CN1454243A - Dual cure coating compositions having improved scratch resistance, coated substrates and methods related thereto - Google Patents

Dual cure coating compositions having improved scratch resistance, coated substrates and methods related thereto Download PDF

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Publication number
CN1454243A
CN1454243A CN00819844A CN00819844A CN1454243A CN 1454243 A CN1454243 A CN 1454243A CN 00819844 A CN00819844 A CN 00819844A CN 00819844 A CN00819844 A CN 00819844A CN 1454243 A CN1454243 A CN 1454243A
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China
Prior art keywords
composition
coating composition
ground
coating
group
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Inventor
L·G·安德森
S·A·戴索
M·E·哈特曼
D·E·海斯
K·L·卡斯特
R·J·塞德瓦里
D·A·辛普森
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PPG Industries Ohio Inc
PPG Industries Inc
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PPG Industries Inc
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Publication of CN1454243A publication Critical patent/CN1454243A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Coating compositions formed from components including radiation and thermally curable material(s); curing agent(s) and a plurality of particles are provided, wherein each component is different. Also provided are multi-component composite coatings which include a cure basecoat deposited from a pigmented coating composition and a cured topcoat deposited from a topcoating composition. The multi-component composite coatings of the invention provide highly scratch resistant color-plus-clearcoatings.

Description

Double curing coating composition, ground and associated method with improved scratch resistance through applying
Invention field
Certain embodiments of the present invention say briefly and relate to by radiation curable material, thermal curable material, solidifying agent and multiple granuloplastic double curing coating composition that wherein each composition is inequality.Other embodiments of the present invention say briefly and relate to by the material that has at least a radiation curable group and at least a thermal curable group, solidifying agent and multiple granuloplastic double curing coating composition that wherein each composition is inequality.Other embodiments of the present invention relate to the ground that scribbles above-mentioned curing composition.Other embodiments of the present invention relate to the method for improving the ground scratch resistance.For the ordinary skill in the art, obvious specific embodiments of the present invention can relate to some or all and other the desirable aspects in these aspects of the present invention.
Background of invention
In the past during the decade, people are devoted to reduce the topsoil that is caused by the volatile solvent of emitting in the japanning process.But the organic solvent that does not use flowability and levelling property to coating that huge contribution is arranged often is difficult to obtain high quality, slick finishing coat, and these are that industry and car industry are needed.Except needs obtain the nearly flawless outward appearance of seeing, these coatings also need durable wear, and economy applies with being easy to.
The heat-setting thermosetting resin of routine is used for coating composition may be undesirable, because must come letdown resin so that easily be coated on the ground with solvent.Because cost and environment reason, it is unfavorable using solvent, because solvent must during curing be removed from coating composition.
In order to alleviate above problem, to have developed by ionizing rays or actinic radiation and come solidified radiation-sensitive material, it has reduced or eliminated the demand to solvent.Yet the flexibility of radiation-curable couting can be less than desired, and the performance of this coating composition is difficult for being modified to be used for different purposes.
US 4,025, and 407 disclose with radiation-sensitive materials or the traditional thermosetting resin of actinic light sensitive material dilution, and coating is carried out ionizing rays or actinic radiation, and the conventional curing mechanism by thermosetting resin is cured then.In embodiment 1, thermosetting resin is by with radiation-sensitive monomer and radiation non-sensitive type aliphatic vulcabond and TiO 2Mix with black tone, make this coating stand the electron beam irradiation, then by making this coating moisture curing in 24 hours 140 heating.
US 5,571, and 297 disclose a kind of adhesive coating, comprise the mixture of abrasive particle and a kind of compound, and this compound has the functional group and at least a heat-setting functional group of at least a radiation-hardenable.
The color-plus-clear coating system is included in and applies the colored or painted undercoat of one deck on the ground, apply layer of transparent or varnish coating subsequently on this undercoat, this system becomes more and more popular as the original modification (originalfinishes) that comprises as numerous consumer's goods of automobile.The color-plus-clear coating system has outstanding appearance property such as glossiness and reflection sharpness, and these depend primarily on Clear coating.This color-plus-clear coating system becomes more and more popular and is used for automobile, aircraft, the floor covering such as ceramic tile and timber floor, packing coating etc.
The film-forming composition of finishing coat especially is used for forming those of transparent varnish layer in the automobile-used and industrial color-plus-clear coating system, can be subjected to occurring in the destruction that damage in the assembling process and numerous environmental factors produce.Damage in the assembling process comprises the paint film damage when applying or solidify of undercoat or varnish coating.Destructive environmental factors comprises the acidic precipitation thing, be exposed under the ultraviolet radiation from daylight, high relative humidity and high temperature, participant scratch the material that is coated with the surface and contact the little and hard material that the destruction that produced and participant peel off coatingsurface and collide the destruction that is produced.
Generally, harder, highly cross-linked film can show improved scratch resistance, but it is flexible poor, and is easy to very much slabbing and/or heat cracking owing to the caused film embrittlement of high crosslink density.And film softer, low cross-linking is difficult for slabbing or heat cracking, but owing to the lower crosslink density of cured film is easy to scratch, produce water spots and acid etching.
In addition, elastomerics trolley part and accessory, for example elastomerics collision bumper and hood generally are that " away from the scene " applies and shipping arrives automobile assembly plant.The coating composition that is coated on this elastomerics ground is generally prepared to such an extent that flexibility is arranged very much, thereby makes the coating can be with ground bending or deflection and do not ftracture.In order to obtain necessary flexibility, the coating composition that is used on the elastomerics ground is prepared to such an extent that can produce the coating that has than lower crosslink density usually, perhaps contains the toughening auxiliary agent that is useful on the total glass transition temperature (Tg) that reduces film.Although can obtain acceptable flexibility with these compounding processs, this also can produce the softer film that is easy to scratch.Therefore, must pay huge cost and effort and pack the parts that applied, be scratched during automobile assembly plant in shipping with the surface that prevents to apply.
US 4,822,828 propose vinyl-functional silane is used in the aqueous radiation curable coating composition, this coating composition contains: the vinyl-functional silane of (a) counting 50-85% with total dispersion weight, (b) count the polyfunctional acrylic ester of 15-50% and (c) light trigger of optional 1-3wt% with total dispersion weight.This vinyl-functional silane is the partial condensate of silicon-dioxide and silane, is to meet formula (R) thereby at least 60% silane is arranged aSi (R ') b(R ") cVinyl-functional silane, wherein R is the alkyl of allyl group or vinyl-functional; R ' is hydrolyzable alkoxyl group or methoxyl group; R " be alkyl non-hydrolysable, saturated, phenyl or siloxy-, so that a+b+c=4; And a 〉=1; B 〉=1; C 〉=0.This patent disclosure these coating compositions can be coated on the plastic material, and can solidify down by being exposed to the irradiation of ultraviolet ray or electron beam, thus form substantial transparent, the damage resistant coating.
Although recently the color-plus-clear coating system is improved, the car paint field still needs to have the finishing coat of the good scratch resistance and the not embrittlement of filming.In addition, useful provide that the elastomerics ground that uses in a kind of industry and the car industry uses not only have flexibility but also a damage resistant finishing coat.
Summary of the invention
In one embodiment, the present invention relates to a kind of coating composition that is formed by following compositions, described composition comprises: (a) at least a first material, and it comprises the reactive functionality of at least a radiation-hardenable; (b) at least a second material, it comprises at least a heat-setting reactive functionality; (c) at least a solidifying agent, it can with at least a heat-setting reactive functionality reaction, this at least a solidifying agent is selected from the mixture of isocyanic ester, polyepoxide, polyprotonic acid, polyvalent alcohol and aforementioned substances of polyisocyanates, the triazine derivatives of aminoplast(ic) resin, polyisocyanates, sealing; (d) multiple particle, they are selected from the mixture of inorganic particle, composite particles and aforementioned substances, and wherein each composition is different.
In another embodiment, the present invention relates to a kind of coating composition that forms by following compositions, described composition comprises: (a) at least a material, and it comprises at least a reactive functionality capable of being solidified by ultraviolet and at least a heat-setting reactive functionality; (b) at least a solidifying agent, it can with at least a heat-setting reactive functionality reaction, this at least a solidifying agent is selected from the mixture of isocyanic ester, polyepoxide, polyprotonic acid, polyvalent alcohol and aforementioned substances of polyisocyanates, the triazine derivatives of polyisocyanates, sealing; (c) multiple particle, wherein each composition is different.
In addition, disclosed in coated substrate also belongs to scope of the present invention, it comprises ground and the curing composition that is coated at least a portion ground, and this curing composition can be any aforesaid curing composition of the present invention.The present invention also provides a kind of method of coated substrate, is included at least a portion ground and forms cured compositions, and this curing composition can be any aforesaid curing composition of the present invention.Disclosed automotive substrates through applying also belongs in the scope of the invention, and it comprises a kind of automotive substrates that scribbles any aforesaid curing composition of the present invention to small part.The present invention also provides the method for producing the automotive substrates through applying, and comprises obtaining a kind of automotive substrates, and form any aforesaid curing composition of the present invention at least a portion of this automotive substrates.
A kind of polycomponent composite paint also is provided, has comprised the undercoat that forms by painted coating composition deposition, and the finishing coat that forms by any aforesaid curing composition of the present invention on this undercoat.The present invention also provides the method for producing the polycomponent composite paint, comprising: (a) apply painted composition to form undercoat on ground; (b) at least a portion undercoat, apply any aforesaid coating composition as the investment precoat composition; (c) the investment precoat composition is solidified to form any aforesaid curing composition of the present invention.
Another embodiment of the present invention also provides the method for improving the scratch resistance of polymeric substrate or polymeric coating, is included in and forms any aforesaid curing composition of the present invention on polymeric substrate or the polymeric coating.The present invention also provides the method for the glossiness of long-term maintenance polymeric substrate or polymeric coating, is included in and forms any aforesaid curing composition of the present invention at least a portion polymeric substrate or the polymeric coating.The method of recovering the glossiness of polymeric substrate or polymeric coating also is provided, has been included in and forms any aforesaid curing composition of the present invention at least a portion polymeric substrate or the polymeric coating.
In embodiment or in addition explanation, will be understood that on behalf of the numerical value of the quantity of composition, reaction conditions etc., all that use in specification sheets and claims all can change according to term " about " in all cases.Therefore, unless opposite explanation is arranged, otherwise the numerical parameter of listing in the following description book and claims is approximation, the performance that can go for according to the present invention and changing.At least, and be not in order to limit the enforcement of this principle that is equivalent to the claim scope, common rounding-off method be explained and be used to each numerical parameter should according to significant figure at least.
Although listing the numerical range and the parameter of wide region of the present invention is approximation, the records of values of listing in the specific embodiment gets accurate as far as possible.But any one numerical value just had certain error originally, and this error is the inevitable outcome of the standard deviation that draws in its corresponding measuring method.
Detailed description of preferred embodiments
In one embodiment, the present invention relates to a kind of coating composition that is formed by following compositions, described composition comprises: at least a first material, and it comprises the reactive functionality of at least a radiation-hardenable; At least a second material, it comprises at least a heat-setting reactive functionality; At least a solidifying agent, it can react with at least a heat-setting reactive functionality; With multiple particle, wherein each composition is different.Here " material " of usefulness is meant compound, monomer, oligopolymer or polymkeric substance.In a selectable embodiment, replace first and second materials or except first and second materials, film forming material can comprise at least a by heat energy solidified functional group and at least a by ionizing rays or actinic radiation solidified functional group.
Here the term of usefulness " each composition is inequality " is meant that the chemical structure of each composition is inequality in the composition.
Here usefulness and term " composition " logotype " curing ", for example " curing composition " is meant that the crosslinkable composition that at least a portion constitutes composition takes place partial cross-linked at least.In certain embodiments of the invention, the cross-linking density of crosslinkable composition, i.e. degree of crosslinking is crosslinked fully 5% to 100%.In another embodiment, cross-linking density is fully crosslinked 35% to 85%.In another embodiment, cross-linking density is fully crosslinked 50% to 85%.The cross-linking density scope can be the arbitrary combination that comprises these values of cited value.Those skilled in the art should understand, crosslinked existence and degree of crosslinking, i.e. and cross-linking density, the mensuration that can in all sorts of ways is as the dynamic mechanics heat analysis method (DMTA) that adopts TA Instruments DMA 2980 DMTA analysers to carry out in nitrogen.This method is measured the second-order transition temperature and the cross-linking density of coating or polymkeric substance free film.These physicalies of solidify material are relevant with the structure of cross-linked network.
As discussed above, composition of the present invention is formed by the composition that comprises at least a first material, and this first material contains the reactive functionality of at least a radiation-hardenable, and this reactive functionality can be solidified by ionizing rays and/or actinic radiation.
Here " ionizing rays " of usefulness be meant energy-rich radiation and/or be converted into neutron radiation or inferior energy that gamma radiation produced that described energy is at least 30,000 ev, and can be 50,000-300,000 ev by electron energy or other particle energys.Although have polytype ionizing rays such as X-ray, gamma-radiation and beta-rays all to be suitable for this purpose, also can use by quickening the radiation that high-energy electron or electron beam device produce.What be used to solidify the present composition can be according to changing such as the thickness of coating on the composition of formulation for coating material, the ground, the factors such as temperature of coating composition in the ionizing rays amount of rad.Usually, the wet film of the coating composition of the present invention that 1 mil (25 microns) is thick under the ionizing rays through being exposed to the 0.5-5 megarad, can be cured to and run through the state that its thickness reaches surface drying in the presence of oxygen.
" actinic radiation " is meant that the wavelength region of its electromagnetic radiation enters the light of infrared light region by ultraviolet ray (" UV ") zone through the visible region.The electromagnetic radiation wavelength scope that is used for solidifying the actinic radiation of coating composition of the present invention is generally 150-2,000 nanometer (nm), 180-1,000nm or 200-500nm.In one embodiment, can use the ultraviolet radiation of wavelength region as 10-390nm.The example of suitable ultraviolet source comprises mercury arc, carbon arc, low pressure, medium-pressure or high pressure mercury lamp, the diode of eddy flow plasma arc and emission UV-light.Suitable ultraviolet light emission lamp is that output area is the middle pressure mercury vapor lamp of 200-600 watt of/inch (79-237 watt/centimetre) fluorescent tube length.Usually, the wet film of the coating composition of the present invention that 1 mil (25 microns) is thick can run through the state that its thickness reaches surface drying by being exposed to be cured under the actinic radiation, and method is that to make this film be to pass through under the middle pressure mercury vapor lamp of 200-1000 millijoule/square centimeter wet film at four exposed amounts with the speed of 20-1000 feet per minute clock (6-300 rice/minute).
The reactive functionality of described at least a radiation-hardenable can be selected from the combination of vinyl, vinyl ether group, epoxy group(ing), dimaleoyl imino, fumaric acid ester group and aforementioned group.Suitable first material that has vinyl-functional comprise following will discuss have those of unsaturated ester group and vinyl ether group.The non-limiting example of suitable epoxy group(ing) comprises the alicyclic epoxy base.
Suitable first material that contains unsaturated ester group comprises and contains acrylate-based, methacrylate based and/or the ethyl propylene perester radical.Unsaturated ester group can be acrylate-based.The available materials that contains unsaturated ester group comprises the ester of acrylic or methacrylic acid and the comonomer of acid amides or this ester and other copolymerisable monomers.Suitable ester comprises (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) ethyl acrylate, (methyl) 2-Hydroxy ethyl acrylate, (methyl) glycidyl acrylate, two (methyl) vinylformic acid glycol ester, (methyl) vinylformic acid glycol ether ester, two (methyl) vinylformic acid Tetraglycol 99 ester, two (methyl) vinylformic acid glyceryl ester, three (methyl) vinylformic acid glyceryl ester, two (methyl) vinylformic acid-1, the ammediol ester, two (methyl) vinylformic acid dipropylene glycol ester, two (methyl) vinylformic acid-1, the 4-butanediol ester, three (methyl) vinylformic acid-1,2,4-trihydroxybutane ester, two (methyl) vinylformic acid-1,6-hexylene glycol ester, two (methyl) vinylformic acid-1,4-cyclohexanediol ester, two (methyl) vinylformic acid-1,4-Benzenediol ester, four (methyl) vinylformic acid pentaerythritol ester, two (methyl) vinylformic acid-1, the 5-pentadiol ester, TriMethylolPropane(TMP) two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxy propionate, (methyl) isobornyl acrylate, (methyl) vinylformic acid tetrahydrofuran ester, by aromatic glycidyl ethers (as bisphenol A diglycidyl ether) and aliphatic diglycidylether deutero-(methyl) acrylate, acrylamide or Methacrylamide, as (methyl) acrylamide, two acetone (methyl) acrylamide, N-(beta-hydroxyethyl) (methyl) acrylamide, N, two (beta-hydroxyethyl) (methyl) acrylamides of N-, methylene-bis (methyl) acrylamide, 1, two (methyl) acrylamides of 6-hexa-methylene, diethylenetriamine three (methyl) acrylamide, two (γ-(methyl) acrylamide propoxy-) ethane, the mixture of β-(methyl) acrylamide ethyl propylene acid esters and aforementioned substances.
First material that other available contain unsaturated ester group comprises hydroxy-functional unsaturated polyester carboxylicesters and polycaprolactone.Suitable hydroxy-functional unsaturated polyester carboxylicesters can be formed by ethylenically unsaturated carboxylic acids and polyvalent alcohol.The available ethylenically unsaturated carboxylic acids has at least two acid functional groups and/or its corresponding acid anhydride.The non-limiting example of ethylenically unsaturated carboxylic acids and acid anhydride comprises: the mixture of toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid and aforementioned substances.Unsaturated carboxylic acid can mix with following saturated carboxylic acid, as phthalic acid, m-phthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid, tetrahydro-phthalic acid, hexahydro-phthalic acid, tetrachloro phthalic acid, hexanodioic acid, nonane diacid, sebacic acid, succsinic acid, pentanedioic acid, propanedioic acid, pimelic acid, suberic acid, 2,2-dimethyl succinate, 2,2-dimethylated pentanedioic acid, 3, the acid anhydride of 3-dimethylated pentanedioic acid, aforementioned acid and the mixture of any aforementioned substances.
The polyvalent alcohol that can be used to prepare hydroxy-functional unsaturated polyester carboxylicesters comprises glycol ether, ethylene glycol, propylene glycol, dipropylene glycol, butyleneglycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, sorbyl alcohol, 1,6-hexylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1, two (hydroxyethyl) hexanaphthenes, 2 of 2-, 2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxy propionate, neopentyl glycol, 2-methyl isophthalic acid, the mixture of ammediol and aforementioned substances.If desired, can be with monofunctional alcohol such as C 1-C 15Monohydroxy-alcohol mixes with above-mentioned polyvalent alcohol.
The number-average molecular weight of unsaturated ester material can be 500-50,000 gram/mole, and this is standard test with the polystyrene with gel permeation chromatography.The unsaturated ester material can prepare with any method known in those skilled in the art, for example composition mixed, and 150-250 ℃ temperature range internal heating 1-10 hour, and remove the water that produces during the esterification.Can use conventional catalyst for esterification reaction to increase speed of response, as tosic acid, butyl stannonic acid, dibutyl tin oxide, tin protofluoride and stannous octoate.
Be suitable for vinyl ether functional formed material used in this invention and comprise the vinyl ether for preparing under pressure according to method known in those skilled in the art by two, three or four functionalized polyvalent alcohols, acetylene and basic catalyst.Also can use with the polyester of vinyl as end group, as US5, those disclosed (this paper introduces this patent as a reference) in 286,835.The non-limiting example of available vinyl ether functional formed material comprises tripropylene glycol divinyl ether, diethylene glycol divinyl ether, 1,4-butyleneglycol divinyl ether, Tetraglycol 99 divinyl ether, triethylene glycol divinyl ether, trimethylolpropane tris vinyl ether, polytetrahydrofuran divinyl ether, is the polyester of end group and the mixture of aforementioned substances with the vinyl ether.Available has the unsaturated ester class material and the urethane vinyl ethers material of vinyl ether functional group in addition, as US5, in 942,556 disclosed (this paper introduces this patent).
