fluorinated copolymer A～G of 100 mass parts, drop into the solvable type isocyanate curing agent of mineral turpentine (the ケ ネ-ト D-177N of the amount of Table 2 (mass parts), trade(brand)name, Mitsui Takeda Chemical Co., Ltd's system), flow promotor (BYK-320, trade(brand)name, polyether-modified methyl alkyl polysiloxane, the BYK-Chemie corporate system), as the dibutyl tin dilaurate of curing catalysts, make coating A～G.
In addition, example 10 is except the mineral turpentine solution (nonvolatile component 70 quality %) with the fluorinated copolymer G of 80 mass parts replaces the mineral turpentine solution (nonvolatile component 60 quality %) of fluorinated copolymer G of 100 mass parts, other operation is identical with example 9, makes coating.
Nco index in the table 2 is 1, the NCO=1/1 of the OHV/ solidifying agent of expression fluorinated copolymer.
Gardner viscosity in the table 2 is meant with gardner bubble viscometer the rise time of the bubble in the sample is measured, and can represent this viscosity with the viscosity mark by this rise time conversion stokes viscosity.The viscosity mark with following stokes viscosity (unit: St) expression, U:5.89～7.56, V:7.57～9.77, X:11.9～15.2, Z3:41.3～54.8.
At solvent-borne type propenyl urethane coating through the external coating white of the alumina plate of chromate treating, form thick the filming of 25 μ m, distinguish the coating of the aforementioned coating A～G of application on its surface again, form thick the filming of 20 μ m respectively, in 20 ℃ thermostatic chamber, carry out the maintenance in 2 weeks.Gained filmed carry out following evaluation.
[binding property of filming]: judge zero with finger touch: no binding property, *: binding property is arranged.
[charcoal contaminative] sprinkles carbon black #5 (Degussa Co., Ltd. system, trade(brand)name) equably in film coated surface, after shaking off, and this place and the difference of the pollution level that does not sprinkle sooty place Δ L value representation.Δ L is the value of the difference of expression brightness, and Δ L is more than 10, and expression has contaminative.Δ L is with SQ-2000 (colour-difference meter: Japanese electric look Industrial Co., Ltd system) measure.
[cross cut test]: quote JIS5400 8.5 standards
[mirror surface luster of filming]: quote JIS5400 7.6 standards
Table 2
| ????8 | ????9 | ????10 | ????11 | ????12 | ????13 | ????14 | ????15 | |
| Fluorinated copolymer | ||||||||
| ??A(47mgKOH/g) | ??100 | ????- | ????- | ????- | ????- | ????- | ????- | ????- |
| ??B(90mgKOH/g) | ??- | ????- | ????- | ????100 | ????- | ????- | ????- | ????- |
| ??C(46mgKOH/g) | ??- | ????- | ????- | ????- | ????100 | ????- | ????- | ????- |
| ??D(46mgKOH/g) | ??- | ????- | ????- | ????- | ????- | ????100 | ????- | ????- |
| ??E(36mgKOH/g) | ??- | ????- | ????- | ????- | ????- | ????- | ????100 | ????- |
| ??F(46mgKOH/g) | ??- | ????- | ????- | ????- | ????- | ????- | ????- | ????100 |
| ??G(45mgKOH/g) | ??- | ????100 | ????80 | ????- | ????- | ????- | ????- | ????- |
| Nonvolatile component in the mineral turpentine solution (quality %) | ??60 | ????60 | ????70 | ????60 | ????60 | ????60 | ????60 | ????60 |
| ケ ネ-ト D-177N BYK-320 dibutyl tin dilaurate nco index | ??10.5 ??0.1 ??0.001 ??1 | ????10.3 ????0.1 ????0.001 ????1 | ????10.3 ????0.1 ????0.001 ????1 | ????19.7 ????0.1 ????0.001 ????1 | ????10.7 ????0.1 ????0.001 ????1 | ????8.0 ????0.1 ????0.001 ????1 | ????8.5 ????0.1 ????0.001 ????1 | ????10.5 ????0.1 ????0.001 ????1 |
| The gardner viscosity of coating | ??V | ????V | ????Z3 | ????X | ????V | ????U | ????U | ????V |
| The binding property charcoal contaminative of filming | ??○ ????6.5 | ????○ ????????7.2 | ????○ ????????7.1 | ????○ ????????5.8 | ????○ ????????6.9 | ????× ????????14.3 | ????× ????????13.7 | ????○ ????????6.9 |
| The cross cut test | ??100/ ??100 | ????100/ ????100 | ????100/ ????100 | ????100/ ????100 | ????100/ ????100 | ????100/ ????100 | ????100/ ????100 | ????100/ ????100 |
| The mirror surface luster of filming | ??85 | ????88 | ????84 | ????86 | ????85 | ????89 | ????86 | ????85 |
In the table 1, the mineral turpentine of fluorinated copolymer B, C, F dilution property is below 4 times.In the painting operation, when being used for the utensil of application with the mineral turpentine washing, mineral turpentine dilution property is below 4 times, and undissolved resin residue is in utensil, because can be, so used the coating of example 11,12,15 of fluorinated copolymer B, C, F undesirable to painting operation generation detrimentally affect.Corresponding to this, fluorinated copolymer A of the present invention, G have the good mineral turpentine dilution property more than 10 times, are suitable for using as coating.
