CN102532432A - Fluorine-containing polymerizable resin, active energy ray-curable composition using the same and cured product thereof - Google Patents

Fluorine-containing polymerizable resin, active energy ray-curable composition using the same and cured product thereof Download PDF

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CN102532432A
CN102532432A CN2011103032532A CN201110303253A CN102532432A CN 102532432 A CN102532432 A CN 102532432A CN 2011103032532 A CN2011103032532 A CN 2011103032532A CN 201110303253 A CN201110303253 A CN 201110303253A CN 102532432 A CN102532432 A CN 102532432A
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methyl
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resin
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CN102532432B (en
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野口润
铃木秀也
森永邦裕
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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    • C08G2150/90—Compositions for anticorrosive coatings
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    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
    • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers

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Abstract

A fluorine-containing polymerizable resin is provided to offer excellent staining resistance, scratch resistance, and liquid-proof properties to the surface of a cured film, and to be used as a fluorine-containing polymerizable surfactant. A fluorine-containing polymerizable resin, which is a polymer obtained by polymerization of polymerizable unsaturated monomers, comprises a poly(perfluoroalkylene ether) chain, an admantyl group, and a polymerizable unsaturated group in the structure. The fluorine-containing polymerizable resin is obtained by the reaction of a compound and a polymer. The polymer is obtained by copolymerization of a compound having poly(perfluoroalkylene ether) chain and polymerizable unsaturated group in both ends, and a polymerizable unsaturated monomer having an adamantly group which has a reactive functional group. The compound comprises a functional group reactable with the reactive functional group, and a polymerizable functional group.

Description

Fluoropolymer property resin, the active energy ray-curable composition that uses it and cured article thereof
Technical field
The present invention relates to a kind ofly can give the fluoropolymer property resin as fluorochemical surfactant, fluorochemical surface properties-correcting agent of excellent stain, lyophobicity and scuff resistance to film coated surface.In addition, also relate to active energy ray-curable composition, its cured article that uses this fluoropolymer property resin and article with its cured coating film.
Background technology
All the time, on the most surperficial Polarizer of liquid-crystal display, the front protecting sheet is set further usually.This front protecting sheet can use resin board (vinylformic acid (PMMA) sheet material, polycarbonate (PC) sheet material, the compound sheet material of PMMA/PC) or glass with transparency.Resin sheet when thickness is 0.3mm～2mm, with glassy phase ratio, softness, and easily because of scratching produces damage, therefore is provided with hard coat in its surface and gives its scuff resistance.
Improve the method for scuff resistance as above-mentioned hard coat is set, known have on substrate surface form the method that makes the hard coat material that contains polyfunctional monomers such as multifunctional (methyl) propenoate solidify the cured coating film of gained.Yet existing cured coating film when having adhered to dirt such as fingerprint, sebum, sweat, makeup, has dirt and becomes very showy, does not see the problem that Chu's picture shows.In addition, show and will remove dirt also be very difficult in order to see picture clearly.
Therefore; Prevent that in order to give dirt from adhering to, also further can be easy to the didirtresistance except that the dirt of attachment removal; Studying in hard coat material cooperate fluorochemical surfactant or fluorochemical surface properties-correcting agent (below, they are lumped together are referred to as " fluorochemical surfactant ".) as additive.Particularly; In order to keep didirtresistance; And proposed a kind ofly to be designed to have polymerizable group and to be fixed on the aggretion type fluorochemical surfactant in the cured coating film through covalent linkage; It is the aggretion type fluorochemical surfactant with unsaturated group (for example, with reference to patent documentation 1) that obtains through the polymer reaction that makes mono acrylic ester with fluoro-alkyl and the acrylic monomer copolymerization with active hydrogen, then make acrylic monomer with NCO and gained.This aggretion type fluorochemical surfactant has polymerizable group, as the additive of hard coat material the time, through covalent linkage and polymerization composition in the said composition combine to be fixed on film on.Yet, have when the repeated multiple times wiping causes the film coated surface wearing and tearing attached to the lip-deep dirt of the cured coating film of hard coat material the problem that didirtresistance descends.In addition, also have when wearing and tearing cured coating film surfaces such as use steel wire lump, easily the problem of damage.
In addition; Also proposed to have (perfluorinated alkylidene ether) chain and to be the aggretion type fluorochemical surfactant (for example, referring to patent documentation 2) that having of raw material manufacturing gathered (perfluorinated alkylidene ether) chain and unsaturated group at the compound that its two end has two (methyl) acryl.The material of record is same in this aggretion type fluorochemical surfactant and the patent documentation 1, and the didirtresistance that also has after the wearing and tearing reduces greatly, and when using wearing and tearing cured coating film surface such as steel wire lump, easily the problem of damage.
Therefore, for the dirt that wiping is repeatedly adhered to, even require a kind of film coated surface of having worn and torn, also can keep didirtresistance, and have the material of high scuff resistance.
The prior art document
[patent documentation 1] TOHKEMY 2007-246696 communique
[patent documentation 2] International Publication WO2009/133770 communique
Disclosure of the Invention
The problem that invention will solve
The problem that the present invention will solve provides a kind of didirtresistance and the scuff resistance that can give excellence to the cured coating film surface, and can be as the fluoropolymer property resin of fluorochemical surfactant.In addition; Also provide a kind of after coating, solidifying; Even form wiping times without number attached to the lip-deep dirt of cured coating film, make the cured coating film surface abrasion; Also can keep excellent didirtresistance, and have active energy ray-curable composition, its cured article and the article of the cured coating film of excellent scuff resistance with its cured coating film.
The method of dealing with problems
The inventor etc. have carried out active research in order to address the above problem; The result finds in its polymer architecture, to have polymkeric substance that gathers (perfluorinated alkylidene ether) chain, adamantyl and polymerizability unsaturated group and the active energy ray-curable composition that contains this polymkeric substance; Can give excellent didirtresistance to the cured coating film surface, even and times without number wiping make the film coated surface wearing and tearing attached to the dirt on the film coated surface; Also can keep excellent didirtresistance, accomplish the present invention thus.
That is to say; The present invention relates to a kind of fluoropolymer property resin; It is characterized in that this resin is the polymkeric substance that makes polymerizability polymerization of unsaturated monomers gained; And in the structure of said polymkeric substance, have and gather (perfluorinated alkylidene ether) chain, adamantyl and polymerizability unsaturated group, and relate to the active energy ray-curable composition that uses this resin.
Further; The present invention relates to a kind of said fluoropolymer property resin or active energy ray-curable composition are coated on the base material; And the irradiation active energy beam makes it solidify formed cured article, and article with cured coating film of said fluoropolymer property resin or active energy ray-curable composition.
The invention effect
Fluoropolymer property resin of the present invention can be given didirtresistance to substrate surface through being coated on formation cured coating film on the base material separately.In addition; Added the active energy ray-curable composition of said fluoropolymer property resin as fluorochemical surfactant; When coating base material; Can produce the minimized effect of the distinctive surface free energy of fluorine atom that makes, and this polymerizability fluorine based compound is segregated on the film coated surface, can carries out only film coated surface being given the surface-treated of didirtresistance etc.Further; Since said fluoropolymer property resin can with other composition polymerization in the active energy ray-curable composition with solidified nature; Therefore polymerizability fluorine based compound of the present invention is fixed in the cured coating film more firmly; Even and then implemented thermal treatment, washing etc., also can suppress polymerizability fluorine based compound or its resolvent from cured coating film surface volatilization or break away from.
In addition; Use the cured coating film of fluoropolymer property resin of the present invention; Has excellent didirtresistance on its surface; Even and the repeated multiple times wiping attached to the lip-deep dirt of cured coating film the film coated surface of having worn and torn, also can keep excellent didirtresistance, so it is exceedingly useful with hard coat as being arranged on the most lip-deep front of liquid-crystal display protecting sheet.
Description of drawings
Fig. 1 is the IR spectrogram of the fluoropolymer property resin (1) of gained among the embodiment 1.
Fig. 2 is the fluoropolymer property resin (1) of gained among the embodiment 1 13The C-NMR spectrogram.
Fig. 3 is the GPC figure of the fluoropolymer property resin (1) of gained among the embodiment 1.
The invention embodiment
Fluoropolymer property resin of the present invention is characterized in that this resin is the polymkeric substance that makes polymerizability polymerization of unsaturated monomers gained, and in the structure of said polymkeric substance, has and gather (perfluorinated alkylidene ether) chain, adamantyl and polymerizability unsaturated group.
Fluoropolymer property resin of the present invention, for example, can be through following 2 kinds of method manufacturings.
(method of manufacture 1)
The polymerizability unsaturated monomer (B1) that gathers (perfluorinated alkylidene ether) chain to have and have the compound (A) of polymerizability unsaturated group and have an adamantyl that has reactive functional group (b1) at its two end carries out copolymerization and obtains polymkeric substance (P1) as necessary monomer component, and makes polymkeric substance (P1) and contain with respect to said functional group (b1) and have the method that the compound (C) of reactive functional group (c) and polymerizability unsaturated group reacts.