First material that other available contain epoxy-functional comprises the epoxy-functional monomer, has the polymkeric substance of at least two epoxy group(ing) or Oxyranyle as glycidyl methacrylate and per molecule.These materials are commonly called diepoxide or polyepoxide.Usually, the epoxy equivalent (weight) of epoxy functionalized fluidized polymer can be 128-2800, this with methyl violet as indicator, measure with perchloric acid and the titration of bromination quaternary ammonium.
Suitable epoxy functionalized fluidized polymer can be saturated or undersaturated, ring-type or acyclic, aliphatic, alicyclic, aromatics or heterocyclic.If desired, this epoxy functionalized fluidized polymer can have pendant hydroxyl group or terminal hydroxy group.They can have the substituting group such as halogen, hydroxyl and ether.The available types of these materials comprises by epihalohydrin (as Epicholorohydrin or epibromohydrin) and dibasic alcohol or polyvalent alcohol reacts the polyepoxide that obtains in the presence of alkali.Suitable polyvalent alcohol comprises polyphenol, as Resorcinol, pyrocatechol, quinhydrones, two (4-hydroxy phenyl)-2,2-propane (being dihydroxyphenyl propane), two (4-hydroxy phenyl)-1,1-Trimethylmethane, 4,4-dihydroxy benaophenonel, two (4-hydroxy phenyl)-1,1-ethane, two (2-hydroxy phenyl)-methane and 1,5-hydroxyl naphthalene.
The example of available polyepoxide comprises the diglycidylether of dihydroxyphenyl propane, as EPON  828 Resins, epoxy, can be buied by Shell Chemical Company.Other available polyepoxides comprise the poly glycidyl ester of polyglycidyl ether, the polycarboxylic acid of polyvalent alcohol, by the polyepoxide, the epoxy phenolics that have oxyalkylene group in the epoxidation institute deutero-polyepoxide of olefinic unsaturated cycloaliphatic compound, the epoxy molecule, and partly go functionalized with carboxylic acid, alcohol, water, phenol, mercaptan or other compounds that contains reactive hydrogen and formed the polyepoxide of hydroxyl polymer-containing.
In the time of in first material being joined other compositions that constitute coating composition, its amount in coating composition accounts for the 1-99wt% of resin solid gross weight in the composition that constitutes coating composition, accounts for 25-95wt%, or accounts for 50-95wt%.
" account in the composition resin solid gross weight " used herein is meant that amount that composition adds composition during forming is based on the gross weight of the solid (non-volatile content) of following compositions, described composition refers to any film forming component, any polysiloxane, the any solidifying agent that exists during coating composition forms, the material silyl-capped (but not comprising described particle) with the usefulness of any existence, any solvent, or any such as sterically hindered amine stabilizer, light trigger, the pigment that comprises pigment extender and filler, catalyzer, the additive solids of FLOW IMPROVERS and ultraviolet absorbers and so on.
In one embodiment, the present invention relates to a kind of coating composition, wherein first material comprises and can come the polysiloxane of solidified reactive functionality by ionizing rays or actinic radiation at least a having.In another embodiment, polysiloxane can comprise at least a by heat energy solidified functional group and at least a by ionizing rays or actinic radiation solidified functional group.
In one embodiment of the invention, described at least a polysiloxane has the functional group of at least a above radiation-hardenable of setting forth, and these functional groups are selected from the combination of vinyl, epoxy group(ing), dimaleoyl imino, fumaric acid ester group and aforementioned group.The general formula of polysiloxane will be discussed when heat-setting second material of following argumentation again.At least a polysiloxane that has the functional group of at least a radiation-hardenable can be present in the composition that constitutes coating composition with following amount, this amount is counted 0.5-95wt% with the gross weight of the resin solid in the composition that constitutes coating composition, also can be 25-95wt%, or be 50-95wt%.The content range of first material can be the arbitrary combination that comprises these values of cited value.
The composition that constitutes coating composition is except first material, can also comprise at least a other ethylenically unsaturated monomers or oligopolymer as required, include but not limited to vinyl monomer, as vinyl-acetic ester, vinylbenzene, Vinyl toluene, Vinylstyrene, methylvinylether, ethyl vinyl ether, butyl vinyl ether and their mixture.At least a other ethylenically unsaturated monomers or oligopolymer can be present in the composition that constitutes coating composition with following amount, this amount is counted 1-99wt% with the gross weight of the resin solid in the composition that constitutes coating composition, also can be 25-95wt%, or can be 50-95wt%.The content range of at least a other ethylenically unsaturated monomers or oligopolymer can be the arbitrary combination that comprises these values of cited value.
In coating is to solidify or combine with heat energy in another embodiment of solidified by actinic radiation by actinic radiation, and at least a free radical or positively charged ion light trigger or the photosensitizers with the initiated polymerization process of providing can also be provided the composition of formation coating composition.The absorption region of available light trigger is 150-2,000nm.The non-limiting example of available light trigger comprises butyl isomer, the α of bitter almond oil camphor, benzophenone, dihydroxy benaophenonel, anthraquinone, thioxanthone, substituted bitter almond oil camphor such as benzoin ether;-diethoxy phenyl methyl ketone, α; alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl third-1-ketone, 2; 4, the mixture of 6-trimethylbenzoyl diphenyl phosphine oxide and aforementioned substances.The non-limiting example of suitable cation light initiator comprises salt compounded of iodine, as FC 509  available from 3M, and sulfonium salt, as UVI-6991 and UVI-6974 available from Union Carbide.Light trigger can be 2-hydroxy-2-methyl-1-phenyl third-1-ketone and 2,4, and 50: 50 mixtures of 6-trimethylbenzoyl diphenyl phosphine oxide are as the DAROCURE4265 available from Ciba-Geigy Corporation.
In one embodiment, the composition of formation coating composition comprises at least a second material that has at least a heat-setting reactive functionality.Useful thermal curable reactive functionality comprises isocyanate group, epoxy group(ing), acidic group, amido, acid anhydride base and the '-aziridino of hydroxyl, vinyl, urethane groups, urea groups, amide group, carbamate groups, isocyanate group, sealing.In one embodiment, described at least a second material can have at least a reactive functionality that is selected from hydroxyl, carbamate groups, epoxy group(ing), isocyanate group and carboxyl.In another embodiment, described at least a second material can have at least a reactive functionality that is selected from hydroxyl and carbamate groups.
Second material can be following film-forming polymer, and described film-forming polymer is selected from the multipolymer and the mixture of hydroxy-functionalized polymer, polyester, acrylate copolymer, urethane, polyureas, polymeric amide, carbamate functional polymer, the polyisocyanates that is different from solidifying agent (c), the polyisocyanates that is different from the sealing of solidifying agent (c), the polyepoxide that is different from solidifying agent (c), polyethers, the polyacid that is different from solidifying agent (c), polyamines, many acid anhydrides and aforementioned substances.
The non-limiting example of suitable hydroxyl polymer-containing comprises the mixture of acrylic polyol, polyester polyol, polyurethane polyol, polyether glycol and any aforementioned substances.The polymkeric substance of hydroxyl can be that hydroxyl equivalent is the normal acrylic polyol of 1000-100 gram/solid.Term " equivalent " is based on the relative quantity of the various compositions that are used for preparing concrete material and based on the solid calculated value of concrete material.Relative quantity is meant the theoretical weight of the material (as the polymkeric substance of being made by these compositions) that can draw in gram and draws the particular functional group's who exists in the resulting polymers those of theoretical value.What obtain divided by the above-mentioned theory value with the theoretical weight of polymkeric substance is exactly equivalent.For example, hydroxyl equivalent is based on the reactive pendant hydroxyl group in the hydroxyl polymer-containing and/or the equivalent of terminal hydroxy group.
The suitable hydroxyl and/or the acrylate copolymer of carboxyl can be prepared by polymerisable ethylenically unsaturated monomer, and can be the multipolymer of (methyl) vinylformic acid and/or (methyl) acrylic acid hydroxy alkyl ester and one or more other polymerisable ethylenically unsaturated monomer, described other polymerisable ethylenically unsaturated monomers for example are (methyl) alkyl acrylates, comprise (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate and ethyl acrylate, and vinyl aromatic compounds, as vinylbenzene, alpha-methyl styrene and Vinyl toluene.Here " (methyl) acrylate " and the similar terms of usefulness are intended to comprise acrylate and methacrylic ester.
Acrylate copolymer can be by the unsaturated beta-hydroxy esters functionalized monomer preparation of olefinic.This monomer can be obtained by ethylenic unsaturated acid functional monomer such as monocarboxylic acid (for example vinylformic acid) and epoxy compounds reaction, described epoxy compounds do not participate in free radical that cause with polyreaction unsaturated acid monomer.The non-limiting example of this epoxy compounds is glycidyl ether and glycidyl ester.The non-limiting example of suitable glycidyl ether comprises the glycidyl ether of alcohols and phenols, as butylglycidyl ether, octyl glycidyl ether, phenyl glycidyl ether etc.The non-limiting example of suitable glycidyl ester comprises that the trade name available from Shell ChemicalCompany is those of CARDURA E, and is those of GLYDEXX-10 available from the trade name of ExxonChemical Company.Perhaps, this beta-hydroxy esters functionalized monomer is prepared with saturated carboxylic acid such as saturated monocarboxylic acid (for example Unimac 5680) as (methyl) glycidyl acrylate and glycidyl allyl ether by the unsaturated epoxy-functional monomer of olefinic.
Can be by making the monomer (as (methyl) glycidyl acrylate and glycidyl allyl ether) that contains ethylene oxide group carry out copolymerization and epoxy-functional being incorporated in the polymkeric substance that is prepared by polymerisable ethylenically unsaturated monomer with other polymerisable ethylenically unsaturated monomers (as previously discussed those).The preparation method of this epoxy-functional acrylate copolymer elaborates at US 4,001, and in the 156 3-6 hurdles, this paper introduces this patent as a reference.
Can carbamate-functional be incorporated in the polymkeric substance that is prepared by polymerisable ethylenically unsaturated monomer by making for example above-mentioned ethylenically unsaturated monomer and carbamate functional vinyl monomer (as the alkyl methacrylate of carbamate functional) carry out copolymerization.Available carbamate functional alkyl ester can prepare by hydroxyalkyl carbamate (it can be the reaction product of ammonia and ethylene carbonate or Texacar PC) and methacrylic anhydride are reacted.
Other available carbamate functional vinyl monomers for example comprise the reaction product of hydroxyethyl methylacrylate, isophorone diisocyanate and carboxylamine hydroxypropyl acrylate; The reaction product of Rocryl 410, isophorone diisocyanate and methyl alcohol.Also can use other carbamate functional vinyl monomer, as the reaction product of isocyanic acid (HNCO) with the acrylic or methacrylic acid mono (as Hydroxyethyl acrylate) of hydroxy-functional, and US3,479, those monomers of setting forth in 328, this paper introduces this patent as a reference.
Also can carbamate-functional be incorporated in the acrylate copolymer by making the reaction of hydroxy-functional acrylate copolymer and low-molecular-weight alkyl carbamate (as Urethylane).Also can by " commentaries on classics carbamoylation " reaction side carbamateyl is incorporated in the acrylate copolymer, " commentaries on classics carbamoylation " reaction in, the hydroxy-functional acrylate copolymer with react by alcohol or glycol ethers deutero-low molecular weight carbamate.Carbamate groups can exchange to produce carbamate functional acrylate copolymer and initial alcohol or glycol ethers with hydroxyl.And, can make hydroxy-functional acrylate copolymer and isocyanate reaction to produce side carbamateyl.Equally, can make the reaction of hydroxy-functional acrylate copolymer and urea to produce side carbamateyl.
Can be by the polymkeric substance that polymerisable ethylenically unsaturated monomer is made by in the presence of suitable catalyst; prepare with solution polymerization process known in those skilled in the art; described catalyzer such as organic superoxide or azo-compound; for example benzoyl peroxide or N, the N-Diisopropyl azodicarboxylate.Polyreaction can be carried out in making monomer dissolved organic solution with ordinary method in the art.Perhaps, these polymkeric substance can prepare with aqueous emulsion polymerization well known in the art or aqueous dispersion polymerization method.Ratio and reaction conditions to reactant are selected, and have the acrylate copolymer of required side functional group with generation.
Polyester polymers also can be used in the coating composition of the present invention as additional polymer.The available polyester polymers can comprise the condensation product of polyvalent alcohol and polycarboxylic acid.The non-limiting example of suitable polyvalent alcohol comprises ethylene glycol, neopentyl glycol, TriMethylolPropane(TMP) and tetramethylolmethane.The non-limiting example of suitable polycarboxylic acid comprises hexanodioic acid, 1,4-cyclohexyl dicarboxylic acid and six hydrogen phthalic acids.Except above-mentioned polycarboxylic acid, can also use the function equivalent of acid such as the acid anhydride that they exist, or the lower alkyl esters such as the methyl esters of acid.Also can use a small amount of monocarboxylic acid such as stearic acid.Ratio and reaction conditions to reactant are selected, and have the polyester polymers of required side functional group (being carboxyl or hydroxy functional group) with generation.
For example, the polyester of hydroxyl can be reacted with 1: 2 mol ratio as six hydrogen phthalic anhydrides and glycol such as neopentyl glycol by the acid anhydride of dicarboxylic acid and prepare.Owing to wish to strengthen dry air, thereby can use suitable drying oil fatty acid, and can comprise by Toenol 1140, soya-bean oil, Yatall MA, synourin oil or tung oil deutero-those.
The carbamate functional polyester can prepare by at first forming a kind of polyprotonic acid that can use when forming polyester and the hydroxyalkyl carbamate of polyol reaction.Perhaps, can will hold carbamate-functional to be incorporated in the polyester by making the reaction of isocyanic acid and hydroxy-functionalized polyesters.And can carbamate-functional be incorporated in the polyester by making the reaction of hydroxyl polyester and urea.In addition, also can carbamate groups be incorporated in the polyester by changeing the carbamoylation reaction.The preparation method of the polyester of suitable amido-containing acid ester functional group is US5, and 593,733 the 2nd hurdles the 40th walk to those of setting forth in the 4th hurdle the 9th row, and this paper quotes this patent as a reference.
The polyether polyols with reduced unsaturation that contains isocyanate terminated base (can seal) or hydroxyl also can be as the other polymkeric substance in the coating composition of the present invention.Operable polyurethane polyol or end group are that the urethane of NCO-is to react those that make by polyvalent alcohol that comprises polymerized polyalcohol and polyisocyanates.The also operable isocyanate terminated base or uncle and/or the polyureas of secondary amine of containing can be by including, but is not limited to polymerized polyamines at those of interior polyamines and polyisocyanates prepared in reaction.
Can regulate the equivalence ratio of hydroxyl/isocyanate or amine/isocyanic ester and selective reaction condition to obtain required end group.The non-limiting example of suitable polyisocyanates comprises US4, and 046,729 the 5th hurdle the 26th walks to those of setting forth in the 6th hurdle the 28th row, and this paper introduces this patent as a reference.The non-limiting example of suitable polyvalent alcohol comprises US 4,046, and 729 the 7th hurdles the 52nd walk to those of setting forth in the 10th hurdle the 35th row, and this paper introduces this patent as a reference.The non-limiting example of suitable polyamines comprises US 4,046, and 729 the 6th hurdles the 1st walk to the 7th hurdle the 32nd row and US 3,799, those of setting forth during 854 the 3rd hurdle 13-50 are capable, and this paper introduces this patent as a reference.
Can be by making polyisocyanates and having hydroxy functional group and have the pet reaction of side carbamateyl and carbamate-functional is incorporated in the polyether polyols with reduced unsaturation.Perhaps, can prepare urethane by making polyisocyanates and the pure and mild hydroxyalkyl carbamate of polyester polyols or the isocyanate reaction of the independent reactant of conduct.The non-limiting example of suitable polyisocyanates comprises aromatic polyisocyanate, (as 4,4 '-'-diphenylmethane diisocyanate, 1,3-phenylene vulcabond and tolylene diisocyanate), and aliphatic polyisocyanate is (as 1,4-tetramethylene diisocyanate and 1, the 6-hexamethylene diisocyanate).Can use alicyclic diisocyanate, as 1,4-cyclohexyl diisocyanate and isophorone diisocyanate.
The non-limiting example of suitable polyether glycol comprises the polyalkylene ethoxylated polyhydric alcohol, as has following structural formula (VII) or (VIII) those:
Figure A0081984400261
Or
Figure A0081984400262
Wherein substituent R is represented hydrogen or is had the low alkyl group of 1-5 carbon atom, comprises the mixing substituting group, and the value of n is 2-6, and the value of m is 8-100 or higher.The non-limiting example of polyalkylene ethoxylated polyhydric alcohol comprises poly-(oxygen tetramethylene) glycol (poly (oxytetramethylene) glycols), poly-(oxygen four ethylidene) glycol, poly-(oxygen-propylene) two pure and mild poly-(oxygen-1,2-butylidene) glycol.
Same useful can be by the formed polyether glycol of various polyvalent alcohol alkoxylates, above-mentioned various polyvalent alcohols for example are (but being not limited to) glycol, as ethylene glycol, 1, and 6-hexylene glycol, dihydroxyphenyl propane etc., or other higher polyols, as TriMethylolPropane(TMP), tetramethylolmethane etc.The polyvalent alcohol of the higher functionality that can use as required for example can be prepared by the compound alkoxylate such as sucrose or sorbyl alcohol.Operable a kind of alkoxylating method is to make polyvalent alcohol and alkylene oxide reaction in the presence of acidity or basic catalyst, and described alkylene oxide includes but not limited to oxyethane or propylene oxide.The concrete non-limiting example of polyethers comprises the Co. available from E.I.DuPont de Nemours and, and the name of Inc. is called those of TERATHANE and TERACOL.
In one embodiment, second material can comprise at least a polysiloxane that has at least a thermal curable group.This at least a polysiloxane has at least a following structural unit (I):
(I) R 1 nR 2 mSiO (4-n-m)/2Each substituent R wherein 1Can be identical or different, representative is selected from the group of H, OH, monovalence alkyl and monovalence siloxanes; Each substituent R 2Can be identical or different, representative comprises the group of at least a reactive functionality.
Should understand, above " at least a polysiloxane with at least a structural unit (I) " is that a kind of per molecule contains at least two Si bond things.Here the term " polymer " of usefulness " be intended to comprise oligopolymer, and include, but is not limited to homopolymer and multipolymer.It is also understood that that this at least a polysiloxane can comprise is straight chain, branching, dendroid or cyclic polysiloxane.
And the term of usefulness " reactivity " is meant that functional group is being enough to make under the composition solidified condition and can forming covalent linkage with other functional groups here.
Each m and the n that appear in the above at least a structural unit (I) satisfy following the requirement: 0＜n＜4,0＜m＜4, and 2≤(m+n)＜4.When (m+n) was 3, the value of representing with n can be 2, and the value of representing with m is 1.Equally, when (m+n) was 2, the value that n and m represent separately was 1.
Here " the monovalence alkyl " of usefulness is meant that the main chain repeating unit is only based on the univalent perssad of carbon.Here " monovalence " of usefulness be meant the substituting group form, only form the substituting group of a covalent linkage.The univalent perssad that for example is arranged at least a polysiloxane will form a covalent linkage with the Siliciumatom of this at least a polysiloxane polymer main chain.Here " alkyl " of usefulness is intended to comprise the alkyl of branching or non-branching.
