CN1462300A - Coating compositions - Google Patents

Coating compositions Download PDF

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Publication number
CN1462300A
CN1462300A CN01816063.8A CN01816063A CN1462300A CN 1462300 A CN1462300 A CN 1462300A CN 01816063 A CN01816063 A CN 01816063A CN 1462300 A CN1462300 A CN 1462300A
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coating composition
inorganic
hydrolyzable
monomer precursor
coating
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A·泰勒
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Welding Institute England
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Welding Institute England
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Priority claimed from PCT/GB2000/003643 external-priority patent/WO2001025343A1/en
Priority claimed from GB0107233A external-priority patent/GB0107233D0/en
Priority claimed from GB0109301A external-priority patent/GB0109301D0/en
Application filed by Welding Institute England filed Critical Welding Institute England
Publication of CN1462300A publication Critical patent/CN1462300A/en
Pending legal-status Critical Current

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    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences

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

Abstract

A coating composition comprises an inorganic phase homogeneously mixed with an organic phase, the inorganic phase being obtainable by hydrolysis of first and second hydrolysable inorganic monomer precursors, the first hydrolysable inorganic monomer precursors (A1) being different to the second hydrolysable monomer precursors (A2) and having at least two hydrolysable ligands, and the second hydrolysable inorganic monomer precursors having at least one non-hydrolysable ligand, the organic phase comprising polymerisable organci species, characterised in that the molar ratio, R (A), of first hydrolysable inorganic monomer precursors (A1): total hydrolysable inorganic monomer precursors (A1 and A2) is in the range 0.4 t 0.99.

Description

Coating composition
Invention field
The present invention relates to be coated to various different substrate materials,, and keep the coating composition of good optical property simultaneously so that give anti-machinery of those base materials and chemical destruction.
Background of invention
Polymer-based material is used as the substitute of glass routinely under many situations that weight of glass, pulverizing are inclined to or are spent and its purposes is inconsistent, and polymer materials such as vinylformic acid and polycarbonate are especially aspect bad wear resistance, and bad erosion resistance aspect has the inherent shortcoming in bad anti-UV photodegradation and when being exposed to organic solvent.
In order to address these problems, supercoat is coated on the polymer materials.Typically the silica based materials by the manufacturing of colloidal state sol-gel technique has been widely used in this purpose, and in this technology, silicon oxide particle is coalescent, and final gelling, forms silicon oxide network widely.Yet these materials only provide limited protection.In addition, because therefore the inertia essence of these materials and its low crosslinking degree especially aspect its performance or its versatility, exist further room for improvement hardly.
The coating that provides by polymer sol-gel technique has higher degree of crosslinking, and and then has significantly better anti-machinery and chemical than conventional particulate sill.Typically, in polymer sol-gel technique, hydrolysis precursor molecule such as alkoxide in the mixture of water and solvent, and continue by the polycondensation experience from the conversion of colloidal sol to gel state.Yet, regrettably, after gelation, remove the meeting of desolvating and in the gel structure body, introduce stress, and stress can be tending towards causing be full of cracks and performance loss at coat-thickness greater than about 1.5 microns places by forced drying or spontaneous evaporation.A kind of method that overcomes this limitation is the coating of coating multi-layer thin, and it has the practical limit of 20-30 layer coating usually.Yet this is a trouble, and increases production cost, also causes the coating of relative rigidity.
Under need be greater than 1.5 microns coat-thickness situation, use compound inorganic/organic materials.Typically, prepare these materials and these materials and be commonly referred to ORMOCERs  (organically-modified pottery) by polymerisable organic constituent is incorporated in the colloidal state collosol-gelatum system.Can think that ORMOCERs is included in silicon oxide (or other metal oxide) particle network in the organic polymer network.Between these two kinds of networks, intert mutually hardly.
Although about 25% with during above oxide carried (loadings), under the situation that realizes optimal hardness, this class material forms relative hard, abrasion-resistant coating, runs into the transparency problem.In addition, up to nearest relatively, these materials of great majority are tending towards solidifying under about 200 ℃ or higher temperature, and this makes them be unsuitable for being coated on the low base material of softening temperature, are on 150 ℃ or the lower thermoplastic matrix as softening temperature.
Therefore be starved of the low temperature coated material that exploitation does not have employed so far silica based materials shortcoming.
US-A-4921881 discloses the anti-scratch coating that synthetic glass is used, this coating is total to-condenses by (A) 82-64wt%'s, and it is by 90-65wt% vinyltrimethoxy silane or vinyltriethoxysilane or its mixture and 10-35wt% tetramethoxy-silicane or tetraethoxysilane or the preparation of its mixture; (B) 9-27wt% reactive diluent, it comprises at least two vinyl, acrylic or methacrylic acid groups/molecule; (C) 0-9wt% light trigger.
EP-A-0851009 discloses a kind of antifouling paint compositions, it comprises (A) silicon oxide-dispersive organosilane oligomer solution, it obtains by the hydrolyzable organosilane of partial hydrolysis, and wherein the described silane of 50mol% comprises the alkyl with 1-8 carbon atom at least; (B) acrylic copolymer; (C) linear polysiloxanes dialdehyde; (D) contain the organopolysiloxane of silanol group; (E) curing catalysts.Preferred coating compositions comprises 20-35wt% (A), 35-55wt% (B), 5-25wt% (C), 5-25wt% (D) and 0.5-3wt% (E).
US-A-5470910 discloses the matrix material as optical element, but it also requires the application of matrix material as coating.By making the colloidal sol and the polymerizable that contain the organic/inorganic nano grade particles be mixed together reaction, form matrix material to the compound in organic and inorganic or the organic/inorganic network.
In the application WO-A-0125343 of our early stage pending trial, we disclose the new coating composition of making by polymer sol-gel technique.Those of disclosed coating composition and the application consist essentially of two kinds of structural constituents in WO-A-01265343: mutually inorganic and organic phase.This two-phase forms interpenetrating(polymer)networks on nano level, under the electromagnetic radiation of using visible wavelength, be undistinguishable therefore.
In more detail, by the hydrolysis of the different hydrolyzable inorganic monomer precursor of at least two classes with aftercondensated, form inorganic sol, thereby form inorganic phase.With inorganic sol and polymerisable organism uniform mixing, in case described polymerisable organism polymerization then produce organic phase.Importantly before changing into its final gel form, inorganic sol causes organism.