(method of manufacture 2)
Gather (perfluorinated alkylidene ether) chain to have and have the compound (A) of polymerizability unsaturated group at its two end, polymerizability unsaturated monomer (B2) and the polymerizability unsaturated monomer (B3) with reactive functional group (b3) that has the polymerizability unsaturated monomer (B1) of the adamantyl that has reactive functional group (b1) or have an adamantyl of reactive functional group be not with (b1) carries out copolymerization and obtains polymkeric substance (P2) as necessary monomer component, and make polymkeric substance (P2) and contain and have the method that the compound more than a kind (C) of reactive functional group (c) and polymerizability unsaturated group reacts with respect to said functional group (b1) or said functional group (b3).
Then, each raw material that is used to make the invention described above fluoropolymer property resin is described.
In above-mentioned method of manufacture 1 and 2, gather (perfluorinated alkylidene ether) chain and describe at the compound (A) that its two end has a polymerizability unsaturated group as having of fluoropolymer property resin raw material of the present invention.Gathered (perfluorinated alkylidene ether) chain as what said compound (A) had, can enumerate that to have carbonatoms be the segment that 1～3 divalent is fluoridized the structure that alkyl and Sauerstoffatom alternately be connected.Carbonatoms is that 1～3 divalent is fluoridized alkyl, can be a kind of, and mixing that also can be multiple specifically, can be enumerated the represented group of following structural formula (a1).
[changing 1]
(in the said structure formula (a1), X is following structural formula (a1-1)～(a1-5), and the whole X in the structural formula (a1) can be same structure, and in addition, a plurality of structures can randomly or with block-wise ground exist.In addition, n representes repeating unit, and it is the integer more than 1.)
[changing 2]
-CF 2- (a1-1)
-CF 2CF 2- (a1-2)
-CF 2CF 2CF 2-?(a1-3)
Figure BSA00000588122000051
Wherein, Particularly the wiping from the film coated surface dirt is good; And can obtain the excellent viewpoint of filming of didirtresistance and consider, the structure of the perfluor ethylidene structure coexistence that perfluor methylene radical structure that preferred especially said structural formula (a1-1) is represented and said structural formula (a1-2) are represented.Here; The perfluor ethylidene structure that perfluor methylene radical structure that said structural formula (a1-1) is represented and said structural formula (a1-2) are represented have a ratio; Consider that from the didirtresistance viewpoint its mol ratio [structure (a1-1)/structure (a1-2)] is preferably 1/10～10/1 ratio.In addition, the n value in the said structural formula (a1) is preferably 3～100 scope, and more preferably 6～70 scope further is preferably 12～50 scope.
In addition; Said gathering (perfluorinated alkylidene ether) chain; Excellent from didirtresistance and oilness; And raising is the deliquescent viewpoint consideration of curable resin composition to non-fluorine easily, and 1 total of gathering the fluorine atom that contains in (perfluorinated alkylidene ether) chain is preferably 18～200 scope, more preferably 25～150 scope.
As the raw material of said compound (A) to two terminal compounds before importing the polymerizability unsaturated groups, can enumerate following general formula (a2-1)～(a2-6).In addition, the expression of " PFPE-" in following each structural formula above-mentioned gathering (perfluorinated alkylidene ether) chain.
[changing 3]
HO-CH 2-PFPE-CH 2-OH (a2-1)
HO-CH 2CH 2-PFPE-CH 2CH 2-OH (a2-2)
Figure BSA00000588122000061
OCN-PFPE-NCO (a2-5)
Figure BSA00000588122000062
The two terminal polymerizability unsaturated groups that had of the chain of said compound (A) for example, can be enumerated the group with the represented polymerizability unsaturated group of following structural formula U-1～U-5.
[changing 4]
In these polymerizability unsaturated groups; Particularly obtain easily or manufacturing from compound (A) itself; Perhaps with after the excellent viewpoint of polymerizability of the polymerizability unsaturated monomer (B1)～(B3) stated consider acryloxy, the represented methacryloxy of structural formula U-2 that preferred structure formula U-1 is represented.In addition, consider the represented styryl methoxyl group of methacryloxy, structural formula U-5 that preferred structure formula U-2 is represented from the viewpoint that improves chemical reagent resistance.
In said compound (A),, can enumerate the represented compound of following structural formula (A-1)～(A-13) as compound with said acryloxy etc.In addition, the expression of " PFPE-" in following each structural formula gathers (perfluorinated alkylidene ether) chain.
[changing 5]
Figure BSA00000588122000081
Wherein, particularly itself make in industry easily, and when making polymkeric substance (P), carry out the viewpoint consideration of polyreaction, preferred said structural formula (A-1), (A-2), (A-5), (A-6) represented compound easily from compound (A).In addition, consider preferred said structural formula (A-2), (A-4), (A-12), (A-13) from the viewpoint that improves chemical reagent resistance.
In order to make above-claimed cpd (A); For example, can enumerate: make (methyl) acrylate chloride or 1-chloro-4-methyl-benzene carry out the desalination acid-respons with respect to the compound that respectively has 1 hydroxyl at two ends that gather (perfluorinated alkylidene ether) chain and obtain this compound method, make (methyl) vinylformic acid carry out dehydration reaction and obtain this compound method, make 2-(methyl) acryloxy ethyl isocyanate carry out urethane reaction and obtain this compound method, make itaconic anhydride carry out esterification and obtain this compound method, make 4-hydroxybutyl propenoate glycidyl ether carry out esterification with respect to the compound that respectively has 1 carboxyl at two ends that gather (perfluorinated alkylidene ether) chain and obtain this compound method, make SY-Monomer G carry out esterification and obtain this compound method, 2-hydroxyethyl acrylic amide reacted with respect to the compound that respectively has 1 NCO at two ends that gather (perfluorinated alkylidene ether) chain and obtain the method for this compound.Wherein, Consider from easy synthetic viewpoint, especially preferably make (methyl) acrylate chloride or 1-chloro-4-methyl-benzene carry out the desalination acid-respons with respect to the compound that respectively has 1 hydroxyl at two ends that gather (perfluorinated alkylidene ether) chain and obtain this compound method, make 2-(methyl) acryloxy ethyl isocyanate carry out the urethane reaction and obtain the method for this compound.
In addition; In the present invention; " (methyl) propenoate " is meant a side or two sides in methacrylic ester and the propenoate; " (methyl) acryl " is meant a side or two sides in methacryloyl and the acryl, and " (methyl) vinylformic acid " is meant a side or two sides in methylacrylic acid and the vinylformic acid.
In above-mentioned method of manufacture 1, describe as the said monomer (B1) of the raw material of fluoropolymer property resin of the present invention.The adamantyl that said monomer (B1) is had is the organic group with following adamantane structure.
[changing 6]
Figure BSA00000588122000091
In addition, as the reactive functional group that adamantyl had (b1) that said monomer (B1) has, can enumerate hydroxyl, NCO, epoxy group(ing), carboxyl, acid halide group, anhydride group etc.The polymerizability unsaturated group that said monomer (B1) is had; Be preferably and have free-radical polymerised carbon carbon unsaturated double-bond; More particularly; Can enumerate vinyl, (methyl) acryl, dimaleoyl imino etc., and consider, more preferably (methyl) acryl from easy polymeric viewpoint.These said monomers (B1) can only use a kind, also can be with reactive functional group (b1) or different monomer more than 2 kinds and the usefulness of polymerizability unsaturated group.
As having the said monomer (B1) of (methyl) acryl, for example, can enumerate the represented compound of formula (B1-1) as the polymerizability unsaturated group.
[changing 7]
Figure BSA00000588122000101
(in the formula, L representes said reactive functional group (b1), and X and Y represent the organic group or the singly-bound of divalent, and R representes Wasserstoffatoms, methyl or CF 3)
In the above-mentioned general formula (B 1-1)-the represented organic group that contains said reactive functional group (b1) of X-L and the link position of Y, can be connected with any carbon atom in the adamantane structure, in addition, also can have more than 2-X-L.Further, the Wasserstoffatoms that is connected with the carbon atom that constitutes adamantane structure also can be partly or entirely by replacements such as fluorine atom, alkyl.In addition, X in the above-mentioned general formula (B1-1) and Y are the organic group or the singly-bound of divalent, as the organic group of this divalent, can enumerate carbonatomss such as methylene radical, propylidene, isopropylidene and be 1～8 alkylidene group.
As the example more specifically of said monomer (B1), can enumerate following formula represented compounds such as (B1-1-1)～(B1-1-5).
[changing 8]
Figure BSA00000588122000111
In above-mentioned method of manufacture 2, describe as the said monomer (B2) of the raw material of fluoropolymer property resin of the present invention.Said monomer (B2) is the polymerizability unsaturated monomer with adamantyl, and this adamantyl is identical with said monomer (B1).In addition; The polymerizability unsaturated group that said monomer (B2) contains; Be preferably and have free-radical polymerised carbon carbon unsaturated double-bond, more particularly, can enumerate vinyl, (methyl) acryl, dimaleoyl imino etc.; And from easy polymeric viewpoint consideration, more preferably (methyl) acryl.This said monomer (B2) can only use a kind, also can be with also using more than 2 kinds.
As containing the said monomer (B2) of (methyl) acryl, for example, can enumerate the represented compound of formula (B2-1) as the polymerizability unsaturated group.