Like this, when mentioning " monovalence alkyl ", this alkyl can be branching or non-branching, and acyclic or cyclic is saturated or undersaturated, or aromatics, and can contain 1-24 (or under the situation of aryl, being 3-24) carbon atom.The non-limiting example of this alkyl comprises alkyl, alkoxyl group, aryl, alkaryl and alkoxy aromatic yl.The non-limiting example of low alkyl group comprises as methyl, ethyl, propyl group and butyl.Here " low alkyl group " of usefulness is meant the alkyl with 1-6 carbon atom.One or more hydrogen atom of this hydrocarbon can be replaced by heteroatoms.Here " heteroatoms " of usefulness is meant the element outside the de-carbon, for example oxygen, nitrogen and halogen atom.
Here " siloxanes " of usefulness is meant to comprise and has two or the group of the main chain of a plurality of-SiO-group.For example with the R of above argumentation 1And the siloxane groups represented of the following R that will discuss, it can be branching or non-branching, straight chain or cyclic.Organic substituent that siloxane groups can be draped such as alkyl, aryl and alkaryl replace.This organic substituent can be replaced by heteroatoms (as oxygen, nitrogen and halogen atom), reactive functionality (for example above those reactive functionality about R2 of discussing) and the mixture of any aforementioned group.
In another embodiment, identical or different each substituent R 2Representative comprises the group of at least a following reactive functionality, and described reactive functionality is selected from polyisocyanate-based, primary amino, secondary amino group, amide group, carbamate groups, urea groups, urethane groups, vinyl, unsaturated ester group such as acrylate-based and methacrylate based, dimaleoyl imino, fumaric acid ester group, alkali such as sulfonium base and ammonium, acid anhydride base, hydroxyalkylamide groups and the epoxy group(ing) of hydroxyl, carboxyl, isocyanate group, sealing; Wherein m and n satisfy 0＜n＜4,0＜m＜4, and 2≤(m+n)＜4.
In one embodiment, the present invention relates to aforesaid coating composition, wherein, described at least a polysiloxane comprises at least two reactive functionality.The equivalent of the reactive group that this at least a polysiloxane has can be this at least a polysiloxane of 50-1000mg/ gram.In one embodiment, the hydroxyl equivalent of this at least a polysiloxane is this at least a polysiloxane of 50-1000mgKOH/ gram.In another embodiment, the hydroxyl equivalent of this at least a polysiloxane is this at least a polysiloxane of 100-300mg KOH/ gram, and in another embodiment, this hydroxyl equivalent is 100-500mg KOH/ gram.The hydroxyl equivalent scope of this at least a polysiloxane can be the arbitrary combination that comprises these values of cited value.
In another embodiment, the present invention relates to aforesaid coating composition, wherein at least one R 2The group representative comprises the group of at least one following reactive functionality, and described reactive functionality is selected from hydroxyl and carbamate groups.In another embodiment, the present invention relates to aforesaid coating composition, wherein at least one R 2The group representative comprises the group of at least two following reactive functionality, and described reactive functionality is selected from hydroxyl and carbamate groups.In another embodiment, the present invention relates to aforesaid coating composition, wherein at least one R 2The group representative comprises the group of an oxyalkylene group (oxyalkylene) and at least two hydroxyls.
In one embodiment, the present invention relates to aforesaid curing composition, wherein, described at least a polysiloxane has following structural formula (II) or (III):
Figure A0081984400291
Or Wherein the value of m is at least 1; M ' is 0-75; N is 0-75; N ' is 0-75; Each R can be identical or different, is selected from the mixture of H, OH, monovalence alkyl, monovalence siloxanes and any aforementioned group;-R aComprise following structural formula (IV):
(IV)-R 3-X wherein-R 3Be selected from alkylidene group, oxyalkylene group, alkarylene, alkylene group (alkenylene), oxygen alkylene group and inferior alkene aryl; X representative comprises the group of at least a following reactive functionality, and described reactive functionality is selected from polyisocyanate-based, primary amine groups, secondary amine, amide group, carbamate groups, urea groups, urethane groups, vinyl, unsaturated ester group such as acrylate-based and methacrylate based, dimaleoyl imino, fumaric acid ester group, alkali such as sulfonium base and ammonium, acid anhydride base, hydroxyalkylamide groups and the epoxy group(ing) of hydroxyl, carboxyl, isocyanate group, sealing.
Here " alkylidene group " of usefulness is meant acyclic or cyclic, carbon chain lengths are C 2-C 25Saturated hydrocarbyl.The non-limiting example of suitable alkylidene group include but not limited to respectively by propenyl, 1-butylene base, 1-pentenyl, 1-decene base and 1-heneicosene base deutero-those, as (CH 2) 3, (CH 2) 4, (CH 2) 5, (CH 2) 10(CH 2) 23, and derived from those of isoprene and myrcene.
Here " oxyalkylene group " of usefulness is meant that containing at least one links to each other with two carbon atoms and the carbon chain lengths of Sauerstoffatom between these two carbon atoms and alkylidene group is C 2-C 25Alkylidene group.The non-limiting example of suitable oxyalkylene group comprise by TriMethylolPropane(TMP) one allyl ethers, trimethylolpropane allyl ether, tetramethylolmethane one allyl ethers, polyethoxylated allyl alcohol and poly-propoxylation allyl alcohol deutero-those, as-(CH 2) 3OCH 2C (CH 2OH) 2(CH 2CH 2-).
Here " alkylidene aryl " of usefulness is meant that replace and carbon chain lengths alkylidene group is C by at least one aryl (as phenyl) 2-C 25Acyclic alkylidene group.If desired, this aryl can further be substituted.The non-limiting example of the suitable substituent of aryl includes but not limited to hydroxyl, benzyl, carboxylic acid group and aliphatic hydrocarbyl.The non-limiting example of suitable alkylidene aryl include but not limited to by vinylbenzene and 3-different-∝, ∝-dimethylbenzyl based isocyanate deutero-those, as-(CH 2) 2C 6n 4-and-CH 2CH (CH 3) C 6H 3(C (CH 3) 2(NCO)." alkylene group " used herein is meant that the carbon chain lengths with one or more pair key and alkylene group is C 2-C 25Acyclic or cyclic hydrocarbon group.The non-limiting example of suitable alkylene group comprise by propargyl alcohol and alkyne diol deutero-those, for example 2,4,7,9-tetramethyl--5-decine-4,7-glycol, it can be available from Air Products and Chemicals, Inc.Of Allentown, the SURFYNOL 104 of Pennsylvania.
Formula (II) and (III) be schematically, and do not mean that the part in the bracket must be a blocked is although can adopt blocked when needing.In some cases, polysiloxane can comprise multiple siloxane unit.Along with the increase of used siloxane unit quantity, this situation more and more becomes a reality, and when adopting the unitary mixture of multiple different silicones, especially has this situation.Using multiple siloxane unit and hope to form under the situation of block, can form the oligopolymer that can connect into block compound.By selective reaction thing suitably, can use compound with alternating structure or alternating structure block.
In one embodiment, the present invention relates to comprise the coating composition of aforementioned polysiloxane, wherein substituent R 3Represent oxyalkylene group.In another embodiment, R 3Represent oxyalkylene group, and the X representative comprises the group of at least two reactive functionality.
In another embodiment, the present invention relates to any coating composition by aforementioned composition preparation, described composition comprises at least a have said structure (II) or polysiloxane (III), and wherein (n+m) is 2-9.In another embodiment, described composition can comprise at least a have said structure formula (II) or polysiloxane (III), (n+m) is 2-3.In another embodiment, described composition can comprise at least a have said structure formula (II) or polysiloxane (III), (n '+m ') be 2-9.In another embodiment, described composition can comprise at least a have said structure formula (II) or polysiloxane (III), (n '+m ') be 2-3.
In one embodiment, the present invention relates to any aforesaid coating composition, composition wherein comprises at least a following polysiloxane, and wherein the X representative comprises at least a group that is selected from the reactive functionality of hydroxyl and carbamate groups.In another embodiment, the present invention relates to aforesaid polysiloxane as composition, wherein the X representative comprises the group of at least two hydroxyls.In another embodiment, the present invention relates to aforesaid polysiloxane as composition, wherein the X representative comprises the group of at least a following radicals, and described group is selected from the organic group of H, monohydroxy replacement and has the group of following structure formula V:
(V) R 4-(CH 2-OH) pSubstituent R when p is 2 wherein 4Representative And substituent R 3Represent C 1-C 4Alkylidene group, or when p is 3 substituent R 4Representative
Figure A0081984400321
Wherein at least a portion X representative has the group of structure formula V.In another embodiment, the present invention relates to any aforesaid curing composition, wherein m is 2, and p is 2.
In one embodiment of the invention, described at least a polysiloxane does not react with described particle.In another embodiment, the present invention relates to any aforesaid coating composition, wherein said particle is different with described at least a polysiloxane.In another embodiment, the present invention relates to any aforesaid coating composition, the median size of wherein said particle before mixing curing composition is lower than 100 nanometers.The back can elaborate the method for the known measurement median size of those of ordinary skills.
In one embodiment, the present invention relates to comprise at least a any aforementioned coating composition with structural formula (II) or polysiloxane (III), wherein, if there is no solidifying agent, if described at least a polysiloxane is the partial condensate of silanol, the partial condensate below the 70wt% is by CH so 3Si (OH) 3Form.These compositions that are used in these different embodiments can be selected from the above-mentioned coating composition, and other composition also can be selected from above those that enumerate.
In another embodiment, the present invention relates to any aforesaid coating composition, it is the polysiloxane of the reaction product of following reactant at least that the composition that wherein constitutes coating composition comprises at least a: (i) polysiloxane of at least a formula (VI):
Figure A0081984400322
Wherein each substituent R can be identical or different, and representative is selected from the group of the mixture of H, OH, monovalence alkyl, monovalence siloxanes and any aforementioned group; At least one group of representing with R is H, and n ' is 0-100, also can be 0-10, can also be 0-5, is 2-50% thereby make the percentage composition of SiH in the polysiloxane, also can be 5-25%; And (ii) comprising at least a following functional group and at least a at least a molecule that can carry out the unsaturated link(age) of hydrosilylation reactions, described functional group is selected from polyisocyanate-based, primary amino, secondary amino group, amide group, carbamate groups, urea groups, urethane groups, vinyl, unsaturated ester group such as acrylate-based and methacrylate based, dimaleoyl imino, fumaric acid ester group, alkali such as sulfonium base and ammonium, acid anhydride base, hydroxyalkylamide groups and the epoxy group(ing) of hydroxyl, carboxyl, isocyanate group, sealing.In another embodiment, this at least a functional group is selected from hydroxyl.
Will be appreciated that various R bases can be identical or different, and in certain embodiments, the R base can all be the monovalence alkyl, or the mixture of different group (as monovalence alkyl and hydroxyl).
In another embodiment, this reaction product is an agglomerative not.Here " the not gelling " of usefulness be meant that reaction product is not crosslinked basically and have limiting viscosity in being dissolved in suitable solvent the time, this limiting viscosity for example can be measured according to ASTM-D1795 or ASTM-D4243.The limiting viscosity of reaction product is the sign of its molecular weight.On the other hand, the agglomerative reaction product has high molecular weight because of it, the limiting viscosity that can't record so have too high.Here the reaction product of " not crosslinked basically " of usefulness is meant that the weight-average molecular weight (Mw) that records with gel permeation chromatography is lower than 1,000,000.
Should also be noted that and to select the amount of above reactant contained unsaturated body in (ii), to obtain not agglomerative reaction product.In other words, when using the higher polysiloxane that contains silicon hydride (i) of Si-H functionality mean value, reactant (ii) can contain a small amount of unsaturated body.The polysiloxane (i) that for example contains silicon hydride can be a kind of low molecular weight material, and wherein n ' is 0-5, and the mean value of Si-H functionality is 2 or lower.In this case, reactant (ii) can contain two or more unsaturated link(age) that gelling just can be carried out hydrosilylation reactions not take place.
The non-limiting example that contains the polysiloxane (i) of silicon hydride comprise n ' be 0 and the Si-H average functionality be 2 o'clock 1,1,3, the 3-tetramethyl disiloxane; And n ' is about 2 o'clock the poly-methyl polysiloxane that contains silicon hydride for 4-5 and Si-H average functionality, as the MASILWAX BASE  available from BASFCorporation.
Can comprise the allyl ethers of hydroxy functional groups as above reactant material (ii), for example be selected from those of mixture of TriMethylolPropane(TMP) one allyl ethers, tetramethylolmethane one allyl ethers, trimethylolpropane allyl ether, polyoxyalkylenes alcohol (as polyethoxylated alcohols, poly-propoxylation and poly-butoxy alcohol), undecylenic acid-epoxy adduct, glycidyl allyl ether-carboxylic acid adducts and any aforementioned substances.The mixture of hydroxy-functional polyallyl ether and hydroxy-functional one allyl ethers or allyl alcohol also is suitable.In some cases, reactant (ii) can medial end portions contain at least one unsaturated link(age).Reaction conditions and reactant (i) and ratio are (ii) selected to produce required functional group.
The polysiloxane of hydroxy functional groups can form the half ester acidic group and prepares by making the polysiloxane that contains hydroxy functional group and acid anhydride avoid taking place under the reaction conditions of further esterification reaction in the reaction that only helps acid anhydride and hydroxy functional group.The non-limiting example of suitable acid anhydride comprises hexahydro-phthalic anhydride, methyl hexahydro-phthalic anhydride, phthalic anhydride, 1,2, the mixture of 4-benzenetricarboxylic anhydride, succinyl oxide, hexachloroendomethylene-tetrahvdrophthalic anhydride, alkenyl succinyl oxide and substituted alkenyl acid anhydride (as octenyl succinic anhydride) and any aforementioned substances.
The reaction product of making like this that contains the half ester base can further contain the polysiloxane of secondary hydroxyl with formation with the monoepoxide reaction.The non-limiting example of suitable monoepoxide comprises the mixture of phenyl glycidyl ether, n-butyl glycidyl ether, cresyl glycidyl ether, isopropyl glycidyl ether, glycidyl tertiary carbon acid esters (for example available from Shell Chemical Co. CARDURA E) and any aforementioned substances.
In another embodiment, the present invention relates to aforesaid coating composition, the composition that wherein constitutes this coating composition comprises at least a following polysiloxane, and this polysiloxane is the polysiloxane of a kind of amido-containing acid ester functional group, and it comprises the reaction product of following at least reactant:
(i) at least a polysiloxane that contains silicon hydride shown in the above structural formula (VI), wherein R is identical with above description to this structural formula with n ';
(ii) at least a hydroxy functional groups, have one or more above-mentioned material that can carry out the unsaturated link(age) of hydrosilylation reactions; With
(iii) at least a low-molecular-weight carbamate-functional materials comprises the reaction product of alcohol or glycol ethers and urea.
The example of this " low-molecular-weight carbamate-functional materials " includes but not limited to US 5,922,475 and 5,976, the own ester of alkyl carbamate described in 701 and carboxylamine, and glycol ether carbamate, this paper introduces these patents as a reference.
Carbamate-functional can carry out " commentaries on classics carbamoylation " reaction by the polysiloxane and the low-molecular-weight carbamate-functional materials that make hydroxy functional groups and be incorporated in the polysiloxane.Can react with the free hydroxyl group in the polysiloxane polyhydric alcohol (being the material that average per molecule has two or more hydroxyls) by the low molecular weight carbamate functionalised materials that alcohol or glycol ethers obtain, produce carbamate functional polysiloxane and initial alcohol or glycol ethers.To reaction conditions and reactant (i), (ii) and ratio (iii) select to form required group.
Low-molecular-weight carbamate-functional materials can prepare by alcohol or glycol ethers and urea are reacted in the presence of the catalyzer the inferior stannic acid such as butyl.The non-limiting example of suitable alcohol comprises low-molecular-weight aliphatic series, alicyclic and aromatic alcohol, as methyl alcohol, ethanol, propyl alcohol, butanols, hexalin, 2-Ethylhexyl Alcohol and 3-methyl butanol.The non-limiting example of suitable glycol ethers comprises ethylene glycol monomethyl ether and propylene glycol monomethyl ether.Can carbamate-functional be incorporated in the polysiloxane by making the free hydroxyl group reaction in isocyanic acid and the polysiloxane.
As mentioned above, except hydroxyl and/or carbamate-functional or replace hydroxyl and/or carbamate-functional, this at least a polysiloxane can contain one or more other reactive functionality, as the mixture of isocyanate group, carboxylic acid ester groups, uncle and/or secondary amine, amide group, urea groups, urethane groups, epoxy group(ing) and any aforementioned group of carboxyl, isocyanate group, sealing.
When at least a polysiloxane contained carboxyl functional group, this at least a polysiloxane can prepare with poly carboxylic acid or anhydride reactant by making at least a above-mentioned polysiloxane that contains hydroxy functional group.The polycarboxylic non-limiting example that is suitable for using comprises hexanodioic acid, succsinic acid and dodecanedioic acid.The non-limiting example of suitable acid anhydride comprises above-mentioned those.The ratio of reaction conditions and reactant is selected to produce required functional group.
When at least a polysiloxane contained one or more isocyanate functional group, this at least a polysiloxane can prepare by making the reaction of at least a above-mentioned polysiloxane that contains hydroxy functional group and polyisocyanates (as vulcabond).The non-limiting example of suitable polyisocyanates comprises aliphatic polyisocyanate, as aliphatic vulcabond, and for example 1,4-tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate; Alicyclic polyisocyanates, as 1,4-cyclohexyl diisocyanate, isophorone diisocyanate and α, α-eylylene diisocyanate; And aromatic polyisocyanate, as 4,4 '-'-diphenylmethane diisocyanate, 1,3-phenylene vulcabond and tolylene diisocyanate.These and other suitable polyisocyanates is set forth in US 4,046 in more detail, and 729 the 5th hurdles the 26th walk in the 6th hurdle the 28th row, and this paper introduces this patent as a reference.The ratio of reaction conditions and reactant is selected to form required functional group.
It is the polymeric material that contains urethane or urea of end group that substituent X in the structural formula (IV) can comprise with the mixture of isocyanic ester, hydroxyl, uncle or secondary amine functional groups or aforementioned any group.When substituent X comprises this functional group, described at least a polysiloxane can be the reaction product that at least a above-mentioned polysiloxane polyhydric alcohol, one or more polyisocyanates and one or more optional per molecule has the compound of at least two reactive hydrogen atoms, and described reactive hydrogen atom is selected from hydroxyl, primary amine groups and secondary amine.
The non-limiting example of suitable polyisocyanates be above-described those.The non-limiting example that per molecule has the compound of at least two reactive hydrogen atoms comprises polyvalent alcohol and the polyamines that contains uncle and/or secondary amine.
The non-limiting example of suitable polyvalent alcohol comprises the polyalkylene ethoxylated polyhydric alcohol, comprises thioether; Polyester polyol comprises the polyhydroxy polycarboxylic esteramides; And the acrylic copolymer of the polycaprolactone of hydroxyl and hydroxyl.Same available is the polyether glycol that is formed by various polyvalent alcohol alkoxylates, and described various polyvalent alcohols for example are glycol, and as ethylene glycol, 1,6-hexylene glycol, dihydroxyphenyl propane etc., or higher polyol are as TriMethylolPropane(TMP), tetramethylolmethane etc.Also can use polyester polyol.These and other suitable polyvalent alcohol is set forth in US 4,046,729 the 7th hurdle the 52nd walks to the 8th hurdle the 9th row, the 8th hurdle the 29th walks to the 9th hurdle the 66th row and US 3,919,315 the 2nd hurdles the 64th walk in the 3rd hurdle the 33rd row, and this paper introduces these patents as a reference.
The non-limiting example of suitable polyamines comprises uncle or secondary diamine or polyamines, wherein the group that links to each other with nitrogen-atoms can be saturated or undersaturated, aliphatic, alicyclic, aromatics, the aliphatic series that replaced by aromatics, by the aromatics and the heterocycle of aliphatic series replacement.The suitable aliphatic series and the example of alicyclic diamine comprise 1,1,2-propylene diamine, 1,8-octamethylenediamine, isophorone diamine, propane-2,2-hexahydroaniline etc.Suitable aromatic diamine comprises phenylenediamine and tolylene diamine, for example O-Phenylene Diamine and to tolylene diamine.These and other suitable polyamines is set forth in US4, and 046,729 the 6th hurdle the 61st walks in the 7th hurdle the 26th row, and this paper quotes this patent.