The performance of final coating depends on the person's character and the consumption of coating composition integral part.
Summary of the invention
Have now found that, can by changing the consumption of inorganic phase,, make coating composition according to the person's character of base material to be coated and/or the required application of coating with relative consumption that the more important thing is the different components that changes the inorganic phase of formation.
Therefore,, provide the many different coating composition that can be coated on the various different substrate materials according to the present invention, as claim 1 define and following will be in more detail to its description.
Detailed Description Of The Invention
Coating composition of the present invention belongs to identical total class with described in the WO-A-0125343 those.
This coating composition comprises the uniform mixture of following component:
(A) the inorganic oxide polycondensate that forms of the different compounds by at least two kinds of following general formulas of hydrolysis and polycondensation:
MR 1 aR 2 b(OR 3) c???????????????[1]
Wherein M typically represents a kind of Si of being selected from, Ti, and Zr, Fe, Cu, Sn, B, Al, Ge, Ce, the element among Ta and the W is preferably selected from Si, Ti, Al and Zr and Si most preferably; Typically, R 1And R 2Be independently selected from alkyl with 1-10 carbon atom and wherein alkyl can contain ehter bond or ester bond; R 3Typically be hydrogen atom or have the alkyl of 1-10 carbon atom and a and b be independently selected from 0 and integer and C be the integer that equals (x-a-b), wherein x is the valence state of element M,
(B) polymerisable organism for example forms those of thermoplastic polymer or thermosetting polymer when polymerization,
(C) look required, cause the polymerization starter of polymerisable organic polymer,
(D) randomly, non--structure, functional additive such as UV-absorption agent, viscosity modifier, dyestuff and tensio-active agent.
Following component (A) (B) and (C) is called the structural constituent of coating composition, and component (D) be called non--structure, functional components.
Preferably, structural constituent (A) and (B) 85wt% at least of the total coating composition of formation.Be clear that component (C) and (D) only choose wantonly from above.Whether need polymerization starter (C) to depend on the person's character of polymerisable organic person's character and/or component (A).Whether need or must in coating composition, comprise non--structure, functional components (D) depends on the desired performance of this coating composition and/or its Application Areas.
As mentioned above, the hydrolysis and the polycondensation of the different compounds by at least two kinds of general formulas [1] form the inorganic oxide polycondensate.Below two kinds of inhomogeneous compounds [1] are called component A1 and component A2.
Component A1 is main inorganic network-formation thing and preferably defines by general formula [1] (wherein a=b=0), so that component A1 represents with following general formula:
M(OR 3) c??????????????????[2]
In other words, component A1 only contains the hydrolyzable part that is bonded on the inorganic elements M.
These examples for compounds comprise inorganic alkoxide, for example:
I) four-alkoxyl silicone such as tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan and four butoxy silanes;
Ii) four-titan-alkoxide is as four-positive third titanium oxide, four-just different titanium oxide and titanium tetrabutoxides;
Iii) four-aluminum alkoxide is as three Zhong Ding aluminum oxide, three positive fourth aluminum oxide, three AIPs;
Iv) four-zirconium alkoxide is as four-positive third zirconium white, four-different third zirconium white and four fourth zirconium whites; With
V) metal alkoxide such as diformazan cupric oxide, diethyl barium oxide, front three boron oxide, three ethoxyquin galliums, tetrem germanium oxide, four fourth plumbous oxide, five-positive third tantalum oxide and six ethoxyquin tungsten.
Look required, many inhomogeneity component A1 can be included in the coating composition.
Component A2 can be described as second kind of inorganic network-formation thing and it is the compound with general formula [1], and the value of single wherein a and b one or both of is not 0.That is to say that these compounds have the part of at least one non-hydrolysable.These compounds can be described as bifunctional compound.Hydrolyzable has a functionality by polycondensation route sedimentary part in the manufacturing of oxide compound-Ji inorganic network then, and the non-hydrolysable part that is transformed in organic network by polymerization has another functionality.By this difunctionality, can think that whole organic networks have the inorganic-organic hybridization situation.
As mentioned above, the especially preferred compound of general formula [1] expression is that wherein M represents those of Si.This examples for compounds as component A2 comprises:
I) (alkyl) organoalkoxysilane such as Trimethoxy silane, triethoxyl silane, three positive propoxy silane, dimethoxy silane, diethoxy silane, diisopropoxy silane, mono methoxy silane, monosubstituted ethoxy silane, only son's TMOS, methyl dimethoxysilane, the ethyl diethoxy silane, the dimethyl methyl TMOS, di-isopropyl isopropoxy silane, methyltrimethoxy silane, ethyl triethoxysilane, n-propyl three positive propoxy silane, butyl three butoxy silanes, dimethyldimethoxysil,ne, the diethyl diethoxy silane, di-isopropyl diisopropoxy silane, dibutyl dibutoxy silane, the trimethylammonium methoxy silane, triethyl-ethoxy-silicane alkane, three n-propyl positive propoxy silane, the tributyl butoxy silane, phenyltrimethoxysila,e, phenylbenzene diethoxy silane and triphenyl methoxy silane;
(alkyl) organoalkoxysilane such as the 3-propyl isocyanate base Trimethoxy silane that ii) have isocyanato, 3-propyl isocyanate ethyl triethoxy silicane alkane, 3-propyl isocyanate ylmethyl dimethoxy silane, 3-propyl isocyanate base ethyl diethoxy silane, 3-propyl isocyanate base dimethyl isopropoxy silane, 3-propyl isocyanate base diethyl Ethoxysilane, 2-ethyl isocyanate base diethyl butoxy silane, two (3-propyl isocyanate base) diethoxy silane, two (3-propyl isocyanate base) methyl ethoxy silane and oxyethyl group three isocyanato silane;
Iii) have (alkyl) organoalkoxysilane of epoxy group(ing) such as 3-glycidoxy-propyltrimethoxy silane, 3-epoxypropoxy triethoxyl silane, 3-epoxypropoxy methyl dimethoxysilane, 3-epoxypropoxy methyldiethoxysilane, 3-epoxypropoxy dimethylethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane and 3,4-epoxy butyl trimethoxy silane;
(alkyl) organoalkoxysilane such as carboxymethyl triethoxyl silane and the carboxymethyl ethyl diethoxy silane that iv) have carboxyl;
The organoalkoxysilane such as 3-(the triethoxysilyl)-2-methyl-propyl succinyl oxide that v) have anhydride group;
The organoalkoxysilane such as 2-(the 4-chlorine sulfonyl-phenyl) ethyl triethoxysilane that vi) have acyl halide group;
Vii) have amino (alkyl) organoalkoxysilane such as N-2-(aminoethyl)-3-aminopropyl triethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane and N-phenyl-3-aminopropyl trimethoxysilane;
(alkyl) organoalkoxysilane such as 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltriethoxysilane and the 3-mercapto propyl group methyl dimethoxysilane that viii) have sulfydryl;
Ix) have (alkyl) organoalkoxysilane such as vinyltrimethoxy silane, vinyltriethoxysilane and the vinyl methyldiethoxysilane of vinyl;
X) have acrylate or methacrylate based (alkyl) organoalkoxysilane such as 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxyl silane, 3-methacryloxypropyl methyl dimethoxy base silane and 3-acryloxy propyl-triethoxysilicane;
Xi) has (alkyl) organoalkoxysilane such as triethoxy fluoro silane, 3-chloropropyltrimethoxy silane, 3-bromo alkylalkoxy silane and the 2-chloro ethyl-methyl dimethoxy silane of halogen atom;
Xii) has (alkyl) organoalkoxysilane of haloalkyl part as (3,3, the 3-trifluoro propyl) Trimethoxy silane and 1H, 1H, 2H, 2H-perfluor decyl triethoxyl silane; With
Xiii) use (alkyl) organoalkoxysilane such as sec.-propyl three isopropoxy silane and the triisopropyl isopropoxy silane of alkoxyl group as functional group.