[changing 9]
Figure BSA00000588122000121
(in the formula, R representes Wasserstoffatoms, methyl or CF 3)
(methyl) acryl can be connected with any carbon atom in the adamantane structure.In addition, the Wasserstoffatoms that is connected with the carbon atom that constitutes the middle adamantane structure of above-mentioned general formula (B2-1) can be partly or entirely by replacements such as fluorine atom, alkyl.
As the example more specifically of said monomer (B2), can enumerate following formula represented compounds such as (B2-1-1)～(B2-1-3).
[changing 10]
Figure BSA00000588122000122
In above-mentioned method of manufacture 2, describe as the said monomer (B3) of the raw material of fluoropolymer property resin of the present invention.As the reactive functional group (b3) that said monomer (B3) is contained, can enumerate hydroxyl, NCO, epoxy group(ing), carboxyl, acid halide group, anhydride group etc.In addition; The polymerizability unsaturated group that said monomer (B3) is had; Be preferably and have free-radical polymerised carbon carbon unsaturated double-bond, more particularly, can enumerate vinyl, (methyl) acryl, dimaleoyl imino etc.; And from easy polymeric viewpoint consideration, more preferably (methyl) acryl.
Concrete example as said monomer (B3); Can enumerate (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, 1; 4-cyclohexanedimethanol list (methyl) propenoate, N-(2-hydroxyethyl) (methyl) acrylic amide, USP Kosher list (methyl) propenoate, polyethyleneglycol (methyl) propenoate, W 166 list (methyl) propenoate, 2-hydroxyl-3-phenoxy propyl (methyl) propenoate, 2-(methyl) acryloxy ethyl-2-hydroxyethyl phthalic ester, end have hydroxyl in ester modified (methyl) propenoate etc. have the unsaturated monomer of hydroxyl; 2-(methyl) acryloxy ethyl isocyanate, 2-(2-(methyl) acryloyl-oxy base oxethyl) ethyl isocyanate, 1, two ((methyl) acryloyl-oxy ylmethyl) ethyl isocyanates etc. of 1-have the unsaturated monomer of NCO; SY-Monomer G, 4-hydroxybutyl propenoate glycidyl ether etc. have the unsaturated monomer of epoxy group(ing); (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl succinate, 2-(methyl) acryloxy ethylbenzene dicarboxylic acid esters, toxilic acid, methylene-succinic acid etc. have the unsaturated monomer of carboxyl; Maleic anhydride, itaconic anhydride etc. have the acid anhydrides of unsaturated double-bond etc.These monomers (B3) can only use a kind, also can be with also using more than 2 kinds.
In addition; In above-mentioned method of manufacture 1 or 2; Making as the said polymkeric substance (P1) of fluoropolymer property resin intermediate of the present invention or (P2) time; Except said compound (A), monomer (B1), monomer (B2) with the monomer (B3), can also use other polymerizability unsaturated monomer (B4) that can carry out copolymerization with them.As this other polymerizability unsaturated monomer (B4), can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) n-butyl acrylate, (methyl) NSC 20949, (methyl) vinylformic acid n-pentyl ester, the just own ester of (methyl) vinylformic acid, the positive heptyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid n-octyl, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) cyclohexyl acrylate, (methyl) IBOA, have (methyl) esters of acrylic acids such as (methyl) propenoate of polyoxy alkylidene chain; Vinylbenzene, alpha-methyl styrene, p-methylstyrene, to aromatic vinyl classes such as methoxy styrenes; Maleimides such as maleimide, methyl maleimide, ethyl maleimide, propyl group maleimide, butyl maleimide, hexyl maleimide, octyl group maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide etc.
In above-mentioned method of manufacture 1 or 2, describe as the said compound (C) of fluoropolymer property resin raw material of the present invention.Functional group (c) as said compound (C) is had for example, can enumerate hydroxyl, NCO, epoxy group(ing), carboxyl, acid halide group, anhydride group etc.During when said monomer (B1) or the reactive functional group (b1) that (B3) is had or (b3) for hydroxyl; Can enumerate NCO, carboxyl, acid halide group, epoxy group(ing) as functional group (c); When reactive functional group (b1) or (b3) being NCO; Hydroxyl can be enumerated as functional group (c), when when reactive functional group (b1) or (b3) being epoxy group(ing), carboxyl, hydroxyl can be enumerated as functional group (c); When reactive functional group (b1) or (b3) being carboxyl, can enumerate epoxy group(ing), hydroxyl as functional group (c).
Here; In above-mentioned method of manufacture 2; Also with said monomer (B1) and said monomer (B3) time; When reactive functional group (b1) that they had and reactive functional group (b3) are respectively different functional group, and when said reactive functional group (b1) and (b3) and common functional group when reacting, can use to have the a kind of compound (C) that with said reactive functional group (b1) and (b3) all has reactive functional group (c).In addition; When reactive functional group (b1) and reactive functional group (b3) were not reacted with the common functional group, the preferred use had and reactive functional group (b1) has the compound (C) of reactive functional group (c) and has and reactive functional group (b3) has the compound compounds (C) more than 2 kinds such as (C) of reactive functional group (c).
The polymerizability unsaturated group that said compound (C) is had; Be preferably and have free-radical polymerised carbon carbon unsaturated double-bond; More particularly; Can enumerate vinyl, (methyl) acryl, dimaleoyl imino etc., and from after the good viewpoint of solidified nature of the active energy ray-curable resin composition stated consider (methyl) acryl more preferably.
Object lesson as said compound (C); Can enumerate (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, 1; 4-cyclohexanedimethanol list (methyl) propenoate, N-(2-hydroxyethyl) (methyl) acrylic amide, USP Kosher list (methyl) propenoate, polyethyleneglycol (methyl) propenoate, W 166 list (methyl) propenoate, 2-hydroxyl-3-phenoxy propyl (methyl) propenoate, 2-(methyl) acryloxy ethyl-2-hydroxyethyl phthalic acid ester, end have hydroxyl in ester modified (methyl) propenoate etc. have the unsaturated monomer of hydroxyl; 2-(methyl) acryloxy ethyl isocyanate, 2-(2-(methyl) acryloyl-oxy base oxethyl) ethyl isocyanate, 1, two ((methyl) acryloyl-oxy ylmethyl) ethyl isocyanates etc. of 1-have the unsaturated monomer of NCO; SY-Monomer G, 4-hydroxybutyl propenoate glycidyl ether etc. have the unsaturated monomer of epoxy group(ing); (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl succinate, 2-(methyl) acryloxy ethylbenzene dicarboxylic acid esters, toxilic acid, methylene-succinic acid etc. have the unsaturated monomer of carboxyl; Maleic anhydride, itaconic anhydride etc. have the acid anhydrides of unsaturated double-bond etc.In addition, as compound, can use methylacrylic acid 2-hydroxyl-3-acryloxy propyl ester, pentaerythritol triacrylate, Dipentaerythritol five propenoate etc. with a plurality of polymerizability unsaturated groups.These compounds (C) can only use a kind, also can be with also using more than 2 kinds.
In the object lesson of above-claimed cpd (C); The good viewpoint of polymerization-curable during especially from uviolizing is considered; Be preferably vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, vinylformic acid 3-hydroxy propyl ester, vinylformic acid 2-hydroxyl butyl ester, vinylformic acid 4-hydroxyl butyl ester, 1; 4-cyclohexanedimethanol mono acrylic ester, N-(2-hydroxyethyl) acrylic amide, 2-acryloxy ethyl isocyanate, 1, two (acryloyl-oxy ylmethyl) ethyl isocyanates of 1-, 4-hydroxybutyl propenoate glycidyl ether, vinylformic acid.
Then, describe for the method more specifically of using above-mentioned cited raw material to make fluoropolymer property resin of the present invention.
In the above-mentioned method of manufacture 1 or 2; Just make said polymkeric substance (P1) or method (P2) as fluoropolymer property resin intermediate of the present invention; Can be set forth in the organic solvent; Use polymerization starter, when method of manufacture 1, make said compound (A), said monomer (B1) and other polymerizability unsaturated monomer (B4) polymerization as required; In method of manufacture 2, make said compound (A), said monomer (B1), said monomer (B2), said monomer (B3) and other polymerizability unsaturated monomer (B4) polymeric method as required.As organic solvent as used herein; Be preferably ketone, ester class, amides, sulfoxide class, ethers, hydro carbons; Specifically, can enumerate acetone, methylethylketone, MIBK, pimelinketone, ETHYLE ACETATE, butylacetate, propylene glycol methyl ether acetate, N, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, DMSO 99.8MIN., Anaesthetie Ether, Di Iso Propyl Ether, THF, two
Figure BSA00000588122000151
alkane, toluene, YLENE etc.They can be considered boiling point, intermiscibility, polymerizability and suitably select.As polymerization starter, for example, azo cpds such as superoxide, Diisopropyl azodicarboxylate such as the Lucidol of can giving an example etc.Further, can also use chain-transfer agents such as dodecyl mercaptans, 2 mercapto ethanol, thioglycerin, ethyl thioglycolate, Thiovanic acid monooctyl ester as required.
In method of manufacture 1 or 2; Has the compound (C) that to said functional group (b1) or (b3) has reactive functional group (c) and polymerizability unsaturated group through making; With as the polymkeric substance (P1) of above-mentioned gained or (P2) reaction, can obtain fluoropolymer property resin of the present invention.