In one embodiment, the substituent X in the structural formula (IV) can comprise with hydroxyl or carboxylic acid functional being the group that contains polyester of end group.When X was this group, at least a polysiloxane can be one or more above-mentioned polysiloxane polyhydric alcohol, one or more has the reaction product of material and one or more organic polyhydric alcohol of at least one carboxylic acid functional.The non-limiting example of the suitable material that has at least one carboxylic acid functional comprises carboxy-containing acid group's as known in the art polymkeric substance, for example carboxy-containing acid group's acrylate copolymer, polyester polymers and polyether polyols with reduced unsaturation, as US 4,681, those of setting forth in 811.The non-limiting example of suitable organic polyhydric alcohol comprises above-mentioned those.
In order to form at least a polysiloxane that contains epoxy group(ing), the above-mentioned at least a polysiloxane that contains hydroxy functional group is further reacted with polyepoxide.This polyepoxide can be aliphatic series or alicyclic polyepoxide, or the mixture of any aforementioned substances.The non-limiting example of the polyepoxide that is suitable for comprises by at least a ethylenically unsaturated monomer (for example (methyl) glycidyl acrylate and glycidyl allyl ether) of at least one epoxy group(ing) and the epoxy-functional acrylic copolymer that one or more ethylenically unsaturated monomer that does not contain epoxy-functional is made of having.The preparation method of this epoxy-functional acrylic copolymer elaborates at US 4,681, and 811 the 4th hurdles the 52nd walk in the 5th hurdle the 50th row, and this paper introduces this patent as a reference.The ratio of reaction conditions and reactant is selected to form required functional group.
In one embodiment, the present invention relates to aforesaid coating composition, wherein said at least a polysiloxane contains heat-setting reactive functionality.In an interchangeable embodiment, at least a reactive functionality of polysiloxane can be solidified by ionizing rays or actinic radiation.In another interchangeable embodiment, polysiloxane can contain at least a by heat energy solidified functional group and at least a by ionizing rays or actinic radiation solidified functional group.Suitable radiation curable group was discussed in front in detail.
In the time of in second material being joined other compositions that constitute coating composition, its amount in coating composition accounts for the 0.5-98.5wt% of resin solid gross weight in the composition that constitutes coating composition usually.In one embodiment of the invention, in the time of in second material being joined other compositions that constitute coating composition, its amount is at least 25wt% usually.The amount of second material can account for the 5wt% at least of resin solid gross weight in the composition that constitutes coating composition, generally is at least 50wt%.And when in other compositions that second material joined coating composition, its amount is usually less than 98.5wt%.Its amount can account for below the 95wt% of resin solid gross weight in the composition that constitutes coating composition, is generally below the 90wt%.The amount scope of second material in coating composition can be to comprise the arbitrary combination of cited value in these interior values.
In another embodiment, replace first and second materials or except first and second materials, can use one or more pair solidify material to form coating composition, this pair solidify material comprises at least a by heat energy solidified functional group and at least a by ionizing rays or actinic radiation solidified functional group.The example of this material in front and application number be all to have disclosedly in the EP application of EP 940 422, this paper introduces this application as a reference.If there are two solidify material, in the time of in it being joined other compositions that constitute coating composition, its amount in coating composition accounts for the 0.5-99wt% of resin solid gross weight in the composition that constitutes coating composition usually, comprises cited value.
In one embodiment, the composition that constitutes coating composition comprise at least a can with the solidifying agent of thermal curable radical reaction in second material.This at least a solidifying agent can be selected from the mixture of isocyanic ester, polyepoxide, polyprotonic acid, polyvalent alcohol and aforementioned substances of polyisocyanates, the triazine derivatives of aminoplast(ic) resin, polyisocyanates, sealing.
Exist in the embodiment of two solidify material at another, the composition that constitutes coating composition comprises the solidifying agent of mixture of isocyanic ester, polyepoxide, polyprotonic acid, polyvalent alcohol and the aforementioned substances of at least a polyisocyanates that is selected from polyisocyanates, sealing, triazine derivatives.
In another embodiment, solidifying agent is an aminoplastics.Is known in the field with the aminoplast(ic) resin that comprises phenoplast as the solidifying agent that contains the material of hydroxyl, carboxylic acid group and carbamate-functional.Suitable aminoplastics (for example above those that discuss) persons skilled in the art are known.Aminoplastics can be obtained by the condensation reaction of formaldehyde and amine or acid amides.The non-limiting example of amine or acid amides comprises trimeric cyanamide, urea or benzo guanamine.Also can adopt with the condenses of other amine or acid amides, the aldehyde condensate of glycoluril for example, it has produced a kind of high-melting-point crystallized product that can be used in the powder coating.Although the most frequently used aldehyde is formaldehyde, also can use other aldehyde, as acetaldehyde, crotonic aldehyde and phenyl aldehyde.
Aminoplastics contains imino-and methylol, and in some cases, has carried out etherificate to the small part methylol with alcohol and solidified sensitivity to improve.Any monohydroxy-alcohol all can be used for this purpose, comprises methyl alcohol, ethanol, propyl carbinol, isopropylcarbinol and hexanol.
The non-limiting example of aminoplastics comprises carbamide, melocol or benzoguanamine-formaldehyde condensation products, is monomeric in some cases and has carried out to the small part etherificate with one or more alcohol with 1-4 carbon atom.The non-limiting example of suitable aminoplast(ic) resin is available from as Cytec Industries, and the trade mark of Inc. is the product of CYMEL , and available from Solutia, the trade mark of Inc. is the product of RESIMENE .
In another embodiment, the present invention relates to aforesaid curing composition, wherein, in the time of in the aminoplastics solidifying agent being joined other compositions that constitute coating composition, its amount accounts for the 0.5-65wt% of resin solid gross weight in the composition that constitutes coating composition usually.
Other solidifying agent that are suitable for include but not limited to polyisocyanate curing agent.Here the term of usefulness " polyisocyanates " is intended to comprise (or end capped) polyisocyanates and the untight polyisocyanates of sealing.This polyisocyanates can be aliphatic series or aromatic polyisocyanate, or this mixture of two kinds of front.Can use vulcabond, but senior polyisocyanates uses always, as the isocyanuric acid ester of vulcabond.Senior polyisocyanates also can be used in combination with vulcabond.Also can use isocyanate prepolymer, for example the reaction product of polyisocyanates and polyvalent alcohol.Can use the mixture of polyisocyanate curing agent.
If polyisocyanates is sealing or end capped, then can be with any suitable aliphatic series known to those skilled in the art, alicyclic or aromatic alkyl monohydroxy-alcohol end-capping reagent as polyisocyanates.Other suitable end-capping reagents comprise oxime and lactan.If use polyisocyanate curing agent, when in other compositions that it joined coating composition, its amount generally accounts for the 5-65wt% of resin solid gross weight in the composition that constitutes coating composition, and this amount can be 10-45wt%, and this amount 15-40wt% normally.
Other available solidifying agent comprise the isocyanic ester of triazine derivatives, as elaborate at US5, the triamino formyl radical triaizine compounds in 084,541, and this paper introduces this patent as a reference.If use the isocyanic ester of triazine derivatives, when in other compositions that it joined coating composition, its amount can account for the 20wt% at the most of resin solid gross weight in the composition that constitutes coating composition, and this amount can be 1-20wt%.
Acid anhydride as the solidifying agent of hydroxy functional groups material also is known in the field, and in the present invention available.Be suitable in coating composition of the present invention non-limiting example as the acid anhydride of solidifying agent comprise per molecule have at least two carboxylic acid anhydride groups, by the mixture deutero-of monomer that comprises the ethylenically unsaturated carboxylic acids acid anhydride and at least a vinyl copolymerisable monomer (as vinylbenzene, alpha-methyl styrene, Vinyl toluene etc.) those.The non-limiting example of suitable ethylenically unsaturated carboxylic acids acid anhydride comprises maleic anhydride, citraconic anhydride and clothing health acid anhydride.Perhaps, this acid anhydride can be the acid anhydride affixture of diene polymer, as the polyhutadiene of maleation or the butadienecopolymer of maleation (for example butadiene/styrene copolymers).These and other suitable anhydride curing agents is set forth in US 4,798, the capable and US 4,732 of 746 the 10th hurdle 16-50, and during 790 the 3rd hurdle 41-57 were capable, this paper introduced these patents as a reference.
Polyepoxide as the solidifying agent that contains the carboxylic acid functional material is known in the field.The non-limiting example that is suitable for being used in the polyepoxide in the coating composition of the present invention comprises the polyglycidyl ether of polyphenol and the polyglycidyl ether of fatty alcohol, and they can prepare by making polyphenol or fatty alcohol and epihalohydrin (as Epicholorohydrin) carry out etherification reaction in the presence of alkali.These and other suitable polyepoxide is set forth in US 4,681, and during 811 the 5th hurdle 33-58 were capable, this paper introduced this patent as a reference.
Contain the suitable solidifying agent that the material of epoxy-functional uses and comprise the polyprotonic acid solidifying agent, for example the acrylate copolymer that contains acidic group for preparing by the ethylenically unsaturated monomer of the ethylenically unsaturated monomer that contains at least one carboxyl and at least a no hydroxy-acid group.The acid number of this acid-functionalized acrylate copolymer can be 30-150.Also can use the polyester that contains acid functional group.Above-mentioned polyprotonic acid solidifying agent is set forth in US 4,681 in more detail, and 811 the 6th hurdles the 45th walk in the 9th hurdle the 54th row, and this paper quotes this patent.
The solidifying agent that is similarly the isocyanate functional group of being used for known in the field is a polyvalent alcohol, and promptly per molecule has the material of two or more hydroxyls.The non-limiting example that is suitable for being used in this material in the coating composition of the present invention comprises the polyalkylene ethoxylated polyhydric alcohol, comprises thioether; Polyester polyol comprises the polyhydroxy polycarboxylic esteramides; And the acrylic copolymer of the polycaprolactone of hydroxyl and hydroxyl.Same available is the polyether glycol that is formed by various polyvalent alcohol alkoxylates, and described various polyvalent alcohols for example are glycol, and as ethylene glycol, 1,6-hexylene glycol, dihydroxyphenyl propane etc., or higher polyol are as TriMethylolPropane(TMP), tetramethylolmethane etc.Also can use polyester polyol.These and other suitable polyvalent alcohol solidifying agent is set forth in US 4,046,729 the 7th hurdle the 52nd walks to the 8th hurdle the 9th row, the 8th hurdle the 29th walks to the 9th hurdle the 66th row and US 3,919,315 the 2nd hurdles the 64th walk in the 3rd hurdle the 33rd row, and this paper introduces these patents as a reference.
The solidifying agent that polyamines also can be used as the material that contains the isocyanate functional group.The non-limiting example of suitable polyamine curing agent comprises uncle or secondary diamine or polyamines, wherein the group that links to each other with nitrogen-atoms can be saturated or undersaturated, aliphatic, alicyclic, aromatics, the aliphatic series that replaced by aromatics, by the aromatics and the heterocycle of aliphatic series replacement.The suitable aliphatic series and the non-limiting example of alicyclic diamine comprise 1,1,2-propylene diamine, 1,8-octamethylenediamine, isophorone diamine, propane-2,2-hexahydroaniline etc.The non-limiting example of suitable aromatic diamine comprises phenylenediamine and tolylene diamine, for example O-Phenylene Diamine and to tolylene diamine.These and other suitable polyamines elaborates at US 4,046, and 729 the 6th hurdles the 61st walk in the 7th hurdle the 26th row, and this paper introduces this patent as a reference.
If desired, can use suitable curing agent mixture.Should be noted that and coating composition can be mixed with one-component coating compositions that wherein solidifying agent (as previously discussed those aminoplast(ic) resins and/or triaizine compounds) mixes with other coating composition composition.One-component coating compositions can be mixed with stable storing.Perhaps, coating composition can be mixed with double-component paint composition, wherein polyisocyanate curing agent (as above-mentioned those) can join in preformed other coating composition mixture of ingredients before being about to apply.This preformed mixture can comprise solidifying agent those aminoplast(ic) resins and/or triaizine compounds as previously discussed.
In the time of in solidifying agent being joined other compositions that constitute coating composition, its amount in coating composition accounts for the 0.5-65wt% of resin solid gross weight in the composition that constitutes coating composition usually, this amount can be 1-20wt%, and this amount can also be 5-15wt%.
The composition that constitutes coating composition comprises multiple particle, and wherein each composition is inequality,, is different from first and second materials in the coating composition, two solidify material (if existence) and solidifying agent that is.This particle can be formed by the material of the mixture that is selected from polymerization and non-polymeric inorganic materials, polymerization and non-polymeric organic materials, matrix material and any previous materials.Here usefulness " by ... form " be open, " comprise " as the proprietary term of claim.Therefore, the composition that " is formed by cited composition " means and contains these at least and enumerate composition and can contain the composition that other do not enumerate composition in the composition forming process.
Here the term of usefulness " polymeric inorganic materials " is meant the polymeric material of the repeating unit of main chain based on one or more elements outside the de-carbon.More data is seen people's such as James Mark Inorganic Polymers, Prenice Hall Polymer Science andEngineering Series, (1992) page 5, this paper quotes these contents particularly.In addition, the term of usefulness " polymeric organic materials " is meant synthetic polymeric material, semisynthetic polymeric material and natural polymeric material here, and all these all have the main chain repeating unit based on carbon.
Here " organic materials " of usefulness is meant carbon compound, wherein carbon general with himself also and hydrogen bonding, and often also with other element bondings, and do not comprise binary compound such as oxycarbide, carbide, dithiocarbonic anhydride etc.; Ternary compound such as metal cyanides, metallic carbonyls, phosgene, carbonyl sulfide etc.; And carbonaceous ionic compound such as metal carbonate, for example lime carbonate and yellow soda ash.See R.Lewis, Sr., Hawley ' s Condensed Chemical Dictionary, (12 ThEd.1993) 761-762 page or leaf, and M.Silberberg, Chemistry The Molecular Nature of Matter and Change(1996) the 586th pages, this paper quotes these contents.
Here the term of usefulness " inorganic materials " is meant any material that is not organic materials.
Here the term of usefulness " matrix material " is meant the binding substances of two or more differing materials.Its surface hardness of particle that is formed by matrix material is different from subsurface granule interior hardness usually.More specifically, can carry out modification to particle surface, include but not limited to make its surface property generation chemical transformation or physical change with the currently known methods of this area with any method as known in the art.
For example, can be by being formed particle by one or more second coated materials, first material that coats or seal, thus produce the composite particles that has than pressure release surface.In another embodiment, the particle that is formed by matrix material can be by being formed by the first multi-form coated materials, first material that coats or seal.Can be used for particulate additional information of the present invention and see G.Wypych, Handbook of Fillers, 2 NdEd. (1999) 15-202 pages or leaves, this paper quotes these contents.
The particle that is suitable for being used in the coating composition of the present invention can comprise inorganic elements as known in the art or compound.Suitable particle can be formed by the mixture of stupalith, metallic substance and any aforementioned substances.Suitable stupalith comprises the mixture of metal oxide, metal nitride, metallic sulfide, metal silicate, metal boride, metal carbonate and any aforementioned substances.The concrete non-limiting example of metal nitride for example is a boron nitride; The concrete non-limiting example of metal oxide for example is a zinc oxide; The non-limiting example of suitable metallic sulfide for example is molybdenumdisulphide, tantalum disulfide, tungsten disulfide and zinc sulphide; The non-limiting example of suitable metal silicate for example is pure aluminium silicate and Magnesium Silicate q-agent such as vermiculite.
This particle can comprise a core that is essentially single inorganic oxide, described inorganic oxide such as colloid silica, pyrogenic silica or soft silica, aluminum oxide or colloidal alumina, titanium dioxide, Cs2O, yttrium oxide, colloid yttrium oxide, zirconium white such as colloidal zirconia or amorphous oxidation zirconium, and the mixture of any aforementioned substances; Perhaps this particle can comprise the inorganic oxide that a class has deposited another kind of organic oxygen compound on it.Should recognize that when with curing composition of the present invention during as transparent surface coating, for example in the polycomponent composite paint during as varnish coating, this particle should not have serious interference to the optical property of curing composition.Here " transparent " of usefulness is meant that the BYK Haze index of solidified coating is lower than 50, and this index is measured with the BYK/Haze glossometer.
Can be used to form the non-polymeric inorganic materials of particulate of the present invention and be selected from graphite, metal, oxide compound, carbide, nitride, boride, sulfide, silicate, carbonate, vitriol and oxyhydroxide.The non-limiting example of available inorganic oxide is a zinc oxide.The non-limiting example of suitable inorganic sulphide comprises molybdenumdisulphide, tantalum disulfide, tungsten disulfide and zinc sulphide.The non-limiting example of available inorganic silicate comprises pure aluminium silicate and Magnesium Silicate q-agent, as vermiculite.The non-limiting example of suitable metal comprises the mixture of molybdenum, platinum, palladium, nickel, aluminium, copper, gold, iron, silver, alloy and any aforementioned substances.
In one embodiment, the present invention relates to aforesaid curing composition, wherein said particle is selected from the mixture of pyrogenic silica, soft silica, colloid silica, aluminum oxide, colloidal alumina, titanium dioxide, Cs2O, yttrium oxide, colloid yttrium oxide, zirconium white, colloidal zirconia and any aforementioned substances.In another embodiment, the present invention relates to aforesaid curing composition, wherein said particle comprises colloid silica.As mentioned above, these materials can be through or not surface treated.
This coating composition can contain the precursor that is suitable for forming at the scene by sol-gel method silica dioxide granule.Coating composition of the present invention can comprise the organoalkoxysilane that hydrolysis at the scene forms silica dioxide granule.For example, can make tetraethyl orthosilicate hydrolysis and condensation to form silica dioxide granule with the acid of all example hydrochloric acids and so on.Other available particles comprise the silicon-dioxide through surface modification, and as US 5,853,809 the 6th hurdles the 51st walk to sets forth in the 8th hurdle the 43rd row, and this paper introduces this patent as a reference.
In one embodiment of the invention, hardness value can abrade polymeric coating or polymeric substrate greater than the particle of material hardness value.The example that can abrade the material of polymeric coating or polymeric substrate includes but not limited to dirt, sand, stone, glass, brush for vehicle wash etc.Particulate hardness value and the material that can scratch polymeric coating or polymeric substrate can be determined with the hardness measurement method of any routine, as Vickers or Brinell hardness, but also can be that the original Mohs' hardness scale of 1-10 is determined according to the scale of the relative scratch resistance of representing material surface.Listed the Moh's scale number that is suitable for some non-limiting examples of particulate used in this invention, that form by inorganic materials in the following Table A.