As the preferred compound of component A2 is to have those of at least one huge relatively non-hydrolysable part.As for huge relatively, we are meant provides than the bigger sterically hindered part of single vinyl.As the especially preferred ingredient of component A2 is (alkyl) organoalkoxysilane with the epoxy group(ing) of being selected from, amino and methacryloyl, subclass promptly mentioned above iii), viii) and x) in those.Especially preferred compound as component A2 is 3-glycidoxy-propyltrimethoxy silane (GPTS), N-phenyl-3-aminopropyl trimethoxysilane (PAPMS) and 3-methacryloxypropyl trimethoxy silane (MPTMA).
Look required, many inhomogeneity component A2 can be included in the coating composition.
The most preferably combination of component A1 and A2 comprises four alkoxide silicon, particularly tetramethoxy-silicane or tetraethoxysilane and any one GPTS, PAPMS and MPTMA.
Can come hydrolysis component A1 and A2 by the water that adds entry or generate on the spot.Usually the preferred hydrolysis of using mineral acid to cause component A1 and A2.Also preferably cause the hydrolysis of component A1 and A2 independently of one another, then gained blended colloidal sol is mixed with polymerisable organism.
Select the person's character of polymerisable organism (B) according to desired performance in final coating.Typically, select polymerisable organism intensity and wear resistance to be provided and to look required transparency.Yet, importantly, so select polymerisable organism, so that (comprise and remove any volatile constituent in the coating drying, solidified coating subsequently) time, from coating composition, do not lose organic materials basically, because this can reduce inorganic and consistency organic phase, thereby make that finally composition is difficult to maybe can not be coated with, and/or cause poor performance as be full of cracks.
The organic example of suitable polymerizable comprises carbonic ether, ester such as terephthalate, carbamate, the vinylformic acid dipentaerythritol ester, with the monomer or the oligopolymer that contain at least one reactive acrylate or methacrylic ester (i.e. (methyl) acrylate) part, as (methyl) propenoic methyl carbamate, epoxy (methyl) acrylate, polyester (methyl) acrylate, polyethers (methyl) acrylate, amino modified polyethers (methyl) acrylate, (methyl) vinylformic acid (methyl) acrylate, (methyl) acrylate of carbamate precursor and composition thereof.(methyl) acrylate of preferred especially carbamate precursor such as isocyanic ester, vulcabond and polyvalent alcohol, and (methyl) propenoic methyl carbamate and are compared preferred aliphatic series (methyl) acrylate with aromatics (methyl) acrylate.Also can use organometallic monomer, but they will not contain hydrolyzable chemical bond in the case.
Preferably in low relatively temperature as being lower than under 150 ℃, after adding suitable initiator, or by for example UV or IR photoirradiation, or with X-ray or beam bombardment, the polymerisable organism of polymerization is so that can be used as the coating of the thermoplastic material or the thermosetting material of low softening point.Also preferably produce the polymerizable organism of polymkeric substance, and described polymkeric substance has good organic solvent resistance.Therefore, under the carbonic ether situation, preferred aliphatic series carbonic ether, rather than aromatic carbonate.
Suitable polymerization starter (C) be can heat and/or photochemistry cause polymerisable organic polymer and crosslinked those.Polymerization starter also can serve as the non-hydrolysable part of component A2.
The example of suitable polymerization starter be the initiator that is purchased such as Irgacure  184 (1-hydroxycyclohexylphenylketone), Irgacure  500 (the 50%1-hydroxycyclohexylphenylketone: 50% benzophenone) and other Irgacure  type light trigger as available from the Irgacure  819 (two acyl group phosphine oxide) of Ciba Specialty ChemicalsCompany with also available from the Darocur  1173 of Ciba SpecialtyChemicals Company.Other compound that can be used as light trigger comprises benzophenone, 2-clopenthixal ketone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, bitter almond oil camphor, 4,4 '-dimethoxy bitter almond oil camphor, ethoxybenzoin, bitter almond oil camphor, benzyl dimethyl ketal, 1,1,1-tribromo-acetyl benzene and diethoxy phenyl methyl ketone.
Suitable thermal initiator comprises organo-peroxide such as diacyl peroxide, two carbonic ethers, alkyl are crossed ester, dialkyl peroxide, crossed ketal, ketone peroxide and hydrogen peroxide alkyl excessively.The specific examples of this thermal initiator is dibenzoyl peroxide and Diisopropyl azodicarboxylate.