Make said compound (C) and said polymkeric substance (P1) or (P2) method of reaction, the polymerizability unsaturated group that is had at compound (C) etc. does not get final product under the polymeric condition, for example, preferably temperature condition is adjusted to 30～120 ℃ scope and reacts.This reaction is preferred in the presence of catalyzer or stopper, and in the presence of organic solvent, carries out as required.
For example; Be hydroxyl as said functional group (b1) or (b3), and said functional group (c) preferably use p methoxy phenol, quinhydrones, 2 when being NCO; 6-di-tert-butyl-4-methy phenols etc. are as stopper; Using dibutyl tin laurate, dibutyltin diacetate, stannous octoate, zinc octoate etc. as the urethane catalysts, is 40～120 ℃ in temperature of reaction, is in particular 60～90 ℃ of methods of reaction down.In addition; Be epoxy group(ing) as said functional group (b1) or (b3), and said functional group (c) being when being carboxyl, is carboxyl as said functional group (b1) or (b3) perhaps; And when said functional group (c) is epoxy group(ing); Preferred p methoxy phenol, quinhydrones, the 2,6 di tert butyl 4 methyl phenols etc. of using are as stopper, and quaternary phosphine salts such as tertiary phosphine classes such as quaternary ammonium salts such as tertiary amines, Tetramethylammonium chloride, triphenyl phosphine, chlorination 4-butyl-phosphonium such as use triethylamine etc. are as catalyst for esterification reaction; In temperature of reaction is 80～130 ℃, is in particular 100～120 ℃ of reactions down.
Employed organic solvent is preferably ketone, ester class, amides, sulfoxide class, ethers, hydro carbons in the above-mentioned reaction; Specifically, can enumerate acetone, methylethylketone, MIBK, pimelinketone, ETHYLE ACETATE, butylacetate, propylene glycol methyl ether acetate, N, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, DMSO 99.8MIN., Anaesthetie Ether, Di Iso Propyl Ether, THF, two
Figure BSA00000588122000161
alkane, toluene, YLENE etc.They can be considered boiling point, intermiscibility, polymerizability and suitably select.
Like the fluoropolymer property resin of the present invention of above-mentioned gained, consider that from the viewpoint that didirtresistance is excellent its number-average molecular weight (Mn) is preferably 1000～5000 scope, more preferably 1400～4000 scope.In addition, weight-average molecular weight (Mw) is preferably 2000～50000 scope, more preferably 3000～20000 scope.Their number-average molecular weight (Mn) and weight-average molecular weight (Mw) can be measured through above-mentioned GPC and obtain.
Here, number-average molecular weight (Mn) and weight-average molecular weight (Mw) be based on gel permeation chromatography (below, abbreviate " GPC " as.) measure and with the value of polystyrene conversion gained.In addition, the condition determination of GPC is described below.
[GPC condition determination]
Determinator: TOSOH Co., Ltd's system " HLC-8220GPC ",
Chromatographic column: TOSOH Co., Ltd's system guard column " HHR-H " (6.0mm I.D. * 4cm)
+ TOSOH Co., Ltd system " TSK-GEL GMHHR-N " (7.8mm I.D. * 30cm)
+ TOSOH Co., Ltd system " TSK-GEL GMHHR-N " (7.8mm I.D. * 30cm)
+ TOSOH Co., Ltd system " TSK-GEL GMHHR-N " (7.8mm I.D. * 30cm)
+ TOSOH Co., Ltd system " TSK-GEL GMHHR-N " (7.8mm I.D. * 30cm)
Detector: ELSD (Alltech system " ELSD2000 ")
Data processing: TOSOH Co., Ltd's system " GPC-8020II type data analysis 4.30 editions "
Condition determination: 40 ℃ of column temperatures
Launch solvents tetrahydrofurane (THF)
Flow velocity 1.0ml/ minute
Sample: the sample (5 μ l) after the tetrahydrofuran solution that uses micro-filter to count 1.0 quality % to converting with the resin solid composition filters.
Standard specimen:, use the known following monodisperse polystyrene of molecular weight according to the mensuration handbook of said " GPC-8020II type data analysis 4.30 editions ".
(monodisperse polystyrene)
TOSOH Co., Ltd's system " A-500 "
TOSOH Co., Ltd's system " A-1000 "
TOSOH Co., Ltd's system " A-2500 "
TOSOH Co., Ltd's system " A-5000 "
TOSOH Co., Ltd's system " F-1 "
TOSOH Co., Ltd's system " F-2 "
TOSOH Co., Ltd's system " F-4 "
TOSOH Co., Ltd's system " F-10 "
TOSOH Co., Ltd's system " F-20 "
TOSOH Co., Ltd's system " F-40 "
TOSOH Co., Ltd's system " F-80 "
TOSOH Co., Ltd's system " F-128 "
TOSOH Co., Ltd's system " F-288 "
TOSOH Co., Ltd's system " F-550 "
In addition; Fluorine-containing rate in the fluoropolymer property resin of the present invention is from realizing didirtresistance and with the intermiscibility of other composition and deposit and consider, being preferably the scope of 1～50 quality %; The scope of 5～35 quality % more preferably, and further be preferably the scope of 10～25 quality %.In addition, the fluorine-containing rate in the fluoropolymer property resin of the present invention is calculated with respect to the quality ratio of raw materials used total amount by fluorine atom.
Further; Polymerizability unsaturated group equivalent in the fluoropolymer property resin of the present invention; Consider from the viewpoint of the excellent scratch resistance of cured coating film, be preferably the scope of 200～3500g/eq., more preferably the scope of 250～2000g/eq.; Further be preferably the scope of 300～1500g/eq., and be preferably the scope of 400～1000g/eq. especially.
Fluoropolymer property resin of the present invention; Can use itself host as active energy ray-curable composition; But owing to have extremely excellent surface-treated performance; Therefore it can be a tensio-active agent as the fluorine that adds in the active energy ray-curable composition also, thereby gives excellent didirtresistance to cured coating film.
Active energy ray-curable composition of the present invention is the material that adds fluoropolymer property resin of the present invention, as its principal constituent, contains active energy ray curable resin (D) or active energy ray-curable monomer (E).In addition, in active energy ray-curable composition of the present invention, active energy ray curable resin (D) and active energy ray-curable monomer (E) can use separately separately, also can and use.In addition, fluoropolymer property resin of the present invention, in this active energy ray-curable composition, being preferably used as fluorine is tensio-active agent.
Said active energy ray curable resin (D) can be enumerated carbamate (methyl) acrylate resin, unsaturated polyester resin, epoxy group(ing) (methyl) acrylate resin, polyester (methyl) acrylate resin, acryloyl (methyl) acrylate resin, had the resin of dimaleoyl imino etc.In the present invention, consider preferred carbamate (methyl) acrylate resin especially from viewpoints such as the transparency and low-shrinkages.
Carbamate used herein (methyl) acrylate resin can be enumerated the resin with amino-formate bond and (methyl) acryl of aliphatic polyisocyanate compound or aromatic polyisocyanate compound and (methyl) acryliccompound reaction gained with hydroxyl.
As said aliphatic polyisocyanate compound; For example; Can enumerate tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene vulcabond, eight methylene diisocyanates, decamethylene vulcabond, 2-methyl isophthalic acid; 5-pentane vulcabond, 3-methyl isophthalic acid, 5-pentane vulcabond, ten dimethylene diisocyanates, 2-methyl pentamethylene diisocyanate, 2,2; 4-trimethyl hexamethylene diisocyanate, 2; 4,4-trimethyl hexamethylene diisocyanate, isophorone diisocyanate, norbornene alkyl diisocyanate, hydrogenated diphenyl methane diisocyanate, HTDI, hydrogenated xylene diisocyanate, hydrogenation tetramethylxylene diisocyanate, cyclohexyl diisocyanate etc., in addition; As the aromatic polyisocyanate compound; Can enumerate tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, XDI, 1,5-naphthalene diisocyanate, tolidine vulcabond, to phenylene vulcabond etc.
On the other hand; As acryliccompound with hydroxyl; For example; Can enumerate (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, 1,5-pentanediol list (methyl) propenoate, 1, list (methyl) propenoate of divalent alcohol such as 6-pinakon list (methyl) propenoate, neopentyl glycol single (methyl) propenoate, NSC 115936 neopentyl glycol single (methyl) propenoate; List or two (methyl) propenoate of trivalent alcohols such as TriMethylolPropane(TMP) two (methyl) propenoate, ethoxylated trimethylolpropane (methyl) propenoate, propoxylation TriMethylolPropane(TMP) two (methyl) propenoate, USP Kosher two (methyl) propenoate, two (2-(methyl) acryloxy ethyl) hydroxyethyl isocyanuric acid ester, or the list with hydroxyl and two (methyl) propenoate that formed by the 6-caprolactone modification of the part of their alcohol hydroxyl group; Tetramethylolmethane three (methyl) propenoate, two (TriMethylolPropane(TMP)) three (methyl) propenoate, Dipentaerythritol five (methyl) propenoate etc. have 1 official can hydroxyl and 3 officials can above (methyl) acryl compound, or multifunctional (methyl) propenoate of further being formed of this compound with hydroxyl by the 6-caprolactone modification; Dipropylene glycol list (methyl) propenoate, Diethylene Glycol list (methyl) propenoate, W 166 list (methyl) propenoate, polyethyleneglycol (methyl) propenoate etc. have (methyl) acryliccompound of alkylidene oxide chain; Polyethylene glycol-Ucar 35 list (methyl) propenoate, polyoxybutylene-polyoxytrimethylene list (methyl) propenoate etc. have (methyl) acryliccompound of the alkylidene oxide chain of block structure; Gather (terepthaloyl moietie-butyleneglycol) single (methyl) propenoate, gather (methyl) acryliccompound etc. that (Ucar 35-butyleneglycol) single (methyl) propenoate etc. has the alkylidene oxide chain of random structure.