Table A
Particulate material Mohs' hardness (original hardness)
Boron nitride ????2 1
Graphite ????0.5-1 2
Molybdenumdisulphide ????1 3
Talcum ????1-1.5 4
Mica ????2.8-3.2 5
Kaolin ????2.0-2.5 6
Gypsum ????1.6-2 7
Calcite (lime carbonate) ????3 8
Calcium Fluoride (Fluorspan) ????4 9
Zinc oxide ????4.5 10
Aluminium ????2.5 11
Copper ????2.5-3 12
Iron ????4-5 13
Gold ????2.5-3 14
Nickel ????5 15
Palladium ????4.8 16
Platinum ????4.3 17
Silver ????2.5-4 18
Zinc sulphide ????3.5-4 19
1K.Ludema, Friction, Wear, Lubrication, (1996) the 27th pages, this paper introduces these contents. 2R.Weast (editor), Handbook of Chemistry and Physics, CRCPress (1975) F-22 pages or leaves. 3R.Lewis, Sr., Hawley ' s Condensed Chemical Dictionary, (12th Ed.1993) the 793rd page, this paper introduces these contents. 4 Hawley ' s Condensed Chemical Dictionary, (12th Ed.1993) the 1113rd page, this paper introduces these contents. 5 Hawley ' s Condensed Chemical Dictionary, (12th Ed.1993) the 784th page, this paper introduces these contents. 6 Handbook of Chemistry and PhysicsThe F-22 page or leaf. 7 Handbook of Chemistry and PhysicsThe F-22 page or leaf. 8 Friction, Wear, Lubrication, the 27th page. 9 Friction, Wear, Lubrication, the 27th page. 10 Friction, Wear, Lubrication, the 27th page. 11 Friction, Wear, Lubrication, the 27th page. 12 Handbook of Chemistry and PhysicsThe F-22 page or leaf. 13 Handbook of Chemistry and PhysicsThe F-22 page or leaf. 14 Handbook of Chemistry and PhysicsThe F-22 page or leaf. 15 Handbook of Chemistry and PhysicsThe F-22 page or leaf. 16 Handbook of Chemistry and PhysicsThe F-22 page or leaf. 17 Handbook of Chemistry and PhysicsThe F-22 page or leaf. 18 Handbook of Chemistry and PhysicsThe F-22 page or leaf. 19R.Weast (editor), Handbook of Chemistry and Physics, CRCPress (71 StEd.1990) 4-158 page or leaf.
In one embodiment, the particulate Moh's scale number is greater than 5.In certain embodiments, the Moh's scale number of particle (as silicon-dioxide) is greater than 6.
As mentioned above, the Mohs' hardness scale is relevant with the scratch resistance of material.Thereby the present invention has further thought deeply the particle that surface hardness is different from granule interior hardness under this surface.More specifically, as mentioned above, modification can be carried out with any method known in the field in the particulate surface, described method includes but not limited to the currently known methods in this area the particulate surface property be carried out chemical modification, thereby make the particulate surface hardness than the hardness height that can scratch the material of polymeric coating or polymeric substrate, and the pellet hardness under the surface is lower than the hardness of the material that can scratch polymeric coating or polymeric substrate.
As another replaceable scheme, particle can be by being formed by one or more second coated materials, first material that coats or seal, thereby form the matrix material that has than crust.Perhaps, particle can be by being formed by the first multi-form coated materials, first material that coats or seal, thereby form the matrix material that has than crust.
At one is not to be used for limiting in the example of the present invention, can give inorganic particle coated with silicon dioxide, carbonate or the millimicro clay coating that is formed by inorganic materials (as silicon carbide or aluminium nitride), thereby forms the available composite particles.In another non-limiting example, the silane coupling agent that has alkyl group side chain can interact with the inorganic particle that is formed by inorganic oxide, thereby produces a kind of available composite particles with " softer " surface.Other examples comprise to being coated by non-polymeric or particle that polymeric material forms, sealing or be coated with and are covered with different non-polymeric or polymeric materials.The concrete non-limiting example of this composite particles is DUALITE TM, it is a kind of synthetic aggregated particles that scribbles lime carbonate, can be from Pierce and StevensCorporation of Buffalo, and NY buys.
In an indefiniteness embodiment of the present invention, particle is formed by the solid lubrication agent material.Here the term of usefulness " solid lubricant " is meant and is used between two surfaces, and it is injury-free and/or alleviate any solid of friction and wear in order to protection in the process of relatively moving.In one embodiment, solid lubricant can be an inorganic solid lubricant.Here " inorganic solid lubricant " of usefulness is meant such solid lubricant, and its feature crystal habit cuts into it and is easy to the sheet of the Bao Erping of slip mutually, thereby produces the antifriction lubricant effect.See R.Lewis, Sr., Hawley ' s Condensed Chemical Dictionary, (12th Ed.1993) the 712nd page, this paper quotes these contents particularly.Frictional force is the resistance that solid slides each other.F.Clauss, Solid Lubricants and Self-Lubricating Solids(1972) page 1, this paper are quoted these contents particularly.
In an indefiniteness embodiment of the present invention, particle has laminate structure.Particle with laminate structure is made up of sheet that is arranged in hexagonal atom or plate, and it has Van der Waals bonding power between linkage force in the strong sheet and weak sheet, produces shearing resistance between low sheet.The non-limiting example of laminate structure is a hexagonal crystallographic texture.Inorganic solid particles with stratiform soccerballene (fullerene) (being bucky-ball (buckyball)) structure also can be with in the present invention.
Can be used to form the mixture that non-limiting example that particulate of the present invention has the suitable material of laminate structure comprises boron nitride, graphite, metal dithionite genusization thing, mica, talcum, gypsum, kaolin, calcite, cadmium iodide, silver sulfide and any aforementioned substances.Suitable metal dithionite genusization thing comprises the mixture of molybdenumdisulphide, two selenizing molybdenums, tantalum disulfide, two selenizing tantalums, tungsten disulfide, two selenizing tungsten and any aforementioned substances.
This particle can be formed by non-polymeric organic materials.The non-limiting example of available non-polymeric organic materials in the present invention includes but not limited to stearate (as Zinic stearas and aluminum stearate), diamond, carbon black and stearylamide.
This particle can be formed by inorganic polymeric material.The non-limiting example of the inorganic polymeric material of available comprises the mixture of polyphosphonitrile, polysilane, polysiloxane, polygeremanes, polymeric sulphur, polymeric selenium, siloxanes and any aforementioned substances.Being suitable for the concrete non-limiting example of particulate that is formed by inorganic polymeric material used in this invention is TOSPEARL 20( 20See R.J.Perry " Application for Cross-Linked SiloxaneParticles " Chemtech, in February, 1999,39-44 page or leaf), it is the particle that is formed by crosslinked siloxanes, can be available from Toshiba Silicones Company, Ltd.ofJapan.
This particle can be formed by the synthetic organic polymer materials.The non-limiting example of suitable organic polymer materials includes but not limited to thermosetting material and thermoplastic material.Here " thermoplasticity " material of usefulness is meant when exposing at high temperature and softens, and returns the material of its virgin state when cool to room temperature.The non-limiting example of suitable thermoplastic material comprises thermoplastic polyester such as polyethylene terephthalate, polybutylene terephthalate and PEN, polycarbonate, polyolefine such as polyethylene, polypropylene and polyisobutene, the multipolymer of acrylate copolymer such as vinylbenzene and Acrylic Acid Monomer and the polymkeric substance that contains methacrylic ester, polymeric amide, thermoplastic polyurethane, vinyl polymer, and the mixture of any aforementioned substances.
The non-limiting example of suitable thermosetting material comprises the mixture of thermosetting polyester, vinyl ester, epoxy material, phenoplast, aminoplastics, heat-curable urethane and aforementioned any material.The concrete non-limiting example of synthesized polymer particulate that is formed by epoxy material is an epoxy micro gel particle.Here " thermoset " material of usefulness be meant irreversibly solidify after the heating or " curing " material.Thermosetting material has formed cross-linked network.Here the polymeric material of usefulness " crosslinked " is meant and has at least a part of polymeric material to form converging network.Those skilled in the art should understand, and crosslinked existence and degree of crosslinking (cross-linking density) mensuration that can in all sorts of ways is as the dynamic mechanics heat analysis method (DMTA) that adopts TA Instruments DMA 2980 DMTA analysers to carry out in nitrogen.This method is measured the second-order transition temperature and the cross-linking density of coating or polymkeric substance free film.These physicalies of solidify material are relevant with the structure of cross-linked network.
This particle also can be the hollow bead that is formed by following material, and described material is selected from the mixture of polymerization and non-polymeric inorganic materials, polymerization and non-polymeric organic materials, matrix material and any aforementioned substances.The non-limiting example that can form the suitable material of hollow bead was set forth in front.In one embodiment, hollow bead can be a hollow glass ball.
Being used in polymeric substrate or polymeric coating can the form with dispersion, suspension or emulsion exist in carrier as the particle of the present invention in (but being not limited to) electrodeposited coating, undercoat or the finishing coat.The non-limiting example of suitable carrier includes but not limited to the mixture of water, solvent, tensio-active agent or any aforementioned substances.The non-limiting example of suitable solvent includes but not limited to the mixture of mineral oil, the alcohol such as methyl alcohol or butanols, the ketone such as Methyl amyl ketone, the aromatic hydrocarbons such as dimethylbenzene, the glycol ethers such as ethylene glycol monobutyl ether, ester class, aliphatic cpd and any aforementioned substances.
Before blending, the spendable class particle of the present invention comprises particulate colloidal sol, as organic colloidal sol.These colloidal sols can be that median size is in as various small-particles, colloid silica in the scope of above regulation.
Colloid silica can or carry out surface modification during the initial formation of particle afterwards.According to the performance of specific silicon-dioxide, the silicon-dioxide of these surface modifications can contain the carbon part that contains of chemical bonding in its surface, and such as anhydrous SiO 2The group of group and SiOH group and so on, physical bond or be chemically bound in various ionic groups in the silica sphere, the organic group of absorption, or the mixture of any aforementioned substances.The silicon-dioxide of this surface modification elaborates at US 4,680, and in 204, this paper is for introducing this patent as a reference particularly.
This material can in all sorts of ways and make various forms, and its non-limiting example comprises organosol and mixed sols.Here the term of usefulness " mixed sols " is intended to comprise the dispersion of those colloid silicas, and wherein dispersion medium comprises organic liquid and water.This small-particle colloid silica is easy to obtain, they are colourless basically, and its specific refractory power makes and to be included in when not containing in the composition of composition that other pigment or meeting as known in the art make the painted or transparent reduction of this composition when it, generation be water white coating.
The non-limiting example of suitable particles comprises colloid silica, is ORGANOSILICASOLS as the trade mark available from NissanChemical Company TMThose, as ORGANOSILICASOLS TMMT-ST, and available from the HIGHLINK of Clariant Corporation TMColloidal alumina is those of NALCO8676  as the trade mark available from Nalco Chemical; And colloidal zirconia, be those of HIT-32M  as trade mark available from Nissan Chemical Company.
This particle can be incorporated in the present composition with the form of stabilising dispersions.When particle was colloidal form, dispersion can prepare like this: under agitation with particles dispersed in carrier, and the solvent that remove to exist of vacuum at room temperature.In certain embodiments, carrier can not be a solvent, for example is with the tensio-active agent at following detailed description, and it includes but not limited to described at least a polysiloxane (a).
Perhaps, dispersion can be according to US 4,522, and the narration in 958 or 4,526,910 prepares, and this paper introduces these patents as a reference.Particle can be before being incorporated into the present composition and described at least a polysiloxane " cold mixing ".Perhaps, particle can join later in the mixture of any all the other composition components (including but not limited at least a polysiloxane (a)), and is dispersed in wherein with dispersing method as known in the art.
When particle is non-colloid form, when for example (but being not limited to) is the agglomerate form, can prepare dispersion in the carrier by agglomerate is dispersed in, described carrier for example (but being not limited to) is at least a polysiloxane (a), thereby will be dispersed in wherein particle stabilizedly.Can use known any other pigment dispersion method in dispersing method such as grinding, pulverizing, Micro Fluid, ultrasonic wave or the coating formulation art.Perhaps, can be with any other dispersing method as known in the art with particles dispersed.If desired, join in the mixture of other composition components after can will being the particle of non-colloidal form with any dispersing method as known in the art.
In one embodiment, the present invention relates to comprise multiple grains of composition, wherein, first part's particle is present in the surf zone of curing composition, and its concentration ratio is present in the second section particulate concentration height of curing composition interior body region.
Here " surf zone " of the curing composition of usefulness is meant and is coated with parallel substantially zone, the airborne surface of being exposed to of ground, and its thickness is extended to the degree of depth of the 20-150 nanometer under this exposed surface usually by the Surface Vertical of solidified coating.In certain embodiments, this thickness of surf zone is at least 20 nanometers to 100 nanometer, and can be at least 20 nanometers to 50 nanometer, comprises cited value.Here " interior body region " of the curing composition of usefulness is meant to be positioned at and also is parallel to the zone that is coated with the ground surface under the surf zone substantially.The thickness of interior body region is extending to ground or extending to the part of the coating under this curing composition through solidified coating at the interface from it and surf zone.
In the embodiment of the present invention of particulate median size greater than 50 nanometers, the thickness of surf zone generally is that the Surface Vertical by solidified coating extends to the degree of depth that is three times in the particle median size, and can be to extend to the degree of depth that is twice in the particle median size by this Surface Vertical.
Granule density in the curing composition can in all sorts of ways and characterize.For example, be dispersed in the particulate average number density (being the particle mean number or the number of per unit volume) of surf zone greater than the particulate average number density that is dispersed in interior body region.Perhaps, be dispersed in the particulate mean volume fraction (being volume/cumulative volume that particle occupies) of surf zone or the weight in average percentage ratio of per unit volume (being gross weight * 100% of the particle weight/solidified coating unit volume in the solidified coating unit volume) weight in average percentage ratio greater than particulate mean volume fraction that is dispersed in interior body region or per unit volume.
If desired, can measure the particulate concentration (as characterizing) that is present in the solidified coating surf zone, described method such as transmission electron microscope art (" TEM "), surface scan electron microscopy (" X-SEM "), atomic force microscope art (" AFM ") and X-ray photoelectron spectroscopy with various surface analysis methods known in the field in order to upper type.
For example, can measure the particulate concentration that is present in the solidified coating surf zone with the cross section TEM transmission electron microscopy.Following draw outlines of available transmission electron microscope art.Coating composition is coated on the ground, and under the condition that is suitable for said composition and ground, solidifies.Remove or peel one deck solidified coating sample from ground then, and it is embedded in solidified Resins, epoxy with method well known in the art.Then can be at room temperature with method well known in the art (for example by forming a section) the sample section that embedding is good.Can have 45 ° of diamond blades that are used in the anchor clamps in " ship shape chamber " of water and cut this section with being installed in one.In the cutting process, section swims on the surface of the water in the ship shape chamber.In case when having a little otch to reach the bright gold look (about 100-150 nanometer thickness) to dark golden interference color, generally with independent sample collection on the grid that scribbles formvar-carbon, and drying on slide glass at room temperature.Then sample is placed in the suitable transmission type microscope (as Philips CM12TEM), and (as amplifying 105,000 times) detection under various magnifications, so that note the particle intensity of surf zone by electron microscope.The particle intensity of solidified coating surf zone can be determined according to the visual observation of electron microscope.
Should understand, particle can be present in the surf zone like this: the part particle is given prominence at least in part more than the solidified coating surface, is not subjected to the protection of organic coating basically.Perhaps, particle can be present in the surf zone like this: organic coating is between the airborne interface of being exposed to of particle and surf zone.
In one embodiment, the present invention relates to aforesaid curing composition, wherein the median size of particle before being added into coating composition is lower than 100 microns, and the median size before being added into coating composition can be lower than 50 microns.In another embodiment, the present invention relates to aforesaid curing composition, wherein the average particle size range of particle before being added into coating composition is 1 to being lower than 1000 nanometers.In another embodiment, the present invention relates to aforesaid curing composition, wherein the average particle size range of particle before being added into coating composition is the 1-100 nanometer.
In another embodiment, the present invention relates to aforesaid curing composition, wherein the average particle size range of particle before being added into composition is the 5-50 nanometer.In another embodiment, the present invention relates to aforesaid curing composition, wherein the average particle size range of particle before being added into composition is the 5-25 nanometer.Particle size range can be to comprise the arbitrary combination of cited value in these interior values.
The particulate median size greater than 1 micron embodiment in, this median size can be measured according to known laser scanning method.For example, this class particulate median size can be measured with Horiba Model LA 900 laser diffraction particle diameter instrument, and its employing wavelength is that the helium-neon laser of 633nm is measured the particulate size, and the supposition particle is spherical, that is, " particle diameter " is meant the size of the ball of the minimum of enwrapped granule fully.
In particle size is less than or equal to an embodiment of the present invention of 1 micron, median size can be measured like this: the Photomicrograph to the image of transmission type microscope (" TEM ") carries out visual detection, particle diameter in the measurement image, and calculate median size according to the magnification of TEM image.One of ordinary skill in the art should understand how to make this TEM image, and has narrated a kind of such method in following listed examples.In an indefiniteness embodiment of the present invention, made magnification and be 105,000 TEM image, conversion factor is obtained divided by 100 by magnification.When carrying out visual detection, measure the micron number of particle diameter, with conversion factor observed value is converted into nanometer again.The particulate diameter is meant the size of the ball of the minimum diameter of enwrapped granule fully.
Coating of particles (or form) can estimate that purposes changes according to specific embodiments of the present invention and particulate.For example, can use spheroidal particle (as solid pearl, microballon or hollow ball) usually, also can use cube shaped, flats or needle-like (elongated or fibrous) particle.In addition, the particulate internal structure can be hollow, porous or atresia, or the combination of any aforementioned structure, for example has the particle of porous or closely knit outer wall and hollow core.The more information of relevant suitable particles characteristic is seen people such as H.Katz (editor), Handbook of Fillers and Plastics(1987) 9-10 pages or leaves, this paper are quoted these contents particularly.
It should be recognized by those skilled in the art that and one or more particulate mixture with different median sizes can be joined in the present composition, thereby give required performance of said composition and characteristic.For example, the particle with different-grain diameter can be used in the composition of the present invention.
In one embodiment, the present invention relates to aforementioned compositions, in the time of wherein in particle being joined other compositions that constitute said composition, its amount in composition accounts for the 0.01-75wt% of resin solid gross weight in the composition that constitutes said composition.In another embodiment, the present invention relates to aforementioned compositions, in the time of wherein in particle being joined other compositions that constitute said composition, its amount in composition accounts for the 0.1wt% at least of resin solid gross weight in the composition that constitutes said composition, can account for 0.5wt% at least, can also account for more than the 5wt%.
In another embodiment, the present invention relates to aforesaid curing composition, in the time of wherein in particle being joined other compositions that constitute said composition, its amount in composition accounts for below the 75wt% of resin solid gross weight in the composition that constitutes said composition.In another embodiment, the present invention relates to aforementioned compositions, in the time of wherein in particle being joined other compositions that constitute said composition, its amount in composition accounts for below the 50wt% of resin solid gross weight in the composition that constitutes said composition.In another embodiment, the present invention relates to aforementioned compositions, in the time of wherein in particle being joined other compositions that constitute said composition, its amount in composition accounts for below the 20wt% of resin solid gross weight in the composition that constitutes said composition.In another embodiment, the present invention relates to aforementioned compositions, in the time of wherein in particle being joined other compositions that constitute said composition, its amount in composition accounts for below the 10wt% of resin solid gross weight in the composition that constitutes said composition.Particulate amount scope can be to comprise the easy combination of cited value in these interior values.
In addition, in another embodiment, the present invention relates to such composition, wherein at least a tensio-active agent may reside in during the foregoing formation.This at least a tensio-active agent can be selected from anionic, non-ionic type and cationic surfactant.
Here " tensio-active agent " of usefulness is meant any material that the solid surface tension that can make cured compositions and coating or surface energy reduce.That is to say that curing composition that is formed by the composition that comprises tensio-active agent or coating are compared with the solidified coating that is formed by the similar composition that does not contain tensio-active agent has lower solid surface tension or surface energy.
For the present invention, solid surface tension can be according to the Owens-Wendt method, and adopting with distilled water and methylene iodide is Rame '-Hart contact angle goniometer measurement of reagent.Usually, a kind of reagent of a 0.02cc is dropped on the solidified coating surface, and measure contact angle and supplementary angle thereof with the standard microscope that goniometer is housed.Each measures contact angle and supplementary angle thereof with three.Repeat this process with other reagent.Carry out six times with every kind of reagent and measure, calculate its mean value.Calculate solid surface tension with the Owens-Wendt equation then:
{ γ 1 (1+cos Φ) }/(γ 1 for 2= dγ s d) 1/2+ (γ l pγ s p) 1/2Wherein γ 1 is the surface tension (methylene iodide=50.8, distilled water=72.8) of liquid, γ dAnd γ pBe surface tension (the methylene iodide γ of dispersion and polar component d=49.5, γ p=1.3; Distilled water γ d=21.8, γ p=51.0); Measure the Φ value and determine cos Φ.Set up two equatioies then, one is methylene iodide, and one is water.Unique the unknown be γ s dAnd γ s pThen these two equatioies are found the solution to draw above two unknown numbers.This two number combines and represents the total solids surface tension.