The person's character that depends on polymerisable organism and component A2 can be used the mixture of different polymerization starters requiredly, or can select the person's character of polymerizable organism and component A2 requiredly, uses single, common polymerization starter so that make.
As mentioned above, coating composition can comprise that also sense transfers additive, and described functional additive chemically is not incorporated into by component (A) with (B) in inorganic and organic network of generation.Suitable additive comprises that tensio-active agent is as the commercially available Fluorad  FC430 from 3M; UV absorption agent and photostabilizer such as Tinuvin  product from Ciba Specialty Chemicals Company; Dyestuff; Viscosity modifier; Corrosion inhibitor; Sterilant and algicide.
Use for some, for example will be exposed under the situation of sunlight or other UV light in coating, special preferred coatings composition comprises the UV absorption agent, rather than the light trigger of any UV-absorption of mixing for initiated polymerization.In the case, the UV that preferred UV absorption agent has absorbs finger printing and is different from the finger printing that is included in any UV light trigger in the composition, makes it not damage the polymerization of coating composition.The UV absorption agent can be included in the final coating composition, but preferably it is included in the inorganic sol or before forming blended colloidal sol with one of hydrolyzable inorganic monomer precursor together.The UV absorption agent that is included in the typical amount in the coating composition in the 1-15wt% scope, preferred 5-15wt%, more preferably 10-15wt%.
Develop into the mutually inorganic of final coating and by component (B) and (C) develop into organic phase by component A1 and A2.Think between inorganic phase and organic phase, can form certain chemical bond, but this is not main concerning the success of coating.Can be by component (A), (B) and relative proportion (C), calculate the inorganic content in the final coating, when thinking that these components have experienced crosslinked completely or when solidifying on paper." when solidified " component ratio in the coating composition, this is reference that the application plans.In fact can not realize the whole crosslinked of these components or curing although think.
Composition in can estimating on a large scale can be used for producing the coating that comprises the inorganic and organic phase of different ratios.For example, coating composition can comprise the inorganic monomer precursor and the polymerisable organism of consumption like this, so that final cured coating comprises that the organic phase of 1%-99wt% and 99%-1wt%'s is mutually inorganic, based on the gross weight of inorganic and organic phase with think that all components all solidifies in final coating.Yet as general rule, the coating that provides better preserved to exempt from machinery and/or chemical destruction is wherein ceramic-like or maximized those coatings of inorganic performance.For this reason, preferably should prepare coating composition, to be implemented in 50-99wt% in the final coating, preferred 75-99wt%, mutually inorganic with 90-99wt% most preferably is based on inorganic and gross weight organic phase, think that at this all components all solidifies, even finally in fact this can not realize.As mentioned above, inorganic and organic phase preferably constitutes coating composition and and then the final coating of 85wt% at least together.
It is to keep bonding at the manufacturing processed floating coat that the minimum of producing practical supercoat on concrete base material requires.If coating has and the remarkable unmatched performance of base material, then produce residual stress.If these residual stresses can not be removed or greater than the yield strength of coating, then will produce be full of cracks and coating is failed.Thermal expansivity (CTE) is the salient features of coating, and in order not produce significant tensile stress in coating, it need be complementary with base material.Deposition with coating bigger than base material CTE produces the coating that pressurized is placed, and therefore can withstand manufacturing operation.
Production requirement coating CTE with best anti-scratch coating equals the composition of base material CTE at least, and this coating has maximum ceramic similarity simultaneously.Usually, the ceramic person's character of coating increases and CTE reduces, because the total amount of inorganic phase and the relative quantity of comparing component A1 with component A2 all increase.The relative quantity of component A1 and A2 can be described as mol ratio R (A), wherein R ( A ) = mA 1 ( mA 1 + mA 2 )
Wherein mA1 is that total mole number and the mA2 of component A1 are the total mole numbers of component A2.Under inhomogeneity component A1 and/or A2 were included in situation in the coating composition, mA1 and mA2 represented each the bonded total mole number in those components.
Usually, found that useful coating composition has at 0.40-0.99,0.4-0.95 for example, 0.4-0.9, the mol ratio R (A) in 0.4-0.85 or the 0.4-0.8 scope.But it is also suitable to be lower than 0.4 ratio in some cases.Yet, preferred proportion R (A) in 0.45-0.99 or 0.5-0.99 scope, 0.5-0.95 for example.More preferably ratio R (A) in the 0.5-0.9 scope and most preferably R (A) in 0.5-0.85 or 0.5-0.8 scope.Yet best R (A) value depends on coating sedimentary base material and particularly its CTE and/or the desired final performance of coating usually thereon.
A kind of mode that characterizes different coating compositions here is that they are suitable for being applied on the base material of different CTE.Think according to the present invention, can prepare coating composition and be used to protect large-scale various base material that described base material for example is selected from different plastics, metal, stupalith and natural materials such as leather and timber and its synthetic substitute.Also can successfully coating composition of the present invention be coated in order to protect or decorative purpose has been used on the another kind of material substrates coated.For example, base material can be the base material that painted or painted.
Usually, metal tends to have low relatively CTE value, and wherein aluminium is one of metal that has the highest CTEs, is about 24 * 10 -6/ ℃.Plastic basis material can have large-scale different CTE, for example from about 10 * 10 -6/ ℃ to surpassing 100 * 10 -6/ ℃.
Following and consistent with the application's rest part, provide the inorganic phase content of quoting with the ratio form of the structural constituent in the coating composition, crosslinked fully when thinking that described component has experienced, when promptly being present in the final cured coating.
Usually, for CTE maximum 25 * 10 -6/ ℃ base material, can use coating with any above-mentioned R (A) value.Yet as for the inorganic phase content of height, for example the coating of 95wt% structural constituent at least can be used 0.98 R (A) value at the most requiredly.In addition, in order to be coated to higher slightly CTE, for example at most about 40 * 10 -6/ ℃ base material on, can be required ground even further reduce this upper limit of R (A) scope, for best coating performance.
For CTE at least 40 * 10 -6/ ℃ base material, usually can use R (A) value of above-described wide region at this.Yet, when higher inorganic phase content, can cause be full of cracks in R (A) value of the higher-end of this scope.Therefore, account for the coating of the 95wt% at least of structural constituent, preferably the R in the 0.5-0.95 scope (A) value for inorganic phase content.