Above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound and the reaction with acryliccompound of hydroxyl can use ordinary method to carry out in the presence of the urethane catalyzer.Operable here urethane catalyzer specifically, can be enumerated amines such as pyridine, pyrroles, triethylamine, diethylamine, dibutylamine; Phosphine such as triphenyl phosphine, triethylphosphine class; Organo-tin compounds such as dibutyl tin laurate, three LAURIC ACID 99 MIN tin octylates, oxalic acid tin octylate, dibutyltin diacetate, stannous octoate; Organometallic compounds such as zinc octoate etc.
In these urethane acrylate resin; The material of aliphatic polyisocyanate compound and (methyl) acryliccompound reaction gained with hydroxyl; Excellent from the transparency of cured coating film; And good thereby excellent these aspects of solidified nature, is preferred especially concerning the susceptibility of active energy beam.
Then; Unsaturated polyester resin is through α, the polycondensation of β-unsaturated dibasic acid or its acid anhydrides, aromatic series monounsaturated dicarboxylic acid or its acid anhydrides and glycols and the curable resin that obtains; As α; β-unsaturated dibasic acid or its acid anhydrides can be enumerated toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, citraconic acid, chloromaleic acid, and their ester etc.As aromatic acid or its acid anhydrides, can enumerate phthalic acid, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, nitrophthalic acid, tetrahydronaphthalic anhydride, nadic anhydride, halogenation Tetra hydro Phthalic anhydride and their ester etc.As aliphatics or alicyclic monounsaturated dicarboxylic acid, can enumerate oxalic acid, propanedioic acid, succsinic acid, hexanodioic acid, sebacic acid, nonane diacid, pentanedioic acid, hexahydro phthalic anhydride and their ester etc.As glycols, can enumerate terepthaloyl moietie, Ucar 35, Diethylene Glycol, dipropylene glycol, 1,3 butylene glycol, 1; 4-butyleneglycol, 2-methyl isophthalic acid, ammediol, NSC 6366, triethylene glycol, TEG, 1,5-pentanediol, 1; 6-pinakon, dihydroxyphenyl propane, Hydrogenated Bisphenol A 99, ethylene carbonate, 2; 2-two (4-hydroxyl propoxy-phenylbenzene) propane etc. in addition, can use oxide compounds such as ethylene oxide, propylene oxide equally.
Then; As the epoxy group(ing) vinyl ester resin, can enumerate the material of the epoxy reaction gained that makes epoxy resin such as (methyl) vinylformic acid and bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin.
In addition; As resin with dimaleoyl imino, can enumerate 2 officials that N-hydroxyethyl maleimide and isophorone diisocyanate carry out the urethane gained can maleimide carbamate compounds, maleimide acetate and polytetramethylene glycol carry out 2 officials of esterification gained can the maleimide ester cpds, the 4 officials ability maleimide ester cpds, maleimide acetate and the polyol compound that make four ethylene oxide adducts of maleimide caproic acid and tetramethylolmethane carry out the esterification gained carry out the multifunctional maleimide ester cpds etc. of esterification gained.These active energy ray curable resins (F) can only use a kind, also can be with also using more than 2 kinds.
As said active energy ray-curable monomer (E); For example; Polyoxyethylene glycol two (methyl) propenoate, Ucar 35 two (methyl) propenoate, dipropylene glycol two (methyl) propenoate, tripropylene glycol two (methyl) propenoate, the number-average molecular weight that can enumerate ethylene glycol bisthioglycolate (methyl) propenoate, Diethylene Glycol two (methyl) propenoate, triethylene glycol two (methyl) propenoate, number-average molecular weight and be 150～1000 scopes are W 166 two (methyl) propenoate, NSC 6366 two (methyl) propenoate, 1 of 150～1000 scopes; 3-butyleneglycol two (methyl) propenoate, 1; 4-butyleneglycol two (methyl) propenoate, 1, aliphatic alkyl (methyl) propenoate, (methyl) vinylformic acid glyceryl ester, (methyl) vinylformic acid 2-hydroxy methacrylate, 3-chloro-2-hydroxypropyl (methyl) propenoate, (methyl) glycidyl acrylate, (methyl) allyl acrylate, (methyl) vinylformic acid 2-butoxy ethyl ester, 2-(diethylamino) ethyl (methyl) propenoate, 2-(dimethylamino) ethyl (methyl) propenoate, γ-(methyl) acryloxy propyl trimethoxy silicane, (methyl) vinylformic acid 2-methoxyl group ethyl ester, methoxyl group Diethylene Glycol (methyl) propenoate, methoxyl group dipropylene glycol (methyl) propenoate, Nonylphenoxy polyoxyethylene glycol (methyl) propenoate, Nonylphenoxy W 166 (methyl) propenoate, phenoxy ethyl (methyl) propenoate, phenoxy dipropylene glycol (methyl) propenoate, phenoxy W 166 (methyl) propenoate, polyhutadiene (methyl) propenoate, polyethylene glycol-Ucar 35 (methyl) propenoate, polyethylene glycol-butyleneglycol (methyl) propenoate, PS ethyl (methyl) propenoate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, two cyclopentyl (methyl) propenoate, dicyclopentenyl (methyl) propenoate, (methyl) IBOA, methoxylation ring triolefin in the last of the ten Heavenly stems (methyl) propenoate, (methyl) phenyl acrylates such as 6-pinakon two (methyl) propenoate, hydroxy new pentane acid ester NSC 6366 two (methyl) propenoate, dihydroxyphenyl propane two (methyl) propenoate, trimethylolpropane tris (methyl) propenoate, tetramethylolmethane three (methyl) propenoate, Dipentaerythritol six (methyl) propenoate, tetramethylolmethane four (methyl) propenoate, TriMethylolPropane(TMP) two (methyl) propenoate, Dipentaerythritol five (methyl) propenoate, dicyclopentenyl (methyl) propenoate, (methyl) methyl acrylate, (methyl) propyl acrylate, (methyl) Bing Xisuandingzhi, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, the different stearyl ester of (methyl) vinylformic acid; Maleimide, N-methyl maleimide, N-ethyl maleimide, N-propyl group maleimide, N-butyl maleimide, N-hexyl maleimide, N-octyl group maleimide, N-dodecyl maleimide, N-stearyl maleimide, N-phenylmaleimide, N-cyclohexyl maleimide, 2-maleimide ethyl-ethyl-carbonate, 2-maleimide ethyl-propyl carbonate, N-ethyl-(2-maleimide ethyl) carbamate, N; N-hexa-methylene bismaleimides, W 166-two (3-maleimide propyl group) ether, two (2-maleimide ethyl) carbonic ether, 1, maleimides such as 4-dimaleimide hexanaphthene etc.
Wherein, Particularly consider that from the excellent viewpoint of the hardness of cured coating film 3 officials such as preferred trimethylolpropane tris (methyl) propenoate, tetramethylolmethane three (methyl) propenoate, Dipentaerythritol six (methyl) propenoate, tetramethylolmethane four (methyl) propenoate can above multifunctional (methyl) propenoate.These active energy ray-curable monomers (E) can only use a kind, also can be with also using more than 2 kinds.
In active energy ray-curable composition of the present invention; When using fluoropolymer property resin of the present invention to be tensio-active agent as fluorine; Its usage quantity with respect to total 100 mass parts of said active energy ray curable resin (D) and active energy ray-curable monomer (E), is preferably the scope of 0.01～20 mass parts; The scope of 0.1～15 mass parts more preferably, and further be preferably the scope of 0.5～10 mass parts.If the usage quantity of fluoropolymer property resin of the present invention in this scope, then can fully obtain leveling characteristics, hydrophobic oleophobic property, didirtresistance, and can fully obtain the hardness and the transparency after said composition is solidified.In addition, fluoropolymer property resin of the present invention divides shared ratio in the skin section of filming, along with active energy ray-curable compsn of the present invention forms the thickness when filming and changes; Therefore; Under the situation of thick film, the addition of fluoropolymer property resin of the present invention is set at lower, under the situation of film; Be set at the addition of fluoropolymer property resin of the present invention higher; Thereby can make fluoropolymer property resin of the present invention is not to be present in film coated surface with spreading all over, and can expect high scuff resistance, therefore preferred.