Described at least a tensio-active agent can be selected from the mixture of the amphiphilic polysiloxane, amphiphilic fluoropolymer and any aforementioned substances that have reactive functionality.For water soluble or the dispersible amphiphilic material of water, term " amphiphilic " is meant the polymkeric substance that has hydrophilic polar end and water-fast hydrophobic side.Be suitable for comprising those following polysiloxane as the non-limiting example of the polysiloxane that contains functional group of tensio-active agent.The non-limiting example of suitable amphiphilic fluoropolymer comprises that the trade name available from Asahi Glass Company is vinyl fluoride-alkyl vinyl ether alternating copolymer (as US 4,345, those of setting forth in 057) of LUMIFLON; Fluorochemical surfactant, as available from 3M of St.Paul, the trade name of Minnesota is the fluorine-containing aliphatic polyester of FLUORAD; Functionalized perfluorinated material, as 1H available from FluoroChem USA, 1H-perfluoro-nonyl alcohol; And perfluorination (methyl) acrylate resin.
The non-limiting example that is suitable for being used in other tensio-active agents in curing composition of the present invention or the coating can comprise anionic, non-ionic type and cationic surfactant.The non-limiting example of suitable aniorfic surfactant comprises vitriol or sulfonate.Concrete non-limiting example comprises senior alkyl monocyclic aromatic sulfonate, as having the senior alkyl benzene sulfonate of 10-16 carbon atom in the alkyl, and straight chain or branched chain, for example decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl Phenylsulfonic acid sodium salt and senior alkyl toluene, dimethylbenzene and sulfocarbolic acid sodium salt; Sulfonated alkyl naphathalene and dinonylnaphthalene sulfonic acid sodium.Other non-limiting examples of suitable aniorfic surfactant comprise alkene sulfonate, comprise the mixture of long-chain alkylene group sulfonate, long-chain hydroxyl sulfonated alkane and any aforementioned substances.The non-limiting example of other vitriol or sulfonate detergent is a paraffin sulfonate, as the reaction product of alpha-olefin and hydrosulphite (as sodium bisulfite).The vitriol that also comprises higher alcohols is as the vitriol (for example glyceryl monostearate monosulfate) of Sodium Lauryl Sulphate BP/USP, tallow alcohol sodium sulfate or lipid acid list or two glyceryl ester; Alkyl gathers (oxyethyl group) ether sulfate, includes but not limited to the vitriol (per molecule has 1-5 oxyethylene group usually) of the condensation product of oxyethane and lauryl alcohol; Lauryl or other senior alkyl Racemic glycidol ether sulfonates; Aromatics gathers (oxyethylene group) ether sulfate, includes but not limited to the vitriol (per molecule has 1-20 oxyethylene group usually) of the condensation product of oxyethane and nonyl phenol.
Other non-limiting example comprises salt, sulfated alkyl ether and/or the alkylaryl ethoxy sulfate that is called the sulfated fatty alcohol of ABEX available from the general commodity name of Rhone-Poulenc.Also can use phosphoric acid salt list-or two-ester type aniorfic surfactant.These aniorfic surfactant are as known in the art, and can buy with general trade mark GAFAC from GAF Corporation, and can be from Rohm﹠amp; Hass Company buys with general trade mark TRITON.
The non-limiting example that is suitable for being used in the nonionic surface active agent in curing composition of the present invention or the coating comprise contain ehter bond and represent with following general formula those: RO (R ' O) nH, wherein the substituent R representative contains the alkyl of 6-60 carbon atom, and substituent R ' representative contains the alkylidene group of 2 or 3 carbon atoms and the mixture of any aforementioned group, and n is the integer of 2-100.
This nonionic surface active agent can prepare by handling to Fatty Alcohol(C12-C14 and C12-C18) or by the phenol that alkyl replaces with excessive oxyethane or propylene oxide.Alkyl carbon chain can contain 14-40 carbon atom, and can be derived from the long chain aliphatic alcohol such as oleyl alcohol or stearyl alcohol.Can be with this class non-ionic type polyoxyethylene surfactant that following formula is represented by AirProducts Chemicals, Inc. buys with general commodity trade mark SURFYNOL; Also can be PLURONIC or TETRONIC available from BASF Corporation; TERGITOL available from UnionCarbide; And available from the SURFONIC of Huntsman Corporation.Other non-limiting examples of suitable nonionic surface active agent comprise based on the oxyethane of glycol (as ethylene glycol or propylene glycol) and the segmented copolymer of propylene oxide, include but not limited to that the general commodity trade mark available from BASF Corporation is those of PLURONIC.
As mentioned above, also can use cationic surfactant.The non-limiting example that is suitable for being used in the cationic surfactant in curing composition of the present invention or the coating comprises the hydrochlorate of alkylamine, and as ARMAC HT, it is the acetate available from the positive alkylamine of Akzo Nobel Chemicals; Imidazolidine derivatives is as the CALGENE C-100 available from Calgene Chemicals Inc.; The amine of ethoxylation or acid amides, as DETHOX Amine C-5, it is the coconut amine ethoxylate available from Deforest Enterprises; Ethoxylated fatty amine is as the ETHOX TAM available from Ethox Chemicals Inc.; And glyceryl ester, as LEXEMUL AR, it is available from the amino ethyl diethylamine of the stearin of Inolex Chemical Co./stearyl.
Other examples of suitable tensio-active agent can comprise polyacrylic ester.The non-limiting example of suitable polyacrylic ester comprises the homopolymer and the multipolymer of acrylate monomer, the multipolymer of butyl polyacrylate and derived from propylene acid ester monomer (as (methyl) ethyl propenoate, ethyl acrylate, (methyl) butyl acrylate and isobutyl acrylate) and (methyl) Hydroxyethyl acrylate and (methyl) Acrylic Acid Monomer for example.In one embodiment, polyacrylic ester can have amino and hydroxy functional group.Suitable amino and hydroxy functional acrylate are disclosed among following embodiment 26 and the US 6,013,733, and this paper introduces this patent as a reference.Available other examples amino and the hydroxy-functional multipolymer are the multipolymers of Hydroxyethyl acrylate, ethyl acrylate, isobutyl acrylate and dimethylaminoethyl methacrylate.In another embodiment, polyacrylic ester can have acid functional group, and it for example can produce by acid functional monomer's (as (methyl) vinylformic acid) being incorporated in the composition used of preparation polyacrylic ester.In another embodiment, polyacrylic ester can have acid functional group and hydroxy functional group, and they for example can produce by acid functional monomer's (as (methyl) vinylformic acid) and hydroxy functional monomers (as (methyl) Hydroxyethyl acrylate) being incorporated in the composition that the preparation polyacrylic ester uses.
In an interchangeable embodiment, reactant can comprise at least a following material, and this material has at least a with the reversible reactive functionality that is closed of silyl.The silyl-capped material of this usefulness is different from first material, second material, two solidify material (if existence) and the solidifying agent in the composition.The hydrolysis of silyl makes can regenerate with the reactive functionality that solidifying agent further reacts on the material.
Suitable silyl-capped group can have following structural formula (IX):
Figure A0081984400571
Each R wherein 1, R 2And R 3Can be identical or different, representative has alkyl, phenyl or the allyl group of 1-18 carbon atom.
Can be comprised hydroxyl, carbamate groups, carboxyl, amide group and their mixture by the non-limiting example of silyl-capped appropriate functional group.In one embodiment, this functional group is a hydroxyl.
Can comprise hexamethyldisilazane, trimethylchlorosilane, trimethyl silyl diethylamine, tert-butyldimethylsilyl chloride thing, diphenyl methyl silyl chlorination thing, hexamethyl dimethyl silanyl trinitride, hexamethyldisiloxane, trimethyl silyl triflate, hexamethyl dimethylamino silane yl acetamide, N, the mixture of N '-two [trimethyl silyl]-urea and any aforementioned substances with the non-limiting example of the suitable combination thing that forms silyl with this functional group reactions.
Be used for other examples of the suitable combination thing of silylation reactive, and the appropriate reaction condition and the reagent that are used for the trimethyl silyl reaction is described in people such as T.Greene, Protective Groups in Organic Synthesis, (second edition 1991) 68-86 page or leaf and 261-263 page or leaf, this paper introduces these contents and carries out reference.
The main chain of described material can be the compound that comprises at least a following key, and described key is selected from ester bond, urethane bond, urea key, amido linkage, siloxane bond and ehter bond; Or a kind of polymkeric substance, as the multipolymer of polyester, acrylate copolymer, urethane, polyethers, polyureas, polymeric amide and any aforementioned substances.
Having the suitable compound of ester group and at least a reactive functionality or polymkeric substance comprises by at least a polyvalent alcohol and at least a 1, the half ester that the 2-anhydride reactant forms.This half ester is preferred, because they have lower molecular weight and very easily react with epoxy-functional.
Half ester is by polyvalent alcohol and 1, and the 2-acid anhydride is being enough to make the acid anhydride open loop to form half ester and is not taking place basically that under the condition of polyesterification reaction reaction obtains.This reaction product has lower molecular weight and narrow molecular weight distribution and low viscosity." polyesterification reaction not to take place basically " be meant carboxyl that anhydride reactant forms no longer in the multiple mode further by the polyvalent alcohol esterification.This means and formed the high molecular weight polyesters that is lower than 10wt% or is lower than 5wt%.
Usually with 1,2-acid anhydride and polyvalent alcohol mix, and rare gas element (as nitrogen) and be used for the dissolved solids composition and/or reduce reaction mixture viscosity solvent (as ketone or aromatic hydrocarbons) in the presence of react.
For the formation of ideal ring-opening reaction and half ester, can use 1, the 2-dicarboxylic anhydride.Replace acid anhydrides and polyol reaction to come esterification with carboxylic acid, and must remove the water deviate from by distillation by condensation.Under this condition, this can promote undesirable polyesterification reaction.In addition, temperature of reaction can be lower,, is lower than 135 ℃ or for 70-135 ℃ that is.Reaction times can change along with temperature of reaction, and general scope is 10 minutes to 24 hours.
The equivalence ratio of the hydroxyl in acid anhydride and the polyvalent alcohol can be at least 0.8: 1 (acid anhydride is considered as simple function), thereby obtains the maximum conversion rate that transforms to required half ester.Can adopt to be lower than 0.8: 1 ratio, but this ratio has increased the formation of low functionality half ester.
The available acid anhydride comprises aliphatic series, alicyclic, olefinic, the cyclenes genus and aromatics acid anhydride.Also can use substituted aliphatic series and aromatics acid anhydride, precondition is that these substituting groups can not have disadvantageous effect to the reactive of acid anhydride or to the performance of resulting polymers.This substituent example comprises chlorine, alkyl and alkoxyl group.The example of acid anhydride comprises succinyl oxide, methyl succinyl oxide, dodecylene succinyl oxide, vaccenic acid succinyl oxide, phthalic anhydride, tetrahydro-phthalic anhydride, methyltetrahydro phthalic anhydride, hexahydro-phthalic anhydride, alkyl hexahydro-phthalic anhydride (as methyl hexahydro-phthalic anhydride), tetrachloro phthalic anhydride, endo-methylene group tetrahydro-phthalic anhydride, hexachloroendomethylene-tetrahvdrophthalic anhydride, clothing health acid anhydride, citraconic anhydride and maleic anhydride.
Operable in the polyvalent alcohol is simple polyvalent alcohol, promptly contains those of 2-20 carbon atom; And polymerized polyalcohol, as polyester polyol, polyurethane polyol and acrylic polyol.
Simple polyvalent alcohol has glycol, triol, tetrol and their mixture.The non-limiting example of these polyvalent alcohols comprises those that contain 2-10 carbon atom, as aliphatic polyol.Specific examples includes but not limited to following composition: two-TriMethylolPropane(TMP) (two (2, the 2-dihydroxymethyl) dibutyl ether), tetramethylolmethane, 1,2,3, the 4-butantetraol, sorbyl alcohol, TriMethylolPropane(TMP), trimethylolethane, 1,2, the 6-hexanetriol, glycerine, tris(2-hydroxy ethyl)isocyanurate, dimethylol propionic acid, 1,2, the 4-trihydroxybutane, TMP/ 6-caprolactone triol, ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 2-ethyl-1, the 3-hexylene glycol, neopentyl glycol, glycol ether, dipropylene glycol, 1,4 cyclohexane dimethanol and 2,2,4-trimethylpentane-1, the 3-glycol.In one embodiment, this polyvalent alcohol is a TriMethylolPropane(TMP).
With regard to oligomeric polyols, suitable polyvalent alcohol is the polyvalent alcohol of being made by diacid and triol (as TriMethylolPropane(TMP)/cyclohexane diacid and TriMethylolPropane(TMP)/hexanodioic acid) reaction.
With regard to polymerized polyalcohol, polyester polyol carries out esterification by organic poly carboxylic acid or its acid anhydride and organic polyhydric alcohol and/or epoxide and makes.Usually, poly carboxylic acid and polyvalent alcohol are diprotic acid or the acid anhydrides and the dibasic alcohol of aliphatic series or aromatics.
The polyvalent alcohol that is commonly used to prepare polyester comprises TriMethylolPropane(TMP), two-TriMethylolPropane(TMP), aklylene glycol (as ethylene glycol), neopentyl glycol and other glycol, as the reaction product (for example reaction product of 6-caprolactone and ethylene glycol) of Hydrogenated Bisphenol A, cyclohexanediol, cyclohexanedimethanol, caprolactone and glycol, hydroxyalkylation bis-phenol, polyester polyol (for example poly-(oxygen tetramethylene) glycol) etc.
Sour composition in the polyester mainly is made up of monocarboxylic acid or acid anhydride that per molecule has a 2-18 carbon atom.Operable in the acid is phthalic acid, m-phthalic acid, terephthalic acid, tetrahydro-phthalic acid, hexahydro-phthalic acid, methyl hexahydro-phthalic acid, hexanodioic acid, nonane diacid, sebacic acid, toxilic acid, pentanedioic acid, chlorendic acid, tetrachloro phthalic acid and other kinds dicarboxylic acid.And can use senior poly carboxylic acid, and as 1,2,4-benzenetricarboxylic acid and tricarballylic acid.Yet the poly carboxylic acid that uses these higher functionality is not preferred, because can produce high viscosity.
Except the polyester polyol that forms by polyprotonic acid and polyvalent alcohol, can also use polylactone type polyester.This product is by forming such as the lactone of 6-caprolactone and polyol reaction such as ethylene glycol, glycol ether and TriMethylolPropane(TMP).
Except polyester polyol, can also use polyurethane polyol, for example the polyester-polyurethane ester polyol that forms by organic multiple isocyanate and polyester polyol (as above-mentioned those) reaction.Organic multiple isocyanate and polyvalent alcohol contain hydroxyl with the ratio reaction of OH/NCO equivalence ratio greater than 1: 1 thereby make in the products therefrom.The organic multiple isocyanate that is used for preparing this polyurethane polyol can be aliphatic series or aromatic polyisocyanate or its mixture.Can use vulcabond, although also can use the senior polyisocyanates such as triisocyanate, these can produce higher viscosity.
The example of suitable vulcabond is 4,4 '-'-diphenylmethane diisocyanate, 1,4-tetramethylene diisocyanate, isophorone diisocyanate and 4,4 '-methylene-bis (cyclohexyl isocyanate).The example of suitable higher functionality polyisocyanates is a polymethylene polyphenol isocyanic ester.
At least a portion or whole acid functional groups can be by silylanizings.Perhaps, at least a portion or whole acid functional group can by with epoxy functionalized material (as above-mentioned those) or with can change into hydroxyl for silylation reactive provides the aliphatic diol reaction of alcoholic extract hydroxyl group.
The available epoxy functionalized material comprises the epoxy-functional monomer, mixture as glycidyl methacrylate, oxyethane, butylene oxide ring, propylene oxide, epoxy cyclohexane, glycidyl ether (as phenyl glycidyl ether, n-butyl glycidyl ether, cresyl glycidyl ether and isopropyl glycidyl ether), glycidyl ester (as tertiary carbonic acid glycidyl ester (glycidylversatate), for example available from the CARDURA of Shell Chemical Co.) and any aforementioned substances.The epoxy group(ing) in the ester and the equivalence ratio of acidic group are generally 0.1: 1 to 2: 1, and can be 0.5: 1 to 1: 1, typically are 0.8: 1 to 1: 1.
The available aliphatic diol comprises the glycol that contains primary hydroxyl, as 1, and 2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,3 butylene glycol, 1,2-pentanediol, 1,4-pentanediol, 1,2-hexylene glycol, 1,5-hexylene glycol, 2-ethyl-1,3-hexylene glycol, glycol ether, dipropylene glycol, 1,4 cyclohexane dimethanol, 2,2,4-trimethylammonium-1,3-pentanediol and 3,3-dimethyl-1, the 2-butyleneglycol.
Be used in the non-limiting example that silylanizing in the coating composition of the present invention contains ester group compound and have following structural formula (X):
Figure A0081984400611
Have ester, urethane, urea, acid amides and/or ether and at least a other available materialss that are suitable for the functional group of silylation reactive are disclosed in the above argumentation about other suitable polymkeric substance.
Perhaps, the available reactant comprises the acrylate copolymer (for example being polymerized by vinyl monomer and methacrylic acid trimethylsiloxy methyl esters) that has with the hydroxyl of hydrolyzable siloxy-sealing, for example be disclosed in people such as I.Azuma " Acrylic Oligomerfor High Solid Automotive Top Coating System HavingExcellent Acid Resistance ", among Progress in Organic Coating 32 (1997) 1-7, this paper introduces these contents as a reference.
In one embodiment, the present invention relates to aforementioned compositions, wherein, in the time of in silyl-capped reactant being joined other compositions that constitute said composition, its amount in composition accounts for the 0.1-90wt% of resin solid gross weight in the composition that constitutes said composition.In another embodiment, the present invention relates to aforementioned compositions, wherein, in the time of in silyl-capped reactant being joined other compositions that constitute said composition, its amount in composition accounts for the 0.1wt% at least of resin solid gross weight in the composition that constitutes said composition.In another embodiment, the present invention relates to aforementioned compositions, wherein, in the time of in silyl-capped reactant being joined other compositions that constitute said composition, its amount in composition accounts for the 1wt% at least of resin solid gross weight in the composition that constitutes said composition.In another embodiment, the present invention relates to aforementioned compositions, wherein, in the time of in silyl-capped reactant being joined other compositions that constitute said composition, its amount in composition accounts for the 5wt% at least of resin solid gross weight in the composition that constitutes said composition.
In another embodiment, the present invention relates to aforementioned compositions, wherein, in the time of in silyl-capped reactant being joined other compositions that constitute said composition, its amount in composition accounts for below the 60wt% of resin solid gross weight in the composition that constitutes said composition.In another embodiment, the present invention relates to aforementioned compositions, wherein, in the time of in silyl-capped reactant being joined other compositions that constitute said composition, its amount in composition accounts for below the 30wt% of resin solid gross weight in the composition that constitutes said composition.In another embodiment, the present invention relates to aforementioned compositions, wherein, in the time of in silyl-capped reactant being joined other compositions that constitute said composition, its amount in composition accounts for below the 10wt% of resin solid gross weight in the composition that constitutes said composition.The content range of silyl-capped reactant can be the arbitrary combination that comprises these values of cited value.