For CTE at least 60 * 10 -6/ ℃ base material, the preferred coatings composition that inorganic phase content accounts for the 90wt% at least of structural constituent has R (A) value in the 0.5-0.9 scope.
For CTE at least 80 * 10 -6/ ℃ base material, the preferred coatings composition that inorganic phase content accounts for the 90wt% at least of structural constituent has R (A) value in the 0.5-0.85 scope.
For CTE at least 100 * 10 -6/ ℃ base material, the preferred coatings composition that inorganic phase content accounts for the 90wt% at least of structural constituent has R (A) value in the 0.5-0.8 scope.
Be to be understood that above-mentioned R (A) scope may be used in the following coating composition, and described coating composition have those low inorganic phase contents of specifically mentioning than above.
Below provide specific examples based on the coating composition of following component:
I) component A1 is a tetraethoxysilane
Ii) component A2 is the 3-methacryloxypropyl trimethoxy silane
Iii) polymerisable organism is the aliphatic amino acrylates monomer of Akcros Chemicals with product code 260GP25 supply
Iv) light trigger is the Irgacure500 of CIBA Specialty Chemicals supply.
Being deposited on thermal expansivity is 12 * 10 -6/ ℃ metal base on preferred limit coating composition value be:
A) the inorganic phase content of 99wt%, R (A)＜0.98
B) the inorganic phase content of 95wt%, R (A)＜0.99
Being deposited on thermal expansivity is 68 * 10 -6/ ℃ plastic basis material, promptly the preferred limit coating composition value on the polycarbonate is:
A) the inorganic phase content of 99wt%, R (A)＜0.81
B) the inorganic phase content of 95wt%, R (A)＜0.83
C) the inorganic phase content of 90wt%, R (A)＜0.85
D) the inorganic phase content of 75wt%, R (A)＜0.96
(wherein paint has 100 * 10 to be deposited on the base material that painted -6/ ℃ thermal expansivity) on preferred limit coating composition value be:
A) the inorganic phase content of 99wt%, R (A)＜0.65
B) the inorganic phase content of 95wt%, R (A)＜0.67
C) the inorganic phase content of 90wt%, R (A)＜0.70
D) the inorganic phase content of 75wt%, R (A)＜0.75
The another way that characterizes different coating compositions is according to its final performance.Usually, the coating composition with higher R (A) value causes best hardness and wear resistance, and for example R (A) value is in 0.7-0.95 or 0.75-0.90 scope.Astoundingly, also find to have R (A) value at 0.4-0.8,0.5-0.8 for example, preferably 0.5-0.75 and more preferably the coating composition of 0.5-0.7 have improved stability to hydrolysis.In other words, this coating can tolerate in water dipping a couple of days or be exposed to moisture and heat under and do not chap.Usually, for the application that requires stability to hydrolysis, R (A) value is low more, and then coating is good more.
Other useful coating composition has 0.4 to less than the R in 0.624 scope (A) value, for example 0.4 arrive less than 0.62 or the 0.4-0.61 scope in, for example about 0.5, or in 0.63-0.99 or 0.63-0.95 scope.
In use, coating composition is coated on the surface of base material, wherein said coating composition comprises and polymerisable organism blended inorganic sol.Polymerisable organic polymerization can be before being coated on the base material or more typically be coated on the base material after cause, but in either case, cause this polymerization before the polymerization of the inorganic monomer that importantly exists is finished in inorganic sol.The employed method of solidified coating depends on the person's character of the component A2 in polymerisable organism and/or the inorganic sol.Can or required the combination of using different curing technologies.For example, can use a kind of technology to cause and solidify, use another kind of technology to finish curing then.For example, when component A2 thermal curable and polymerisable organism UV-curable, can cause by UV irradiation and solidify,, also can carry out the curing of inorganic sol wherein by its IR component.Then, by another technology, for example by thermal treatment or finish the curing of inorganic sol basically with the IR photoirradiation.
Now further set forth the present invention by following embodiment.
Embodiment
The hard coat that embodiment 1-transparent plastics is used
Be prepared as follows colloidal sol:
The A part
Be placed on 25.0g tetraethoxysilane (TEOS) in the beaker and to the uniform mixture that wherein adds 22.1g methyl alcohol and 4.32g distilled water and 0.3g hydrochloric acid.
The B part
Be placed on 6.0g methacrylic acid 3-(trimethoxysilyl) propyl diester (MPTMA) in the beaker and to the uniform mixture that wherein adds 4.4g methyl alcohol and 0.65g distilled water and 0.2g hydrochloric acid.
The R of said composition (A) value is 0.83.
In the beaker of sealing, stirred A and B part about 30 minutes independently then, afterwards they were mixed about 30 minutes in the beaker of sealing once more.
About 24 hours of 50 ℃ of following ageing gained colloidal sols, make inorganic network form then.In this colloidal sol, add 5.0g distilled water then.In airtight container, after the stir about 1 hour, mix this colloidal sol and 0.60g aliphatic amino acrylates (AkcrosChemicals sells with product code 260GP25) and 0.1g 50%1-hydroxycyclohexylphenylketone then: the mixture of 50% benzophenone as light trigger.Thoroughly mixed gained solution at least 1 hour, in airtight container, store then and in the storage cabinet of dark, preserve.
When needs, this solution is deposited on polycarbonate, vinylformic acid and the polyester base material with coating form, volatile matter is at room temperature flashed away and make coating carry out UV irradiation from the UV lamp, solidify organic constituent.Coating has the organic phase content (being that inorganic phase content is 95wt%) of 5wt%.
Embodiment 2-has the hard coat of stability to hydrolysis
Be prepared as follows colloidal sol:
The A part
Be placed on 130.0gTEOS in the beaker and to the uniform mixture that wherein adds 115g methyl alcohol and 22.5g distilled water and 0.3g hydrochloric acid.
The B part
Be placed on 51.0gMPTMA in the beaker and to the uniform mixture that wherein adds 38g methyl alcohol and 5.5g distilled water and 0.2g hydrochloric acid.
The R of said composition (A) value is 0.75.
In the beaker of sealing, stirred A and B part about 30 minutes independently then, afterwards they were mixed about 30 minutes in the beaker of sealing once more.