Fluoropolymer property resin of the present invention or active energy ray-curable composition can form cured coating film through irradiation active energy beam after coating base material.This active energy beam is meant ultraviolet ray, electron beam, alpha-ray, β ray, the such ionizing radiation of gamma-rays.When irradiation ultraviolet radiation forms cured coating film as active energy beam, preferably in this fluoropolymer property resin or active energy ray-curable composition, add Photoepolymerizationinitiater initiater (F), to improve solidified nature.In addition, if necessary, can also add photosensitizers, to improve solidified nature.On the other hand, when using the such ionizing radiation of electron beam, alpha-ray, β ray, gamma-rays,, therefore, do not need to add especially Photoepolymerizationinitiater initiater (F) or photosensitizers even do not use Photoepolymerizationinitiater initiater or photosensitizers can solidify rapidly yet.
As said Photoepolymerizationinitiater initiater (F), can enumerate intramolecularly decomposition type Photoepolymerizationinitiater initiater and dehydrogenation type Photoepolymerizationinitiater initiater.As intramolecularly decomposition type Photoepolymerizationinitiater initiater; For example, can enumerate diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzil dimethyl ketal, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-methyl-2-morpholinyl (4-thiomethyl phenyl) propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-methyl phenyl ketone based compounds such as butanone; Bitter almond oil camphor classes such as bitter almond oil camphor, benzoin methyl ether, bitter almond oil camphor isopropyl ether; 2,4,6-Three methyl Benzene acyloin diphenyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl)-acylphosphine oxide based compounds such as phenyl phosphine oxide; Benzil, aminomethyl phenyl glyoxylic ester etc.
On the other hand, as dehydrogenation type Photoepolymerizationinitiater initiater, for example; Can enumerate UVNUL MS-40, o-benzoyl yl benzoic acid methyl esters-4-phenyl benzophenone, 4; 4 '-dichloro benzophenone, dihydroxy benaophenonel, 4-benzoyl--4 '-methyl-diphenyl sulfide, propylene acidylate UVNUL MS-40,3,3 ', 4; 4 '-four (tert-butyl hydroperoxide carbonyl) UVNUL MS-40,3,3 '-dimethyl--UVNUL MS-40 based compounds such as 4-methoxy benzophenone; 2-isopropyl thioxanthone, 2,4-dimethyl-thioxanthone, 2,4-diethyl thioxanthone, 2, thioxanthone based compounds such as 4-two clopenthixal ketones; Michaelis ketone, 4, aminobenzophenone based compounds such as 4 '-diethylamino UVNUL MS-40; 10-butyl-2-chloro-acridine ketone, 2-ethyl-anthraquinone, 9,10-phenanthrenequione, camphorquinone etc.
In above-mentioned Photoepolymerizationinitiater initiater (F); From with active energy ray-curable composition the excellent viewpoint of intermiscibility of said active energy ray-curable resin (D) and active energy ray-curable monomer (E) consider; Preferred 1-hydroxycyclohexylphenylketone and UVNUL MS-40, preferred especially 1-hydroxycyclohexylphenylketone.These Photoepolymerizationinitiater initiaters (F) can use separately, also can be with also using more than 2 kinds.
In addition, as said photosensitizers, for example, can enumerate sulphur compounds such as ureas such as amines such as fatty amine, aromatic amine, adjacent toluene thiocarbamide, diethylammonium curing sodium phosphate, s-benzylisothiourea-tosilate etc.
The usage quantity of these Photoepolymerizationinitiater initiaters and photosensitizers; With respect to 100 mass parts of the nonvolatile component in the active energy ray-curable composition; Be preferably 0.01～20 mass parts separately, 0.1～15 mass parts more preferably, and further be preferably 0.3～7 mass parts.
Further; Active energy ray-curable composition of the present invention; According to purposes such as its purposes, characteristics; In the scope of not damaging effect of the present invention; Can be also with being used to adjust viscosity or specific refractory power; Or the adjustment tone of filming; Or adjust the various compounding ingredients of other coating proterties or the rerum natura of filming, and for example, various resins such as various organic solvents, vinyl resin, resol, vibrin, polystyrene resin, urethane resin, urea resin, melamine resin, Synolac, epoxy resin, polyamide resin, polycarbonate resin, petroleum resin, fluoro-resin; Various organic or inorganic particles such as PTFE (tetrafluoroethylene), Vilaterm, Vestolen PP 7052, carbon, titanium oxide, aluminum oxide, copper, silicon dioxide microparticle, polymerization starter, stopper, static inhibitor, skimmer, viscosity modifier, photostabilizer, weather-proof stablizer, thermo-stabilizer, oxidation inhibitor, rust-preventive agent, lubricant, wax, gloss regulator, releasing agent, compatilizer, conduction regulator, pigment, dyestuff, dispersion agent, dispersion stabilizer, silicon-type, hydrocarbon system tensio-active agent etc.
In above-mentioned each gradation composition, organic solvent is that effectively particularly in order to carry out film coated, it regulates thickness easily for the soltion viscosity of suitable adjusting active energy ray-curable composition of the present invention.As operable organic solvent here, for example, can enumerate aromatic hydrocarbonss such as toluene, YLENE; Alcohols such as methyl alcohol, ethanol, Virahol, the trimethyl carbinol; Ester such as ETHYLE ACETATE, propylene glycol methyl ether acetate class; Ketones such as methylethylketone, MIBK, pimelinketone etc.These solvents can use separately, also can be with also using more than 2 kinds.
Here, the usage quantity of organic solvent according to the thickness of purposes or purpose, viscosity and difference, but with respect to the total mass of cure component, in quality criteria, is preferably the scope of 0.5～50 times of amount.
As making active energy ray-curable composition solidified active energy beam of the present invention; As stated; Be ultraviolet ray, electron beam, alpha-ray, β ray, the such ionizing radiation of gamma-rays; As concrete energy source or solidification equipment; For example, can enumerate sterilizing lamp, ultraviolet ray with luminescent lamp, carbon arc, xenon lamp, duplicating with high pressure mercury vapour lamp, medium-pressure or high pressure mercuryvapour lamp, extra-high-pressure mercury vapour lamp, electrodeless lamp, metal halide lamp, with the ultraviolet ray as light source such as natural light, or by sweep type, the formed electron beam of curtain type electron-beam accelerator etc.
Wherein, be preferably ultraviolet ray especially, and hinder, preferably irradiation ultraviolet radiation under non-active gas atmosphere such as nitrogen for fear of the curing that causes because of oxygen etc.In addition, can also as required and use hotwork to be energy source, also can after being cured, heat-treat through ultraviolet ray.
The coating process of active energy ray-curable composition of the present invention; According to purposes and difference; For example; Can enumerate and use intaglio plate coating machine, roller coating machine, half-angle wheel coating machine, knife coater, Kohler coater, curtain to be coated with machine, kiss-coating coating machine, curtain coater, wheel to be coated with the coating process that machine, spin coater, dip coater, silk screen printing, spraying machine, spreader, rod are coated with machine etc., or use the forming method etc. of various moulds.
The cured coating film of fluoropolymer property resin of the present invention owing to have excellent didirtresistance (oleophobic China ink property, anti-finger printing), scuff resistance etc., therefore is coated with it and solidifies on the surface of article, can give didirtresistance and oilness to the surface of article.In addition; Fluoropolymer property resin of the present invention through being that tensio-active agent or fluorine are that surface-modifying agent adds in the coating material as fluorine, can be given leveling characteristics to this coating material; Therefore active energy beam solidify material compsn of the present invention has high-leveling.
As using fluoropolymer property resin of the present invention or active energy ray-curable composition, can give the article of didirtresistance and oilness to its surface, can enumerate the Polarizer of liquid-crystal display (LCD) such as TAC film and use film; Various indicator screens such as plasma display (PDP), OLED display; Touch pad; The housing of electric terminals such as portable phone or screen; Color filter for liquid crystal display (below, be called " CF ".) use transparent protective film; The liquid crystal tft array is used organic insulating film; Circuit forms uses jetted ink; Optical record mediums such as CD, DVD, blu-ray disc; Insert molding (IMD, IFD) is used transfer film; OA such as duplicating machine, stamping machine equipment is used rubber rollers; The glass surface of the reading section of OA such as duplicating machine, scanner equipment; The optical lens of photographic camera, pick up camera, glasses etc.; The windshield glass face of clock and watch such as wrist-watch; Various windows of vehicles such as automobile, rail vehicle; Used for solar batteries glass cover or film; Various building materials such as decorative sheet; The dwelling house window-glass; Various plastic molded articles such as the housing of carpenter's materials such as furniture, synthetic leather, household electrical appliances, FRP bathtub etc.Through coating fluoropolymer property resin of the present invention or active energy ray-curable composition on these article surfaces, and irradiation ultraviolet radiation isoreactivity energy-ray formation cured coating film, can give didirtresistance and oilness to article surface.In addition, fluoropolymer property resin of the present invention is added in the various coating that are applicable to various article, coating is also dry, also can give didirtresistance and oilness to article surface.