Coating composition of the present invention can be solvent-based coating composition, water base paint compositions, be solid particulate form (being powder paint compositions) or be powder slurry or the water dispersion form.Being used for forming the composition of the present invention of curing composition of the present invention can be dissolved or be dispersed in the organic solvent.The non-limiting example of appropriate organic solvent comprises alcohols, as butanols; Ketone is as Methyl amyl ketone; Aromatic hydrocarbons is as dimethylbenzene; And glycol ethers, as ethylene glycol monobutyl ether; The ester class; Other solvents; And the mixture of any aforementioned solvents.
In solvent-based compositions, the amount of organic solvent accounts for the 5-80wt% of resin solid gross weight in the composition that constitutes said composition usually, and can be 30-50wt%, comprises cited value.The total solid content of above-mentioned composition can account for the 40-75wt% of resin solid gross weight in the composition that constitutes said composition, and can be 50-70wt%, comprises cited value.Perhaps, the present composition can be solid particulate form, and this form is suitable for use as powder coating, or is suitable for being dispersed in the liquid medium such as water as powder slurry.
In another embodiment, can there be catalyzer in coating composition during forming.The non-limiting example of appropriate catalyst comprises acid material, and acid phosphate for example is as the phenylic acid acid phosphate; And be substituted or unsubstituted sulfonic acid, as Witco 1298 Soft Acid or tosic acid; And other catalyzer, as N, N '-dimethyl dodecyl amine catalyst and tin catalyst such as dibutyl tin laurate.In the time of in catalyzer being joined other compositions that constitute coating composition, its amount accounts for the 0.1-5.0wt% of resin solid gross weight in the composition that constitutes coating composition, comprises cited value.
In another embodiment, as mentioned above, can there be other composition in coating composition during forming.These other compositions include but not limited to similar additive commonly used in toughner, softening agent, tensio-active agent (for example polysiloxane), thixotropic agent, anti gassing agent, organic cosolvent, flow control agent, hindered amine light stabilizer, oxidation inhibitor, UV light stabilizing agent, tinting material or thinner (tint) and this area defined herein, and the mixture that can be included in any aforementioned substances in the coating composition of the present invention.When the composition that these are other joined in other compositions that constitute coating composition, its amount accounted for the 40wt% at the most of resin solid gross weight in the composition that constitutes coating composition, comprises cited value.
The amount that is coated to the coating composition on the ground can be according to such factors vary: the expectation purposes of the kind of ground and ground, that is, and the character of the residing environment of ground and institute's contact material.
In another embodiment, the present invention relates to a kind of ground through applying, it comprises ground and is coated in coating composition at least a portion of this ground that wherein this coating composition is selected from any aforesaid coating composition.In another embodiment, the present invention relates to a kind of method of coated substrate, comprise coating composition is coated at least a portion of this ground that wherein this coating composition is selected from any aforesaid coating composition.
In another embodiment, the present invention relates to a kind of method of coated substrate, further be included in and make its step of curing after coating composition is coated on the ground.In these embodiments, the composition that is used for forming coating composition can be selected from the composition of above argumentation, and other composition can be selected from above those that enumerate.
Here " composition at least a portion of ground " of usefulness is meant the composition at least a portion that directly is coated in ground, and is coated in the composition on any coating that is coated in advance at least a portion ground.
Coating composition of the present invention can be coated on possible any ground, comprises timber, metal, glass, plastics, foam materials, polymeric ground (as the elastomerics ground) etc.In one embodiment, the present invention relates to a kind of aforesaid through coated substrate, wherein should be through coated substrate be a kind of flexible substrates.In another embodiment, the present invention relates to a kind of aforesaid through coated substrate, wherein should be through coated substrate be a kind of rigidity ground.
In another embodiment, the present invention relates to a kind of aforesaid through coated substrate, wherein should be through coated substrate be a kind of ceramic ground.In another embodiment, the present invention relates to a kind of aforesaid through coated substrate, wherein should be through coated substrate be a kind of polymeric substrate.In another embodiment, the present invention relates to a kind of metal substrate through applying, comprise metal substrate and be coated in curing composition at least a portion of this metal substrate, wherein this curing composition is selected from any aforementioned compositions.In these embodiments, the composition that is used for forming curing composition can be selected from the composition of above argumentation, and other composition can be selected from above those that enumerate.
Another embodiment of the present invention relates to a kind of automotive substrates through applying, and comprises automotive substrates and is coated in curing composition at least a portion of this automotive substrates, and wherein this curing composition is selected from any aforementioned compositions.In another embodiment, the present invention relates to a kind of production, comprise a kind of automotive substrates is provided, and at least a portion of this automotive substrates, apply a kind of coating composition that is selected from any foregoing through applying the method for automotive substrates.Equally, in these embodiments, the composition that is used for forming curing composition can be selected from the composition of above argumentation, and other composition can be selected from above those that enumerate.
Suitable flexible elastomer ground can comprise any thermoplasticity as known in the art or thermoset synthetic materials.The non-limiting example of suitable flexible elastomer ground material comprises the urethane (" RIM ") and the thermoplastic polyurethane (" TPU ") of polyethylene, polypropylene, TPO (" TPO "), reaction injection molding(RIM).
The non-limiting example that can be used as the thermosetting material of ground of the present invention comprises the mixture of polyester, epoxy derivative, phenoplast, urethane (as " RIM " thermosetting material) and any aforementioned substances.The non-limiting example of suitable thermoplastic material comprises TPO, as the mixture of polyethylene, polypropylene, polymeric amide (as nylon), thermoplastic polyurethane, thermoplastic polyester, acrylate copolymer, vinyl polymer, polycarbonate, acrylonitrile-butadiene-styrene (ABS) (" ABS ") multipolymer, ethylene propylene diene terpolymers (" EPDM ") rubber, multipolymer and any aforementioned substances.
The non-limiting example of suitable metal substrate comprises the mixture of ferrous metal (for example iron, steel and alloy thereof), non-ferrous metal (for example aluminium, zinc, magnesium and alloy thereof) and any aforementioned metal.In specific auto parts purposes, ground can be by cold-rolled steel, electro-galvanized steel (as the hot dipping electro-galvanized steel), acierage-zinc steel, aluminium and magnesium.
When ground was used as the part of making automobile (including but not limited to automobile, truck and tractor), they can have Any shape, and can be selected from above-mentioned metal and flexible substrates.The typical shape of bodywork parts can comprise car body (vehicle frame), hood, car door, splash pan, collision bumper and upholstery thing.
In another embodiment, the present invention relates to aforesaid automotive substrates through applying, wherein the automotive substrates through applying is a hood.In another embodiment, the present invention relates to aforesaid automotive substrates through applying, wherein the automotive substrates through applying is a car door.In another embodiment, the present invention relates to aforesaid automotive substrates through applying, wherein the automotive substrates through applying is a splash pan.In another embodiment, the present invention relates to aforesaid automotive substrates through applying, wherein the automotive substrates through applying is a dashboard.In these embodiments, be used for forming the composition that the composition that applies the curing composition that automotive substrates uses can be selected from above argumentation.
In the embodiment of the present invention that relates to the automobile application, curing composition for example can be electrodeposited coating, undercoat, priming paint putty and/or finishing coat.Suitable finishing coat comprises single coating and priming paint/varnish compound coating.Single coating is formed by the one layer or more colored coating composition.Priming paint/varnish compound coating comprises one layer or more colored primer composition, and the one layer or more clear coat composition, and wherein paint base composition has at least a composition that is different from clear coat composition.In the embodiment of the present invention that relates to the automobile application, the varnish coating after the coating can be transparent.
In another embodiment, the present invention relates to polycomponent composite curing composition, comprise the undercoat that is formed by colored coating composition deposition and be coated in finishing coat composition on this undercoat, wherein the finishing coat composition is selected from any aforementioned compositions.
In one embodiment, the present invention relates to aforesaid polycomponent composite curing composition, wherein the finishing coat composition is transparent after solidifying, and is selected from any solidified foregoing.In these embodiments, the composition that is used for forming the finishing coat composition can be selected from the coating composition of above argumentation, and other composition can be selected from above those that enumerate.
The priming paint and clear finish (the being varnish) composition that are used in the polycomponent composite curing composition of the present invention can be mixed with liquid high-solid level composition in some cases,, contain 40wt% or greater than the composition of the resin solid of 50wt% that is.Solid content can be definite like this: the curing composition sample is heated to 105-110 ℃ reaches 1-2 hour to drive away volatile materials, measure the relative weight loss subsequently.As mentioned above, although curing composition can be formed by liquid coating composition, also can form by the coating composition that is mixed with powder paint compositions.
In the color-plus-clear system, the coating composition of undercoat can be can be used in the application of paints, any composition during especially automobile is used.The coating composition of undercoat can be by comprising resin glue and forming as the composition of the pigment of tinting material.The non-limiting example of resin glue comprises acrylate copolymer, polyester, Synolac and urethane.
The resin glue that is used for undercoat can be the organic solvent sill, and as US4,220,679 the 2nd hurdles the 24th walk to those of setting forth in the 4th hurdle the 40th row, and this paper quotes this part content.Water base paint compositions also can be used as the tackiness agent in the bottom coating composition, as US 4,403, and those of setting forth in 003,4,147,679 and 5,071,904.This paper introduces these United States Patent (USP)s as a reference.
Bottom coating composition can comprise one or more pigment as tinting material.The non-limiting example of suitable metallic pigment comprises al powder flake, bronze powder sheet and scribbles the mica of metal oxide.
Except metallic pigment, bottom coating composition can also contain the nonmetal coloured pigment that is commonly used in the top coat, and mineral dye for example is as titanium dioxide, ferric oxide, chromic oxide, lead chromate and carbon black; And pigment dyestuff, as phthalocyanine blue and phthalocyanine green.
Optional member in the bottom coating composition can comprise those that preparation top coat known in the field is used, and can comprise tensio-active agent, flow control agent, thixotropic agent, filler, anti gassing agent, organic cosolvent, catalyzer and other usual auxiliaries.The non-limiting example of these materials and suitable amounts is set forth in US 4,220, and in 679,4,403,003,4,147,769 and 5,071,904, this paper introduces these patents as a reference.
Bottom coating composition can adopt the coating method of any routine to be coated on the ground, as brushing, spraying, dip-coating or flow coat.Can adopt artificial or automatic spraying technology and the equipment that is used for aerial spraying, hydraulic spraying and electrostatic spraying as known in the art.
To the ground coating base coat time, the thickness of the undercoat that forms on the ground can be the 0.1-5 mil.In another embodiment, the thickness of the undercoat that forms on the ground can be the 0.1-1 mil, and can be 0.4 mil.
After the film that has formed undercoat on the ground, before the varnish coating coating, undercoat is solidified or implement a drying step, in this drying step, solvent is by heat drying or air-dry and be removed from the film of undercoat.Suitable drying conditions can be decided by concrete bottom coating composition and ambient moisture (if composition is water base), but suitably can be: under 75-200 temperature dry 1-15 minute.
Transparent or varnish finishing coat composition can be coated on the undercoat with the coating method of any routine, includes but not limited to compressed air spraying method, electrostatic spraying and artificial or automated method.Transparent surface coating can be coated in through solidified or before undercoat solidifies on the undercoat of drying.Under latter event, this two layers of coatings can be heated subsequently, thereby this two layers of coatings is solidified simultaneously.The thickness of Clear coating (build) can be the 1-6 mil.
Elaborated as above, coating composition can solidify with combining of heat energy by ionization or actinic radiation.Typical quantity of radiant energy condition of cure elaborated in front.Typical heat energy condition of cure can be to solidify 1-30 minute at 50-475 °F (10-246 ℃).
The second road finishing coat coating composition can be coated on the first road finishing coat to form " varnish-be applied to-varnish " finishing coat.Can the first road finishing coat coating composition be coated on the undercoat according to above-described.The second road finishing coat coating composition can be coated in through solidified or before undercoat and the first road finishing coat solidify on the first road finishing coat of drying.Undercoat, the first road finishing coat and the second road finishing coat can be heated subsequently, thereby these three layers of coatings are solidified simultaneously.
Should understand, the coating composition of second transparent surface coating and first transparent surface coating can be identical or different, precondition is, when carrying out " wetting, it is wet to bump " when applying, a kind of finishing coat can not disturb the curing of another kind of finishing coat basically, and this interference for example is meant that having restrained solvent/water evaporates away from following one coat.In addition, the first road finishing coat, the second road finishing coat or they both can be curing composition of the present invention.The first road transparent surface coating composition can be any possible transparent surface coating composition known in those skilled in the art.The first road transparent surface coating composition can be water base or solvent based, or solid particulate form, i.e. powder coating.
The non-limiting example of the first suitable road finishing coat composition comprises: the crosslinkable coating composition that comprises at least a heat-setting coating and at least a solidifying agent.Suitable water-based varnish is disclosed in US 5,098, and in 974, this paper introduces this patent as a reference, and this varnish is based on the water soluble acrylic resin.Available solvent base varnish is disclosed in US 5,196, and in 485 and 5,814,410, this paper introduces these patents as a reference, and this varnish comprises polyepoxide and polyprotonic acid solidifying agent.Suitable powder clear coatings is disclosed in US 5,663, and in 240, this paper introduces this patent as a reference, and this varnish comprises epoxy-functional acrylate copolymer and polycarboxylic acid curing agent.
Generally, after on ground, having formed the first road finishing coat, before applying the second road finishing coat, the first road finishing coat is implemented a drying step, in this drying step, solvent is by heat drying or air-dry and be removed from film, or implements curing schedule.Suitable drying conditions can be decided by first concrete road finishing coat composition and ambient moisture (if composition is water base), but can be usually: under 75-200 temperature dry 1-15 minute.
Can with the dope applying method of any routine with the second road top coat of polysiloxane that contains of the present invention to the first road finishing coat.Condition of cure can be above-mentioned those of finishing coat of being used for.The build of this second road finishing coat can be 0.1-3 mil (7.5-75 micron).
What deserves to be mentioned is, preferably the coating composition that contains polysiloxane can be mixed with " single layer coating ", that is, form the coating of one deck coating in the time of on being coated to ground basically.This single layer coating composition can be colored.The non-limiting example of suitable pigments comprise above-described those.When being used as single layer coating, the coating composition that contains polysiloxane of the present invention can be applied two to three times continuously, and is in some cases, every dried all over can only dodging through room temperature between applying.Should " layered coating " when solidifying, can form one deck coating basically.
In another embodiment, the present invention relates to a kind of method for preparing multi-component composite coatings, comprise that (a) is coated on the ground painted composition to form undercoat; (b) the finishing coat composition is coated at least a portion of this undercoat to form finishing coat thereon, wherein the finishing coat composition is selected from any aforementioned compositions.In this embodiment, the composition that is used for forming the finishing coat composition can be selected from above-described coating composition, and other composition can be selected from above those that enumerate.
The coating that is formed by curing composition of the present invention can have outstanding appearance property and initial damage resistant (damage) property, and back-weathering resistance or " reservation " damage resistant (damage) property, these performances can be by measuring the glossiness be coated with ground before or after being worn and estimate being coated with ground.
The present invention is coated with initial 20 ° of glossiness of ground can use the Company available from GardnerInstrument, 20 ° of NOVO-GLOSS, the 20 statistics glarimeter measurements of Inc..Can scratch test to being coated with ground, that is, with the sand paper that loads to coating or ground linearly ten of scratchings come and go, use be available from Atlas Electrical DevicesCompany of Chicago, the Atlas AATCC Scratch Tester of Illinois, Model CM-5.Described sand paper is 3M 281Q WETOTDRY TMPRODUCTION TM9 microns polishing papers, available from 3M Company of St.Paul, Minnesota.Wash model with tap water then, and pat dry gently carefully with paper handkerchief.Measure 20 ° of glossiness in the scuffing zone of every test piece.The value of record is the reservation percentage of original gloss after scratching test, that is, and and the glossiness/original gloss after 100% * scuffing.This test method intactly is set forth in following examples.
In one embodiment, the present invention relates to initial 20 ° of glossiness (for example uses above-described available from Gardner Instrument Company, Inc. the curing composition greater than 40 20 ° of NOVO-GLOSS20 statistics glarimeter measurements), said composition can be any aforesaid present composition.In another embodiment, the present invention relates to initial 20 ° of glossiness (for example uses above-described available from Gardner Instrument Company, Inc. 20 ° of NOVO-GLOSS 20 statistics glarimeter measurements) greater than 50 or greater than 70 curing composition, said composition can be any aforesaid present composition.
In addition, in another embodiment, the present invention relates to following curing composition, back-weathering resistance that this curing composition had or " reservation " scratch resistance value make through after scratching test, have the initial 20 ° of glossiness more than 40% to remain.In addition, curing composition of the present invention (for example can have so back-weathering resistance or scratch resistance, after test board without scratching being exposed to accept under the UVA-340 bulb QUV simulation aging in an aging cupboard available from Q Panel Company, with above-mentioned scuffing test method measuring), it can make is having the initial 20 ° of glossiness more than 50% or more than 60% to remain after aging.
In one embodiment, the present invention relates to improve the method for ground scratch resistance, comprise on this ground, applying any present composition that is used for this ground.In another embodiment, the present invention relates to improve the method for ground pollution resistance, comprise on this ground, applying any present composition that is used for this ground.
In another embodiment, the present invention relates to keep for a long time the method for ground glossiness, comprise on this ground, applying any present composition that is used for this ground.In another embodiment, the present invention relates to recover the method for ground glossiness, comprise on this ground, applying any present composition that is used for this ground.
In another embodiment, curing composition of the present invention also can be used as the ornamental or protective coating of coloured plastics (elasticity) ground (as above-mentioned those) or mo(u)lded-in colour (" MIC ") plastic bottom material.In these were used, composition can directly be coated on the plastic bottom material or be comprised in the molding matrix.Not necessarily, can on plastics or elastomerics ground, directly apply adhesion promotor earlier, apply composition then thereon as finishing coat.The present composition also can preferably be formulated into the colored coating composition as undercoat, as the undercoat in the multi-component composite coatings, and the individual layer finishing coat that comprises pigment or tinting material.In these embodiments, the composition that is used for forming composition can be selected from above-described coating composition, and other composition can be selected from above those that enumerate.
In another embodiment of the present invention, a kind of curing composition is provided, said composition comprises the particle that is dispersed in the curing composition that contains one or more thermoplastic material.As mentioned above, the granule density of surf zone is greater than interior region.This curing composition can be derived from the thermoplastic resin dope composition.The non-limiting example of suitable thermoplastic material comprises acrylate copolymer, polyolefin polymer, polyamide polymer and the polyester polymers of the high molecular (being that Mw is greater than 20,000, greater than 40,000 or greater than 60,000) that is used to paint dry system.The non-limiting example that can derive an analog thermoplastic material of curing composition is fluoropolymer-acrylic copolymer, for example by 1, the 1-difluoroethylene is (as KYNAR 500, available from Ausimont USA, Inc.) and thermoplastic propene's acid copolymer (as ACRYLOID B44,65% methyl methacrylate and 25% ethyl propenoate are available from Dock Res in, Inc.) Zhi Bei those.
In another embodiment, the present invention relates to behind predetermined period the method for the glossiness of the ground that keeps polymeric substrate or scribble polymkeric substance, comprise on this ground, applying any present composition that is used for this ground.Described predetermined period is generally at least 6 months, and can be at least 1 year.In another embodiment, the present invention relates to the method for the glossiness of the ground that recovers polymeric substrate or scribble polymkeric substance, comprise on this ground, applying any above-mentioned present composition.
Following examples have further been explained the present invention, but should not think that it is defined as the present invention the details of this embodiment.Unless stated otherwise, all umbers in following examples and the specification sheets full text and percentage number average are by weight.
Embodiment
Prepare a kind of two curing (solidified by ultraviolet ray radiation and thermofixation) coating composition, and estimate by the mode of the following stated.
Assign to prepare coating composition by under agitation adding various one-tenth according to order listed in the following table 1.To join again in other compositions after acrylic polyol and the isocyanuric acid ester premix.