About 24 hours of 50 ℃ of following ageing gained colloidal sols, make inorganic network form then.In this colloidal sol, add 28g distilled water then.In airtight container, after the stir about 1 hour, mix this colloidal sol and 3.9g aliphatic amino acrylates (Akcros Chemicals sells with product code 260GP25) and 0.2g 50%1-hydroxycyclohexylphenylketone then: the mixture of 50% benzophenone as light trigger.Thoroughly mixed gained solution at least 1 hour, in airtight container, store then and in the storage cabinet of dark, preserve.
When needs, this solution is deposited on polycarbonate, vinylformic acid and the polyester base material with coating form, volatile matter is at room temperature flashed away and make coating carry out UV irradiation from the UV lamp, solidify organic constituent.Coating has the organic phase content (being that inorganic phase content is 95wt%) of 5wt%.
When 65 ℃ down dipping reaches 5 days, the gained coating demonstrates the stability of increase, can freedom from cracking and crazing and be able to take under 40 ℃/100%RH exposure greater than 11 days.
Embodiment 3-has the hard coat of stability to hydrolysis
Be prepared as follows colloidal sol:
The A part
Be placed on 80.0gTEOS in the beaker and to the uniform mixture that wherein adds second 71g methyl alcohol and 14g distilled water and 0.3g hydrochloric acid.
The B part
Be placed on 50.0gMPTMA in the beaker and to the uniform mixture that wherein adds 37g methyl alcohol and 5.4g distilled water and 0.2g hydrochloric acid.
The R of said composition (A) value is 0.66.
In the beaker of sealing, stirred A and B part about 30 minutes independently then, afterwards they were mixed about 30 minutes in the beaker of sealing once more.
About 24 hours of 50 ℃ of following ageing gained colloidal sols, make inorganic network form then.In this colloidal sol, add 19.3g distilled water then.In airtight container, after the stir about 1 hour, mix this colloidal sol and 3.1g aliphatic amino acrylates (AkcrosChemicals sells with product code 260GP25) and 0.2g 50%1-hydroxycyclohexylphenylketone then: the mixture of 50% benzophenone as light trigger.Thoroughly mixed gained solution at least 1 hour, in airtight container, store then and in the storage cabinet of dark, preserve.
When needs, this solution is deposited on polycarbonate, vinylformic acid and the polyester base material with coating form, sample by will coating is placed in 80 ℃ the baking oven and evaporated volatile matter through 5 minutes, makes coating carry out UV irradiation from the UV lamp then, solidifies organic constituent.Coating has the organic phase content (being that inorganic phase content is 95wt%) of 5wt%.
When 65 ℃ dipping reaches 10 days down, the gained coating demonstrates the stability of increase, can freedom from cracking and crazing.
The hard coat of embodiment 4-aluminium
Be prepared as follows colloidal sol:
The A part
Be placed on 57.5gTEOS in the beaker and to the uniform mixture that wherein adds 50.8g methyl alcohol and 9.94g distilled water and 0.3g hydrochloric acid.
The B part
Be placed on 11.3gMPTMA in the beaker and to the uniform mixture that wherein adds 8.4g methyl alcohol and 1.23g distilled water and 0.2g hydrochloric acid.
The R of said composition (A) value is 0.86.
In the beaker of sealing, stirred A and B part about 30 minutes independently then, afterwards they were mixed about 30 minutes in the beaker of sealing once more.
About 24 hours of 50 ℃ of following ageing gained colloidal sols, make inorganic network form then.In 120g colloidal sol, add 9.6g distilled water then.In airtight container, after the stir about 1 hour, mix this colloidal sol and 1.1g aliphatic amino acrylates (AkcrosChemicals sells with product code 260GP25) and 0.1g 50%1-hydroxycyclohexylphenylketone then: the mixture of 50% benzophenone as light trigger.Thoroughly mixed gained solution at least 1 hour, in airtight container, store then and in the storage cabinet of dark, preserve.
When needs, this solution is deposited on the aluminum base material with coating form, volatile matter is at room temperature flashed away and make coating carry out UV irradiation from the UV lamp, solidify organic constituent.Coating has the organic phase content (being that inorganic phase content is 95wt%) of 5wt%.
The hard coat of embodiment 5-Stainless Steel Alloy
Be prepared as follows colloidal sol:
The A part
Be placed on 60.0gTEOS in the beaker and to the uniform mixture that wherein adds 53.0g methyl alcohol and 10.37g distilled water and 0.3g nitric acid.
The B part
Be placed on 4.5gMPTMA in the beaker and to the uniform mixture that wherein adds 3.3g methyl alcohol and 0.49g distilled water and 0.2g nitric acid.
The R of said composition (A) value is 0.94.
In the beaker of sealing, stirred component A and B part about 30 minutes independently then, afterwards they were mixed about 30 minutes in the beaker of sealing once more.
About 24 hours of 50 ℃ of following ageing gained colloidal sols, make inorganic network form then.In 120g colloidal sol, add 9.9g distilled water then.In airtight container, after the stir about 1 hour, mix this colloidal sol and 1.0g aliphatic amino acrylates (AkcrosChemicals sells with product code 260GP25) and 0.1g 50%1-hydroxycyclohexylphenylketone then: the mixture of 50% benzophenone as light trigger.Thoroughly mixed gained solution at least 1 hour, in airtight container, store then and in the storage cabinet of dark, preserve.
When needs, this solution is deposited on aluminum (still Stainless Steel Alloy) base material with coating form, volatile matter is at room temperature flashed away and make coating carry out UV irradiation from the UV lamp, solidify organic constituent.Coating has the organic phase content (being that inorganic phase content is 95wt%) of 5wt%.
Embodiment 6-contains the hard coat of aluminium
Be prepared as follows colloidal sol:
The A part
Be placed on 20.0gTEOS in the beaker and to the uniform mixture that wherein adds 19.4g methyl alcohol, 1.73g distilled water and 0.2g hydrochloric acid.After mixing 1 hour, add 2.35g three Zhong Ding aluminum oxide (ASB).Mix this solution then at least 12 hours, and then further added 1.73g distilled water.Stirred solution 1 hour further adds 0.34g distilled water then.
The B part
Be placed on 10.0gMPTMA in the beaker and to the uniform mixture that wherein adds 7.4g methyl alcohol, 1.09g distilled water and 0.2g hydrochloric acid.Stir about 1 hour in the beaker of sealing then.
The R of said composition (A) value is 0.72.