In addition, in active energy ray-curable composition, add the coating material of fluoropolymer property resin of the present invention, can improve leveling characteristics, can give didirtresistance (oleophobic China ink property) and oilness (scratch-resistant) to film coated surface simultaneously.As this coating material, can enumerate the hard coat material of the Polarizer of LCD such as TAC film with film; Anti-dazzle (AG: anti-dazzle) coating material or antireflection (LR) coating material; Various indicator screens such as plasma display (PDP), OLED display are used hard coat material; Touch pad is used hard coat material; The colored resist, printing-ink, jetted ink or the coating that are used to form each pixel of RGB that use among the used CF in the imaging apparatus such as liquid-crystal display, OLED display, CCD, CMOS etc.; Black resist, printing-ink, jetted ink or coating that the black matrix" of CF is used; Resin combination is used in pixel next doors such as plasma display (PDP), OLED display; The housing of electric terminals such as portable phone is with coating or hard coat material; The screen of electric terminals such as portable phone is used hard coat material; The transparent protective film on protection CF surface is used coating; The organic insulating film of liquid crystal tft array is used coating; Circuit forms uses jetted ink; Optical record mediums such as CD, DVD, blu-ray disc are used hard coat material; Insert molding (IMD, IFD) is used hard coat material with transfer film; OA such as duplicating machine, stamping machine equipment is used coating material with rubber rollers; The glass of the reading section of OA such as duplicating machine, scanner equipment is used coating material; The optical lens of photographic camera, pick up camera, glasses etc. is used coating material; The windshield glass face of clock and watch such as wrist-watch is used coating material; Various windows of vehicles such as automobile, rail vehicle are used coating material; The antireflection film of used for solar batteries glass cover or film is used coating; Various building materials such as decorative sheet are with printing-ink or coating; The dwelling house window-glass is used coating material; Carpenters such as furniture use coating; The synthetic leather is used coating material; Various plastic molded articles such as the housing of household electrical appliances are with coating or coating material; The FRP bathtub is with coating or coating material etc.
Further,, can give the article of didirtresistance and oilness, can enumerate as the prismatic lens of LCD backlight unit employing or diffusion sheet etc. to its surface as using fluoropolymer property resin of the present invention or active energy ray-curable composition.In addition,, the leveling characteristics of this coating material be can improve, can also scuff resistance (scratch-resistant) and didirtresistance be given to filming of this coating material simultaneously through adding fluorine-containing curable resin of the present invention in coating material at prismatic lens or diffusion sheet.
In addition, because the cured coating film of fluoropolymer property resin of the present invention has low-refraction, therefore can also use coating material as the low-index layer in the anti-reflection layer that prevents on various display surfaces such as LCD, to mirror luminescent lamp etc.In addition,, can keep the low-refraction of filming, can also give didirtresistance to film coated surface simultaneously through adding fluoropolymer property resin of the present invention with the low-index layer in coating material, the particularly anti-reflection layer in coating material at anti-reflection layer.
Further; As other purposes that can use fluoropolymer property resin of the present invention or active energy ray-curable composition, can enumerate the sealing material of optical fiber coating material, waveguide, liquid crystal panel, various optics with sealing material, optics with caking agent etc.
Especially; LCD with the protective membrane of Polarizer with the coating material purposes in; When using active energy ray-curable composition of the present invention, in above-mentioned each composition, cooperate inorganic or organic fine particles such as silicon dioxide microparticle, vinyl resin particulate, polystyrene resin particulate through 0.1～0.5 times of amount ratio with cure component total mass in the active energy ray-curable composition of the present invention as anti-dazzle coating material; Can obtain excellent anti-dazzle property, therefore preferred.
In addition; Fluoropolymer property resin of the present invention or active energy ray-curable composition are being used for LCD with the protective membrane of Polarizer situation with anti-dazzle coating material; Also go for before coating material solidifies, it being contacted with the mould with convex-concave surface shape; Be cured from the side irradiation active energy beam opposite then, coatingsurface is carried out embossing processing to give the transfer printing of anti-dazzle property with mould.In addition, can also be applicable to before coating material solidifies it is contacted with mould with minute surface or film, from being cured, make the surface of filming form the transfer printing of minute surface then with mould or the opposite side irradiation active energy beam of film.
Embodiment
Below, the present invention will be described in more detail to enumerate concrete embodiment.In addition, the IR spectrum of the fluoropolymer property resin of gained, 13The condition determination of C-NMR spectrum and GPC is described below.
[IR spectrometry condition]
Device: Shimadzu Scisakusho Ltd's system " IRPrestige-21 "
Use the KBr method to measure the resin of gained among the embodiment.
[ 13C-NMR spectrometry condition]
Device: Jeol Ltd.'s system " AL-400 "
Solvent: acetone-d 6
[GPC condition determination]
Determinator: TOSOH Co., Ltd's system " HLC-8220GPC ",
Chromatographic column: TOSOH Co., Ltd's system guard column " HHR-H " (6.0mm I.D. * 4cm)
+ TOSOH Co., Ltd system " TSK-GEL GMHHR-N " (7.8mm I.D. * 30cm)
+ TOSOH Co., Ltd system " TSK-GEL GMHHR-N " (7.8mm I.D. * 30cm)
+ TOSOH Co., Ltd system " TSK-GEL GMHHR-N " (7.8mm I.D. * 30cm)
+ TOSOH Co., Ltd system " TSK-GEL GMHHR-N " (7.8mm I.D. * 30cm)
Detector: ELSD (Alltech system " ELSD2000 ")
Data processing: TOSOH Co., Ltd's system " GPC-8020II type data analysis 4.30 editions "
Condition determination: 40 ℃ of column temperatures
Launch solvents tetrahydrofurane (THF)
Flow velocity 1.0ml/ minute
Sample: the sample (5 μ l) after the tetrahydrofuran solution that uses micro-filter to count 1.0 quality % to converting with the resin solid composition filters.
Standard specimen:, use the known following monodisperse polystyrene of molecular weight according to the mensuration handbook of said " GPC-8020II type data analysis 4.30 editions ".
(monodisperse polystyrene)
TOSOH Co., Ltd's system " A-500 "
TOSOH Co., Ltd's system " A-1000 "
TOSOH Co., Ltd's system " A-2500 "
TOSOH Co., Ltd's system " A-5000 "
TOSOH Co., Ltd's system " F-1 "
TOSOH Co., Ltd's system " F-2 "
TOSOH Co., Ltd's system " F-4 "
TOSOH Co., Ltd's system " F-10 "
TOSOH Co., Ltd's system " F-20 "
TOSOH Co., Ltd's system " F-40 "
TOSOH Co., Ltd's system " F-80 "
TOSOH Co., Ltd's system " F-128 "
TOSOH Co., Ltd's system " F-288 "
TOSOH Co., Ltd's system " F-550 "
(synthetic example 1)
In glass flask with whipping appts, TM, cooling tube, dropper; Add two represented ends of following formula (a2-1-1) have per-fluoro polyether compound 20 mass parts of hydroxyl, as Di Iso Propyl Ether 10 mass parts of solvent, as p methoxy phenol 0.006 mass parts of stopper with as triethylamine 3.3 mass parts of neutralizing agent; Under air draught, begin to stir; And flask interior is remained on 10 ℃ on one side, on one side with 2 hours dropping 3.1 mass parts methacrylic chlorides.After dripping end, stirred 1 hour at 10 ℃, heat up, stirred 1 hour at 30 ℃, be warming up to 50 ℃ then, stirred 10 hours, react, and disappear through gas Chromatographic Determination affirmation methacrylic chloride.Then, append Di Iso Propyl Ether 70 mass parts as solvent after, through hybrid ionic exchanged water 80 mass parts and stir, leave standstill the method that makes water layer separate and remove, repeated washing 3 times then.Then, add p methoxy phenol 0.02 mass parts, add sal epsom 8 mass parts, and left standstill 1 day, it is dewatered fully, filter dehydration agent then as dewatering agent as stopper.
[changing 11]
Figure BSA00000588122000291
(in the formula, X is perfluor methylene radical and perfluor ethylidene, and in per 1 molecule, on average there are 7 in the perfluor methylene radical, and on average there are 8 in the perfluor ethylidene, number of fluorine atoms average out to 46.In addition, the number-average molecular weight by the GPC gained is 1500.)
Then, desolvate, obtain the compound that represented the having of following formula (A-2-1) gathers (perfluorinated alkylidene ether) chain through under reduced pressure heating up in a steamer.
[changing 12]
Figure BSA00000588122000292
(in the formula, X is perfluor methylene radical and perfluor ethylidene, and in per 1 molecule, on average there are 7 in the perfluor methylene radical, and on average there are 8 in the perfluor ethylidene, number of fluorine atoms average out to 46.)
(embodiment 1)
In glass flask with whipping appts, TM, cooling tube, dropper, add MIBK 100 mass parts as solvent, and under stream of nitrogen gas, stir on one side, be warming up to 105 ℃ on one side.Then; The have compound (A-2-1), the 50.1 mass parts 3-hydroxyls-1-adamantyl methacrylic ester (the represented compound of above-mentioned formula (B1-1-1)) that gather (perfluorinated alkylidene ether) chain of gained in the synthetic example 1 of 20 mass parts are dissolved in the monomer solution that forms in the 120 mass parts MIBKs, are dissolved in these the 3 kinds of dropping liquids of polymerization starter solution that form in the 80 mass parts MIBKs as 10.5 mass parts tert-butyl hydroperoxide-2-ethylhexanoate of polymerization starter and are contained in respectively in each Dropping feeder; And flask interior is remained on 105 ℃ on one side, Yi Bian side by side dripped with 2 hours.After dripping end, stirred 5 hours, under reduced pressure heat up in a steamer 262.1 mass parts solvents then, obtain polymkeric substance (P1-1) solution at 105 ℃.