Table 1
Composition Explanation ?? Solid content Weight
??SR355 1 Two-TMP tetraacrylate ????27.3 ????27.3
??Clariant?HJGHLINK ??OG?108-32 Colloid silica in the tripropylene glycol diacrylate ????41.9 ????41.9
??DAROCURE?4265 3 Light trigger ????2.0 ????2.0
??TINUVIN?400 3 UV light absorber ????3.0 ????3.0
??TINUVIN?292 3 Hindered amine light stabilizer ????0.8 ????0.8
??RC-68-1497 2 Acrylic polyol resin ????15.6 ????23.3
??DESMODUR?N-3300 4 The isocyanuric acid ester of HDI ????9.4 ????9.4
Add up to ????100.0 ????107.7
1Two-trimethylolpropane tetra-acrylate is available from Sartomer Company, Inc.
2The acrylic polyol of making by 14.5% butyl acrylate, 14.5% butyl methacrylate, 27.5% isobornyl methacrylate, 22.6% Rocryl 410,20.4% hydroxyethyl methylacrylate, 0.4% vinylformic acid, have following performance: the solid content in Aromatic 100 solvents is 67%, Mw is 2336, Mn is 1236, and hydroxyl value is 116.8.
3Phosphine oxide, as 2-hydroxy-2-methyl-1-phenyl third-1-ketone and 2,4,50: 50 mixtures of 6-trimethylbenzoyl diphenyl phosphine oxide are available from Ciba-Geigy Corporation.
4The isocyanuric acid ester of hexamethylene diisocyanate is available from Bayer Corporation.
Coating composition is coated in following through pre-treatment and scribble on the plate of undercoat.Used plate is to be of a size of 4 inches * 12 inches (cold-rolled steel sheet of 10.16cm * 30.48cm) scribbles the ED5000 electrocoating paint (available from PPG Industries, Inc).This test board can be available from ACT Laboratories, Inc.of Hillsdale, Michigan.(BWB-8555 black water-based primer available from PPGIndustries, Inc), and toasted 30 minutes at 285 °F (141 ℃) entirely to spray the priming paint of 0.6 mil (15 microns) build.Wet film blade coating device with one 7 mil (179 microns) is coated in coating composition of the present invention on the above-mentioned undercoat, makes build be about 1.0-1.2 mil (26-31 micron).(25 ℃) sudden strain of a muscle at room temperature of this Clear coating was done 5 minutes, used 576 millijoules/cm then 2, linear velocity is the ultraviolet light polymerization of 70 feet per minute clocks (21.3 meters/minute), subsequently 285 (141 ℃) thermofixations 30 minutes.
Estimate the scratch resistance of coating on the plate in the following manner.Use N.GardnerCompany, 20 ° of glossiness of NOVO-GLOSS 20 statistics glarimeter measurements of Inc. available from Pual.To being scratched test by coated plate, that is, with the sand paper that loads to coated surface linearly ten of scratchings come and go, use be available from Atlas Electrical Devices Company of Chicago, the Atlas AATCC Scratch Tester of Illinois, Model CM-5.Used sand paper is 3M 281Q WETOTDRY TMPRODUCTION TM9 microns polishing papers, available from 3MCompany of St.Paul, Minnesota.Wash model with tap water then, and pat dry gently carefully with paper handkerchief.Measure 20 ° of glossiness (when using identical glossmeter) in the scuffing zone of every test piece with the initial 20 ° of glossiness of measurement.Minimum 20 ° of gloss values that employing is read by the scuffing zone, scratching outcome record is the reservation percentage of original gloss after scratching test, adopts following method of calculation: the glossiness ÷ original gloss after 100% * scuffing.It is ideal that glossiness keeps the percentage height.
Test-results is listed in the following table 2.
Table 2
Clear coating Initial 20 ° of glossiness Scratch 20 ° of glossiness after testing Glossiness keeps percentage %
The UV/ heat dual curing ????82 ????79 ????96
Composition of the present invention can produce numerous advantages in application of paints, include but not limited to good initial scratch resistance and keep scratch resistance, good surface appearance performance such as glossiness and reflection sharpness, and physicals such as good flexibility and weathering resistance.
It will be understood by those skilled in the art that and can above-mentioned embodiment change not deviated from fundamental principle of the present invention.Therefore, will be understood that to the invention is not restricted to disclosed these specific embodiments, but contained all improvement within the spirit and scope of the present invention, defined as incidental claim.

Claims (87)

1, the coating composition that forms by following composition, described composition comprises:
(a) at least a first material, it comprises the reactive functionality of at least a radiation-hardenable;
(b) at least a second material, it comprises at least a heat-setting reactive functionality;
(c) at least a solidifying agent, it can with at least a heat-setting reactive functionality reaction, this at least a solidifying agent is selected from the mixture of isocyanic ester, polyepoxide, polyprotonic acid, polyvalent alcohol and aforementioned substances of polyisocyanates, the triazine derivatives of aminoplast(ic) resin, polyisocyanates, sealing; With
(d) multiple particle, they are selected from the mixture of inorganic particle, composite particles and aforementioned substances,
Wherein each composition is different.
2, the coating composition of claim 1, wherein the reactive functionality of at least a radiation-hardenable is selected from vinyl, vinyl ether group, unsaturated ester group, epoxy group(ing), dimaleoyl imino and fumaric acid ester group.
3, the coating composition of claim 2, wherein the reactive functionality of at least a radiation-hardenable is the unsaturated ester group that is selected from acrylate-based, methacrylate based and ethyl propylene perester radical.
4, the coating composition of claim 3, wherein unsaturated ester group is acrylate-based.
5, the coating composition of claim 1, wherein first material comprises polysiloxane.
6, the coating composition of claim 1, in the time of wherein in first material being joined other compositions that constitute coating composition, its amount in coating composition accounts for the 1-99wt% of resin solid gross weight in the composition that constitutes coating composition.
7, the coating composition of claim 1, wherein the reactive functionality of at least a radiation-hardenable can be solidified by ionizing rays.
8, the coating composition of claim 1, wherein the reactive functionality of at least a radiation-hardenable can be solidified by actinic radiation.
9, the coating composition of claim 1, wherein the reactive functionality of at least a radiation-hardenable can be passed through solidified by ultraviolet ray radiation.
10, the coating composition of claim 1, wherein at least a heat-setting reactive functionality are selected from isocyanate group, epoxy group(ing), carbonyl, amido, acid anhydride base, hydroxyalkylamide groups and the '-aziridino of hydroxyl, vinyl, urethane groups, urea groups, amide group, carbamate groups, isocyanate group, sealing.
11, the coating composition of claim 1, wherein second material is a kind of film-forming polymer, and this film-forming polymer is selected from the multipolymer and the mixture of hydroxy-functionalized polymer, polyester, acrylate copolymer, urethane, polyureas, polymeric amide, carbamate functional polymer, the polyisocyanates that is different from solidifying agent (c), the polyisocyanates that is different from the sealing of solidifying agent (c), the polyepoxide that is different from solidifying agent (c), polyethers, the polyprotonic acid that is different from solidifying agent (c), polyamines, many acid anhydrides and aforementioned substances.
12, the coating composition of claim 11, wherein second material comprises at least a polysiloxane.
13, the coating composition of claim 12, wherein said at least a polysiloxane comprises at least a following structural unit (I):
(I)R 1 nR 2 mSiO (4-n-m)/2
Each R wherein 1Can be identical or different, represent H, OH, monovalence alkyl or monovalence siloxanes; Each R 2Can be identical or different, representative comprises the group of at least a reactive functionality, and wherein the following number that requires is satisfied in each representative of m and n: 0＜n＜4,0＜m＜4, and 2≤(m+n)＜4.
14, the coating composition of claim 13, wherein each R 2Can be identical or different, representative comprises the group of at least a reactive functionality, and described reactive functionality is selected from polyisocyanate-based, primary amine groups, secondary amine, amide group, carbamate groups, urea groups, urethane groups, vinyl, unsaturated ester group, dimaleoyl imino, fumaric acid ester group, acid anhydride base, hydroxyalkylamide groups and the epoxy group(ing) of hydroxyl, carboxyl, isocyanate group, sealing.
15, the composition of claim 12, wherein said at least a polysiloxane have following structural formula (II) or (III):
Figure A0081984400041
Or Wherein:
The value of m is at least 1;
M ' is 0-75;
N is 0-75;
N ' is 0-75;
Each R can be identical or different, is selected from the mixture of H, OH, monovalence alkyl, monovalence siloxanes and any aforementioned group; With
-R aComprise following structural formula (IV):
(IV)????-R 3-X
Wherein-R 3Be selected from alkylidene group, oxyalkylene group, alkarylene, alkylene group, oxygen alkylene group (oxyalkenylene group) and inferior alkene aryl; With
X representative comprises the group of at least a following reactive functionality, and described reactive functionality is selected from polyisocyanate-based, primary amine groups, secondary amine, amide group, carbamate groups, urea groups, urethane groups, vinyl, unsaturated ester group, dimaleoyl imino, fumaric acid ester group, acid anhydride base, hydroxyalkylamide groups and the epoxy group(ing) of hydroxyl, carboxyl, isocyanate group, sealing.
16, the coating composition of claim 12, the amount of wherein said at least a polysiloxane account for the 0.5-75wt% of resin solid gross weight in the composition that constitutes coating composition.
17, the coating composition of claim 1, in the time of wherein in second material being joined other compositions that constitute coating composition, its amount in coating composition accounts for the 0.5-98.5wt% of resin solid gross weight in the composition that constitutes coating composition.
18, the coating composition of claim 1, wherein solidifying agent is selected from the polyisocyanates of aminoplast(ic) resin, polyisocyanates and sealing.
19, the coating composition of claim 18, wherein solidifying agent is a polyisocyanates.
20, the coating composition of claim 1, in the time of wherein in solidifying agent being joined other compositions that constitute coating composition, its amount accounts for the 0.5-65wt% of resin solid gross weight in the composition that constitutes coating composition.
21, the coating composition of claim 1, wherein said particle are selected from the mixture of pyrogenic silica, soft silica, colloid silica, aluminum oxide, colloidal alumina, titanium dioxide, Cs2O, yttrium oxide, colloid yttrium oxide, zirconium white, colloidal zirconia and any aforementioned substances.
22, the coating composition of claim 1, wherein said particle has passed through surface treatment.
23, the coating composition of claim 1, wherein said particle comprises colloid silica.
24, the coating composition of claim 1, the median size of wherein said particle before being added into composition is lower than 100 microns.
25, the coating composition of claim 24, the median size of wherein said particle before being added into composition is lower than 50 microns.
26, the coating composition of claim 1, the median size of wherein said particle before being added into composition are 1 to being lower than 1000 nanometers.
27, the coating composition of claim 26, the median size of wherein said particle before being added into composition is the 1-100 nanometer.
28, the coating composition of claim 27, the median size of wherein said particle before being added into composition is the 5-50 nanometer.
29, the coating composition of claim 1, in the time of wherein in described particle being joined other compositions that constitute said composition, its amount in composition accounts for the 0.01-75wt% of resin solid gross weight in the composition that constitutes said composition.
30, the coating composition of claim 29, wherein said particulate amount is at least 0.1wt%.
31, the coating composition of claim 30, wherein said particulate amount is at least 0.5wt%.
32, the coating composition of claim 31, wherein said particulate amount is at least 5wt%.
33, the coating composition of claim 1 wherein constitutes in the composition of composition and contains at least a tensio-active agent.
34, the coating composition of claim 33, wherein said at least a tensio-active agent is selected from aniorfic surfactant, nonionic surface active agent and cationic surfactant.
35, the coating composition of claim 1 wherein constitutes in the composition of composition and contains at least a light trigger.
36, the coating composition of claim 35; wherein said at least a light trigger is selected from butyl isomer, the α of bitter almond oil camphor, benzophenone, dihydroxy benaophenonel, anthraquinone, thioxanthone, substituted bitter almond oil camphor such as benzoin ether; α-diethoxy phenyl methyl ketone, α; alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl third-1-ketone, 2; 4, the mixture of 6-trimethylbenzoyl diphenyl phosphine oxide and aforementioned substances.
37, the coating composition of claim 35, wherein said at least a light trigger are 2-hydroxy-2-methyl-1-phenyl third-1-ketone and 2,4,50: 50 mixtures of 6-trimethylbenzoyl diphenyl phosphine oxide.
38, the coating composition of claim 1 wherein constitutes in the composition of composition and contains at least a material that has the silyl-capped reactive functionality of at least a usefulness.
39, the coating composition of claim 38, wherein silyl-capped group has following structural formula (IX): 6
Figure A0081984400071
Each R wherein 1, R 2And R 3Can be identical or different, representative has alkyl, phenyl or the allyl group of 1-18 carbon atom.
40, the coating composition of claim 1, the initial scratch resistance value that wherein cured compositions had make through after scratching test, have the initial 20 ° of glossiness more than 40% to remain.
41, the coating composition of claim 1, the reservation scratch resistance value that wherein cured compositions had make through after scratching test, have the initial 20 ° of glossiness more than 30% to remain.
42, the solidified coating that forms by the composition of claim 1.
43, the curing composition of claim 42, wherein curing composition is to come solidified by being exposed in (1) ionizing rays or actinic radiation and (2) heat energy.
44, the curing composition of claim 42, wherein curing composition is to come solidified by being exposed in (1) ultraviolet radiation and (2) heat energy.
45, a kind of through coated substrate, comprise ground and the composition that is deposited on the claim 1 on this ground of at least a portion.
46, a kind of method that forms solidified coating on ground is included in the coating composition that applies claim 1 at least a portion of this ground.
47, the method for claim 46 comprises the step that coating composition is exposed in (1) ionizing rays or actinic radiation and (2) heat energy.
48, the method for claim 46, wherein said ground is an automotive substrates.
49, a kind of automotive substrates through applying comprises automotive substrates and the composition that is deposited on the claim 1 on this automotive substrates of at least a portion.
50, the automotive substrates through applying of claim 49, wherein this automotive substrates is a collision bumper.
51, the automotive substrates through applying of claim 49, wherein this automotive substrates is a hood.
52, the automotive substrates through applying of claim 49, wherein this automotive substrates is a car door.
53, the automotive substrates through applying of claim 49, wherein this automotive substrates is a splash pan.
54, a kind of polycomponent composite paint comprises the undercoat that is formed by painted coating composition deposition, and the composition that is coated in the claim 1 at least a portion of this undercoat.
55, the polycomponent mixture of claim 54, wherein said composition is a finish paint.
56, the polycomponent mixture of claim 55, wherein said composition is transparent after solidifying.
57, a kind of method of producing the polycomponent mixture comprises:
(a) on ground, apply painted coating composition to form undercoat;
(b) at least a portion of this undercoat, apply coating composition as the claim 1 of finishing coat composition; With
(c) this coating composition is solidified to form solidified coating.
58, the method for claim 57, wherein the finishing coat composition is to come solidified by being exposed in (1) ionizing rays or actinic radiation and (2) heat energy after being applied on the ground.
59, a kind of method of scratch resistance of improving polymeric substrate or scribbling the ground of polymkeric substance is included in the composition that forms claim 1 at least a portion of described ground.
60, a kind of method of glossiness that keeps polymeric substrate or scribble the ground of polymkeric substance in predetermined period is included in the composition that forms claim 1 on the surface of described ground.
61, a kind of method of glossiness of recovering polymeric substrate or scribbling the ground of polymkeric substance is included in the composition that forms claim 1 on the surface of described ground.
62, the coating composition that forms by following composition, described composition comprises:
(a) a kind of first material, it comprises the reactive functionality of at least a radiation-hardenable;
(b) a kind of second material, it comprises at least a heat-setting reactive functionality;
(c) at least a solidifying agent, it can with at least a heat-setting reactive functionality reaction, this at least a solidifying agent is selected from the mixture of isocyanic ester, polyepoxide, polyprotonic acid, polyvalent alcohol and aforementioned substances of polyisocyanates, the triazine derivatives of aminoplast(ic) resin, polyisocyanates, sealing; With
(d) multiple particle,
Wherein each composition is different.
63, the composition of claim 62, the initial scratch resistance value that wherein cured compositions had make through after scratching test, have the initial 20 ° of glossiness more than 40% to remain.
64, the composition of claim 62, the reservation scratch resistance value that wherein cured compositions had make through after scratching test, have the initial 20 ° of glossiness more than 30% to remain.
65, the solidified coating that forms by the composition of claim 62.
66, a kind of through coated substrate, comprise ground and the composition that is deposited on the claim 62 on this ground of at least a portion.
67, a kind of method that forms solidified coating on ground is included in the coating composition that applies claim 62 at least a portion of this ground.
68, the method for claim 67, wherein coating composition is to come solidified by this coating composition being exposed in (1) actinic radiation or ionizing rays and (2) heat energy after being applied on the ground.
69, the method for claim 67, wherein said ground is an automotive substrates.
70, a kind of automotive substrates through applying comprises automotive substrates and the composition that is deposited on the claim 62 on this automotive substrates of at least a portion.
71, a kind of polycomponent composite paint comprises the undercoat that is formed by painted coating composition deposition, and the composition that is coated in the claim 62 at least a portion of this undercoat.
72, a kind of method of producing the polycomponent mixture comprises:
(a) on ground, apply painted composition to form undercoat;
(b) at least a portion of this undercoat, apply coating composition as the claim 62 of finishing coat composition; With
(c) this coating composition is solidified to form solidified coating.
73, a kind of method of scratch resistance of improving polymeric substrate or scribbling the ground of polymkeric substance is included in the composition that forms claim 62 at least a portion of described ground.
74, a kind of method of glossiness that keeps polymeric substrate or scribble the ground of polymkeric substance in predetermined period is included in the composition that forms claim 62 on the surface of described ground.
75, a kind of method of glossiness of recovering polymeric substrate or scribbling the ground of polymkeric substance is included in the composition that forms claim 62 on the surface of described ground.
76, the coating composition that forms by following composition, described composition comprises:
(a) at least a material, it comprises at least a ultraviolet solidifiable reactive functionality and at least a heat-setting reactive functionality;
(b) at least a solidifying agent, it can with at least a heat-setting reactive functionality reaction, this at least a solidifying agent is selected from the mixture of isocyanic ester, polyepoxide, polyprotonic acid, polyvalent alcohol and aforementioned substances of polyisocyanates, the triazine derivatives of polyisocyanates, sealing; With
(c) multiple particle,
Wherein each composition is different.
77, the composition of claim 76, the initial scratch resistance value that wherein cured compositions had make through after scratching test, have the initial 20 ° of glossiness more than 40% to remain.
78, the composition of claim 76, the reservation scratch resistance value that wherein cured compositions had make through after scratching test, have the initial 20 ° of glossiness more than 30% to remain.
79, the solidified coating that forms by the composition of claim 76.
80, a kind of through coated substrate, comprise ground and the composition that is deposited on the claim 76 on this ground of at least a portion.
81, a kind of method that forms curing composition on ground is included at least a portion of this ground and applies the coating composition of claim 76, and is being coated on the ground with this coating composition of after fixing.
82, a kind of automotive substrates through applying comprises automotive substrates and the composition that is deposited on the claim 76 on this automotive substrates of at least a portion.
83, a kind of polycomponent composite paint comprises the undercoat that is formed by painted coating composition deposition, and the composition that is coated in the claim 76 at least a portion of this undercoat.
84, a kind of method of producing the polycomponent mixture comprises:
(a) on ground, apply painted composition to form undercoat;
(b) at least a portion of this undercoat, apply coating composition as the claim 76 of finishing coat composition; With
(c) this coating composition is solidified to form solidified coating.
85, a kind of method of scratch resistance of improving polymeric substrate or scribbling the ground of polymkeric substance is included in the composition that forms claim 76 at least a portion of described ground.
86, a kind of method of glossiness that keeps polymeric substrate or scribble the ground of polymkeric substance in predetermined period is included in the composition that forms claim 76 on the surface of described ground.
87, a kind of method of glossiness of recovering polymeric substrate or scribbling the ground of polymkeric substance is included in the composition that forms claim 76 on the surface of described ground.
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CA2417257A1 (en) 2002-02-07

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