In the table 2, used fluorinated copolymer A example 8, used that the coating of the example 9,10 of fluorinated copolymer G forms film all fine in all assessment items.Corresponding to this, used the example 13 of fluorinated copolymer D, E and the binding property of filming that 14 coating forms relatively poor.In addition, its charcoal contaminative is also relatively poor, so infer that the hardness of filming of example 13 and 14 is lower.
Coating of the present invention is solvable in Weak solvent with fluorinated copolymer, contains this coating and can be used for Weak solvent type coating with the coating composition of fluorinated copolymer, and the coating that contains this coating composition can form higher the filming of hardness.
Claims (7)
1. dissolve in the coating fluorinated copolymer of Weak solvent, it is characterized in that, it be fluoroolefin and can with the monomeric multipolymer of two keys of containing of fluoroolefin copolymerization, based on the fluorine content of fluoroolefin more than 10 quality %, contain in the monomer of two keys and comprise the hydroxyl of 10～30 moles of %, and contain the branched-chain alkyl of carbonatoms more than 3 of 20～80 moles of %.
2. coating fluorinated copolymer as claimed in claim 1, its feature are that also hydroxyl value is 40～55mgKOH/g.
3. coating fluorinated copolymer as claimed in claim 1 or 2, its feature are that also aforementioned fluoroolefin is tetrafluoroethylene or trifluorochloroethylene.
4. as each described coating fluorinated copolymer in the claim 1～3, its feature is that also the aforementioned monomer that contains two keys that comprises hydroxyl is the hydroxyalkyl vinyl ether of carbonatoms 2～4.
5. as each described coating fluorinated copolymer in the claim 1～4, its feature is that also the aforementioned monomer that contains two keys that contains the branched-chain alkyl of carbonatoms more than 3 is a 2-ethylhexyl vinyl ether.
6. coating composition is characterized in that, contains in the claim 1～5 each described coating with fluorinated copolymer and Weak solvent.
7. coating is characterized in that, contains described coating composition of claim 6 and solidifying agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003054600 | 2003-02-28 | ||
| JP200354600 | 2003-02-28 |
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| CN (1) | CN1271100C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101098941B (en) * | 2005-01-07 | 2010-10-13 | 大金工业株式会社 | Curable fluorine-containing coating composition |
| CN101528871B (en) * | 2006-10-16 | 2011-11-30 | 旭化成化学株式会社 | Fluorine coating composition |
| CN101522837B (en) * | 2006-10-05 | 2012-10-17 | 三井化学株式会社 | Composition for two-component fluorine coating material |
| WO2020056663A1 (en) * | 2018-09-20 | 2020-03-26 | Honeywell International Inc. | Fluorocopolymers for coating applications |
| CN110951360A (en) * | 2019-11-29 | 2020-04-03 | 国网山东省电力公司临沂供电公司 | Anticorrosive paint containing graphene oxide special for steel structure and preparation method thereof |
| CN112437795A (en) * | 2018-07-18 | 2021-03-02 | Ａｇｃ株式会社 | Coating material, substrate with coating film, and method for producing substrate with coating film |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101270397B1 (en) * | 2009-03-25 | 2013-06-07 | 다이킨 고교 가부시키가이샤 | Non-fouling ordinary-temperature-curable coating composition |
| KR102428924B1 (en) * | 2022-02-22 | 2022-08-04 | 이에이바이오스 주식회사 | Photoluminescent nano-ceramic organic/inorganic composite line marking paint and manufacturing process thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58133871A (en) * | 1982-02-05 | 1983-08-09 | Asahi Glass Co Ltd | Corrosion preventive coating method |
| JPH0532727A (en) * | 1991-07-30 | 1993-02-09 | Central Glass Co Ltd | Resin composition for coating material |
| JPH05302055A (en) * | 1992-04-24 | 1993-11-16 | Asahi Glass Co Ltd | Chlorine-containing coating composition |
| KR0138142B1 (en) * | 1992-06-10 | 1998-05-15 | 강진구 | Image quality compensation circuit |
-
2004
- 2004-02-26 KR KR1020040013174A patent/KR100874627B1/en not_active IP Right Cessation
- 2004-02-27 CN CNB2004100082154A patent/CN1271100C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101098941B (en) * | 2005-01-07 | 2010-10-13 | 大金工业株式会社 | Curable fluorine-containing coating composition |
| CN101522837B (en) * | 2006-10-05 | 2012-10-17 | 三井化学株式会社 | Composition for two-component fluorine coating material |
| CN101528871B (en) * | 2006-10-16 | 2011-11-30 | 旭化成化学株式会社 | Fluorine coating composition |
| CN112437795A (en) * | 2018-07-18 | 2021-03-02 | Ａｇｃ株式会社 | Coating material, substrate with coating film, and method for producing substrate with coating film |
| WO2020056663A1 (en) * | 2018-09-20 | 2020-03-26 | Honeywell International Inc. | Fluorocopolymers for coating applications |
| CN110951360A (en) * | 2019-11-29 | 2020-04-03 | 国网山东省电力公司临沂供电公司 | Anticorrosive paint containing graphene oxide special for steel structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20040077513A (en) | 2004-09-04 |
| CN1271100C (en) | 2006-08-23 |
| KR100874627B1 (en) | 2008-12-17 |
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