The ratio of TEOS: ASB is 10.1.
Mix A and B part then, and in the beaker of sealing, stirred 30 minutes.Ageing gained colloidal sol at least 24 hours in airtight container makes inorganic network form then.Slowly in this solution, add 4.88g distilled water then.After in airtight container, mixing at least 1 hour, use the aliphatic amino acrylates of the UV-curable that 0.73gAcross Chemicals sells with product code 260GP25 and 0.1g 50%1-hydroxycyclohexylphenylketone: the mixture of 50% benzophenone as light trigger.In airtight container, store gained solution and in the storage cabinet of dark, preserve.
When needs, this solution is deposited on polycarbonate, vinylformic acid and the aluminum base material with coating form, volatile matter is at room temperature flashed away and make coating carry out UV irradiation from the UV lamp, solidify organic constituent.Coating has the organic phase content (being that inorganic phase content is 95wt%) of 5wt%.
The hard coat of embodiment 7-transparent plastics
Be prepared as follows colloidal sol:
The A part
Be placed on 85.0gTEOS in the beaker and to the uniform mixture that wherein adds 75.1g methyl alcohol and 14.69g distilled water and 0.3g hydrochloric acid.
The B part
Be placed on 100.0gMPTMA in the beaker and to the uniform mixture that wherein adds 74.1g methyl alcohol and 10.87g distilled water and 0.2g hydrochloric acid.
The R of said composition (A) value is 0.50.
In the beaker of sealing, stirred component A and B part about 30 minutes independently then, afterwards they were mixed about 30 minutes in the beaker of sealing once more.
About 24 hours of 50 ℃ of following ageing gained colloidal sols, make inorganic network form then.In colloidal sol, add 25.6g distilled water then.In airtight container, after the stir about 1 hour, mix this colloidal sol and 5.1g aliphatic amino acrylates (Akcros Chemicals sells with product code 260GP25) and 0.25g 50%1-hydroxycyclohexylphenylketone then: the mixture of 50% benzophenone as light trigger.Thoroughly mixed gained solution at least 1 hour, in airtight container, store then and in the storage cabinet of dark, preserve.
When needs, this solution is deposited on polycarbonate, vinylformic acid and the polyester base material with coating form, volatile matter is at room temperature flashed away and make coating carry out UV irradiation from the UV lamp, solidify organic constituent.Coating has the organic phase content (being that inorganic phase content is 95wt%) of 5wt%.
At 65 ℃ of following coatings tolerances dipping＞240 hours and under 40 ℃/100%RH, expose＞32 days in water, and not be full of cracks.
The hard coat of embodiment 8-transparent plastics
Repeat embodiment 7, different is after the UV hardening with radiation, with sample 120 ℃ of following thermal treatments 65 hours.
The hard coat of embodiment 9-transparent plastics
Identical coating composition among preparation and the embodiment 7, different is, and employed polymerization starter is 0.25g benzoyl peroxide (with trade mark Luperox A75FP  sale).Thoroughly mixed gained solution at least 1 hour, in airtight container, store then and in the storage cabinet of dark, preserve.
When needs, this solution is deposited on polycarbonate, vinylformic acid and the polyester base material with coating form, volatile matter is at room temperature flashed away, then coating was heated to 130 ℃ through 2 hours, solidify organic constituent.
Embodiment 10-has the hard coat of stability to hydrolysis and UV protection
Be prepared as follows colloidal sol:
The A part
Be placed on 21.0gTEOS and 1.27g Tinuvin  384 (uv-absorbing agent that Ciba SpecialityChemicals sells) in the beaker and to the uniform mixture that wherein adds 18.5g methyl alcohol and 3.63g distilled water and 0.3g hydrochloric acid.
B part is placed on 25.0gMPTMA in the beaker and to the uniform mixture that wherein adds 18.5g methyl alcohol, 2.72g distilled water and 0.2g hydrochloric acid.
The R of said composition (A) value is 0.50.
In the beaker of sealing, stirred component A and B part about 30 minutes independently then, afterwards they were mixed about 30 minutes in the beaker of sealing once more.
About 24 hours of 50 ℃ of following ageing gained colloidal sols, make inorganic network form then.In colloidal sol, add 6.35g distilled water then.In airtight container after the stir about 1 hour, mix this colloidal sol and 1.27g aliphatic amino acrylates (Akcros Chemicals sells with product code 260GP25) and 0.05g then as the benzoyl peroxide of light trigger (with trade mark Luperox A75FP sale).Thoroughly mixed gained solution at least 1 hour, in airtight container, store this solution then and in the storage cabinet of dark, preserve.
When needs, this solution is deposited on the polycarbonate substrate with coating form, volatile matter is at room temperature flashed away, then coating was heated to 130 ℃ through 2 hours, solidify organic constituent.The UV of base material protection below the coating that is provided strengthens.Coating has the organic phase content (being that inorganic phase content is 95wt%) of 5wt%.
When being immersed under 65 ℃ when reaching 5 days in the water, the gained coating demonstrates the stability of increase, can freedom from cracking and crazing.
The hard coat of embodiment 11-transparent plastics
Repeat embodiment 1, different is to use 0.60g polyester acrylate (AkcrosChemicals sells with product code Actilane  505) to substitute the aliphatic amino acrylates.
When needs, this solution is deposited on polycarbonate, vinylformic acid and the polyester base material with coating form, volatile matter is at room temperature flashed away and make coating carry out UV irradiation from the UV lamp, solidify organic constituent.The UV of base material protection below the coating that is provided strengthens.Coating has the organic phase content (being that inorganic phase content is 95wt%) of 5wt%.
Prove some above abrasion property by following table institute results reported, wherein Δ H (%) the 500th becomes to use the ASTM D1003-97 in different apertures according to modification, use is loaded into the CS10F impeller of 500g, after 500 Taibos (Taber) circulation, and the increase of optical haze.In this test, has 7.7 numerical value from the siliceous hard coat AS4000 of GE Bayer.
Embodiment ?1 ?2 ?3 ?7 ?8
ΔH(％)500 ?1.8 ?7.5 ?12.5 ?12.5 ?2.4

Claims (24)

1. coating composition, it comprises mixed uniformly mutually inorganic with organic phase,
Inorganic is that hydrolysis by first kind and second kind hydrolyzable inorganic monomer precursor obtains mutually, wherein first kind of hydrolyzable inorganic monomer precursor (A1) is different from second kind of hydrolyzable monomer precursor (A2), have at least two hydrolyzable parts with first kind of hydrolyzable inorganic monomer precursor, has the part of at least one non-hydrolysable with second kind of hydrolyzable inorganic monomer precursor
Organic phase comprises polymerisable organism,
The mol ratio R (A) that it is characterized in that first kind of hydrolyzable inorganic monomer precursor (A1) and total hydrolyzable inorganic monomer precursor (A1 and A2) is in the 0.4-0.99 scope.
2. the coating composition of claim 1 wherein comprises the inorganic phase of 50-99wt%, when solidified based on inorganic and gross weight organic phase.
3. claim 1 or 2 coating composition wherein comprise 90wt% at least when solidified, and mutually inorganic with preferred 95wt% at least is based on inorganic and gross weight organic phase.
4. the coating composition of aforementioned any one claim, wherein R (A) is in the 0.5-0.99 scope.
5. the coating composition of aforementioned any one claim, wherein R (A) is in the 0.5-0.95 scope.
6. the coating composition of aforementioned any one claim, wherein R (A) is in the 0.5-0.9 scope.
7. the coating composition of aforementioned any one claim, wherein R (A) is in the 0.5-0.85 scope.
8. the coating composition of aforementioned any one claim, wherein R (A) is in the 0.5-0.8 scope.
9. the coating composition of aforementioned any one claim, wherein first kind and second kind of hydrolyzable monomer precursor comprise the inorganic alkoxide of following general formula: MR 1 aR 2 b(OR 3) c,
Wherein M is selected from Si, Ti, Zr, Fe, Cu, Sn, B, Al, Ge, Ce, the inorganic elements among Ta and the W; R 1And R 2Be independently selected from alkyl with 1-10 carbon atom; R 3For hydrogen atom or have the alkyl of 1-10 carbon atom and a and b be independently selected from 0 and integer and C be the integer that equals (x-a-b), wherein x be the valence state of element M and in first kind of hydrolyzable inorganic monomer precursor a=b=0.
10. the coating composition of claim 9, wherein first kind of hydrolyzable inorganic monomer precursor is selected from tetraalkoxysilane and second kind of hydrolyzable inorganic monomer precursor is selected from 3-methacryloxypropyl trimethoxy silane (MPTMA), 3-glycidoxy-propyltrimethoxy silane (GPTS) and N-phenyl-3-aminopropyl trimethoxysilane (PAPMS).
11. the coating composition of claim 10, wherein first kind of hydrolyzable inorganic monomer precursor comprises that tetraethoxysilane and second kind of hydrolyzable inorganic monomer precursor comprise MPTMA.
12. claim 1 or 2 or be subordinated to any one coating composition among the claim 4-11 of claim 1 or 2, prerequisite is that this coating composition is not to comprise that tetraethoxysilane is as first kind of hydrolyzable inorganic monomer precursor, 3-methacryloxypropyl trimethoxy silane (MPTMA) is as second kind of hydrolyzable inorganic monomer precursor, the monomeric coating composition of aliphatic amino acrylates with UV-curable, wherein when coating composition solidifies, the total amount of inorganic phase accounts for the 25wt% of total coating composition, 50wt% or 75wt% and its have 0.624,0.625 or 0.62 R (A).
13. any one coating composition of claim 1-11, prerequisite is that ratio R (A) is not 0.624,0.625 or 0.62.
14. any one coating composition of claim 1-11, prerequisite is that said composition comprises that tetraethoxysilane is as first kind of hydrolyzable inorganic monomer precursor, 3-methacryloxypropyl trimethoxy silane (MPTMA) is as second kind of hydrolyzable inorganic monomer precursor, with the aliphatic amino acrylates monomer of UV-curable as polymerisable organism, ratio R (A) is at least 0.63, and preferably at least 0.65.
15. any one coating composition of claim 1-11, wherein ratio R (A) is at least 0.63, preferably at least 0.65.
16. claim 1 or be subordinated to any one the coating composition of claim 9-11 of claim 1, wherein R (A) is 0.4 in less than 0.624 scope, and preferred 0.4 to less than 0.62, more preferably 0.4-0.61.
17. claim 1 or be subordinated to any one coating composition in the claim 9 and 11 of claim 1, ratio R (A) or i) in 0.5 to 0.74 scope wherein, or ii) in the 0.91-0.99 scope.
18. the coating composition of claim 3, wherein mol ratio R (A) is in the 0.4-0.95 scope, preferred 0.4-0.9, and more preferably 0.4-0.8, and most preferably at least 0.5.
19. the coating composition of aforementioned any one claim, wherein hydrolyzable inorganic precursor and polymerisable organism constitute the 85wt% at least of coating composition gross weight together.
20. the coating composition of aforementioned any one claim wherein further comprises the UV absorption agent outside the polymerization starter.
21. the coating composition of aforementioned any one claim, wherein hydrolysis inorganic monomer precursor A1 and A2 independently of one another, form first kind of colloidal sol and second kind of colloidal sol, then it is mixed together the formation mixed sols and then mixed sols is mixed with polymerisable organism.
22. method that supercoat is provided on base material; this base material is preferably selected from plastics, metal, stupalith, natural materials such as leather and timber; with and synthetic substitute; the base material of base material with precoating as painting and painting; this method comprises and is coated to the defined coating composition of aforementioned any one claim on the base material and solidifies described composition.
23. the method for claim 22, wherein base material is selected from polycarbonate and polyacrylic acid base material.
24. coated substrate by any one defined method acquisition of claim 21-23.
CN01816063.8A 2000-09-22 2001-09-21 Coating compositions Pending CN1462300A (en)

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JP2005036184A (en) * 2003-06-24 2005-02-10 Mitsubishi Chemicals Corp Radiation hardenable resin composition and its hardened product
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CN103374296B (en) * 2012-04-24 2016-02-24 东京应化工业株式会社 Film formation composition and manufacture method, diffusing agent composition and manufacture method thereof
CN103525290A (en) * 2013-09-30 2014-01-22 安徽蓝柯复合材料有限公司 Wear-resistant ultraviolet (UV) photo-curing coating and preparation method thereof

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