Then; In polymkeric substance (P1-1) solution of above-mentioned gained; Adding is as p methoxy phenol 0.1 mass parts of stopper, as stannous octoate 0.03 mass parts of urethane catalyzer; Under air draught, begin to stir, on one side and remain on 60 ℃, Yi Bian with 1 hour dropping 2-acryloxy ethyl isocyanate 29.9 mass parts.After dripping end, after 2 hours, be warming up to 80 ℃ 60 ℃ of stirrings; Stirred 10 hours; Disappearance by IR spectrometry affirmation NCO adds MIBK 53.7 mass parts again, obtains containing the methyl isobutyl ketone solution of 50 quality % fluoropolymer property resins (1).Measure the molecular weight of the fluoropolymer property resin (1) of gained with GPC (polystyrene conversion molecular weight), the number of results average molecular weight is 1500, and weight-average molecular weight is 3900.In addition, the fluorine-containing rate of fluoropolymer property resin (1) is 11 quality %, and polymerizability unsaturated group equivalent is 476g/eq.In addition, the IR spectrogram of fluoropolymer property resin (1) is shown in Fig. 1, 13The C-NMR spectrogram is shown in Fig. 2, and GPC is illustrated in Fig. 3.
(embodiment 2)
In glass flask with whipping appts, TM, cooling tube, dropper, add MIBK 77.6 mass parts as solvent, and under stream of nitrogen gas, stir on one side, be warming up to 105 ℃ on one side.Then; The have compound (A-2-1), the 37.6 mass parts 3-hydroxyls-1-adamantyl methacrylic ester that gather (perfluorinated alkylidene ether) chain of gained in the synthetic example 1 of 40 mass parts are dissolved in the monomer solution that forms in the 139 mass parts MIBKs, are dissolved in these the 3 kinds of dropping liquids of polymerization starter solution that form in the 16.2 mass parts MIBKs as 11.7 mass parts tert-butyl hydroperoxide-2-ethylhexanoate of polymerization starter and are contained in respectively in each Dropping feeder; And flask interior is remained on 105 ℃ on one side, Yi Bian side by side dripped with 2 hours.After dripping end, stirred 5 hours, under reduced pressure heat up in a steamer 190.8 mass parts solvents then, obtain polymkeric substance (P1-2) solution at 105 ℃.
Then; In polymkeric substance (P1-2) solution of above-mentioned gained; Adding is as p methoxy phenol 0.1 mass parts of stopper, as stannous octoate 0.03 mass parts of urethane catalyzer; Under air draught, begin to stir, on one side and remain on 60 ℃, Yi Bian with 1 hour dropping 2-acryloxy ethyl isocyanate 22.3 mass parts.After dripping end, after 2 hours, be warming up to 80 ℃ 60 ℃ of stirrings; Stirred 10 hours; Disappearance by IR spectrometry affirmation NCO adds MIBK 48.7 mass parts again, obtains containing the methyl isobutyl ketone solution of 50 quality % fluoropolymer property resins (2).Measure the molecular weight of the fluoropolymer property resin (2) of gained with GPC (polystyrene conversion molecular weight), the number of results average molecular weight is 1800, and weight-average molecular weight is 5400.In addition, the fluorine-containing rate of fluoropolymer property resin (2) is 22 quality %, and polymerizability unsaturated group equivalent is 640g/eq.
(embodiment 3)
In glass flask with whipping appts, TM, cooling tube, dropper, add MIBK 66.3 mass parts as solvent, and under stream of nitrogen gas, stir on one side, be warming up to 105 ℃ on one side.Then; The have compound (A-2-1), the 56.3 mass parts 3-hydroxyls-1-adamantyl methacrylic ester that gather (perfluorinated alkylidene ether) chain of gained in the synthetic example 1 of 10 mass parts are dissolved in the monomer solution that forms in the 122.6 mass parts MIBKs, are dissolved in these the 3 kinds of dropping liquids of polymerization starter solution that form in the 10 mass parts MIBKs as 9.9 mass parts tert-butyl hydroperoxide-2-ethylhexanoate of polymerization starter and are contained in respectively in each Dropping feeder; And flask interior is remained on 105 ℃ on one side, Yi Bian side by side dripped with 2 hours.After dripping end, stirred 5 hours, under reduced pressure heat up in a steamer 154.7 mass parts solvents then, obtain polymkeric substance (P1-3) solution at 105 ℃.
Then; In polymkeric substance (P1-3) solution of above-mentioned gained; Adding is as p methoxy phenol 0.1 mass parts of stopper, as stannous octoate 0.03 mass parts of urethane catalyzer; Under air draught, begin to stir, on one side and remain on 60 ℃, Yi Bian with 1 hour dropping 2-acryloxy ethyl isocyanate 33.7 mass parts.After dripping end, after 2 hours, be warming up to 80 ℃ 60 ℃ of stirrings; Stirred 10 hours; Disappearance by IR spectrometry affirmation NCO adds MIBK 56.3 mass parts again, obtains containing the methyl isobutyl ketone solution of 50 quality % fluoropolymer property resins (3).Measure the molecular weight of the fluoropolymer property resin (3) of gained with GPC (polystyrene conversion molecular weight), the number of results average molecular weight is 1700, and weight-average molecular weight is 5000.In addition, the fluorine-containing rate of fluoropolymer property resin (3) is 5.6 quality %, and polymerizability unsaturated group equivalent is 420g/eq.
(embodiment 4)
In glass flask with whipping appts, TM, cooling tube, dropper, add MIBK 35 mass parts as solvent, and under stream of nitrogen gas, stir on one side, be warming up to 105 ℃ on one side.Then; The have compound (A-2-1), the 50.1 mass parts 3-hydroxyls-1-adamantyl methacrylic ester that gather (perfluorinated alkylidene ether) chain of gained in the synthetic example 1 of 20 mass parts are dissolved in the monomer solution that forms in the 84.6 mass parts MIBKs, are dissolved in these the 3 kinds of dropping liquids of polymerization starter solution that form in the 10.6 mass parts MIBKs as 10.6 mass parts tert-butyl hydroperoxide-2-ethylhexanoate of polymerization starter and are contained in respectively in each Dropping feeder; And flask interior is remained on 105 ℃ on one side, Yi Bian side by side dripped with 2 hours.After dripping end, stirred 5 hours, under reduced pressure heat up in a steamer 83.5 mass parts solvents then, obtain polymkeric substance (P1-4) solution at 105 ℃.
Then; In polymkeric substance (P1-4) solution of above-mentioned gained; Adding is as p methoxy phenol 0.1 mass parts of stopper, as stannous octoate 0.03 mass parts of urethane catalyzer; Under air draught, begin to stir, on one side and remain on 60 ℃, Yi Bian with 1 hour dropping 2-acryloxy ethyl isocyanate 29.9 mass parts.After dripping end, after 2 hours, be warming up to 80 ℃ 60 ℃ of stirrings; Stirred 10 hours; Disappearance by IR spectrometry affirmation NCO adds MIBK 53.3 mass parts again, obtains containing the methyl isobutyl ketone solution of 50 quality % fluoropolymer property resins (4).Measure the molecular weight of the fluoropolymer property resin (4) of gained with GPC (polystyrene conversion molecular weight), the number of results average molecular weight is 2000, and weight-average molecular weight is 12000.In addition, the fluorine-containing rate of fluoropolymer property resin (4) is 11 quality %, and polymerizability unsaturated group equivalent is 470g/eq.
(embodiment 5)
In glass flask with whipping appts, TM, cooling tube, dropper, add MIBK 100 mass parts as solvent, and under stream of nitrogen gas, stir on one side, be warming up to 105 ℃ on one side.Then; The have compound (A-2-1), the 48.3 mass parts 3-hydroxyls-1-adamantyl methacrylic ester (the represented compound of above-mentioned formula (B1-1-1)) that gather (perfluorinated alkylidene ether) chain of gained in the synthetic example 1 of 20 mass parts are dissolved in the monomer solution that forms in the 166 mass parts MIBKs, are dissolved in these the 3 kinds of dropping liquids of polymerization starter solution that form in the 34 mass parts MIBKs as 10.2 mass parts tert-butyl hydroperoxide-2-ethylhexanoate of polymerization starter and are contained in respectively in each Dropping feeder; And flask interior is remained on 105 ℃ on one side, Yi Bian side by side dripped with 2 hours.After dripping end, stirred 5 hours, under reduced pressure heat up in a steamer 270 mass parts solvents then, obtain polymkeric substance (P1-5) solution at 105 ℃.
Then; In polymkeric substance (P1-5) solution of above-mentioned gained; Adding is as p methoxy phenol 0.1 mass parts of stopper, as stannous octoate 0.03 mass parts of urethane catalyzer; Under air draught, begin to stir, on one side and remain on 60 ℃, Yi Bian with 1 hour dropping 2-acryloxy ethyl isocyanate 31.7 mass parts.After dripping end, after 2 hours, be warming up to 80 ℃ 60 ℃ of stirrings; Stirred 10 hours; Disappearance by IR spectrometry affirmation NCO adds MIBK 70 mass parts again, obtains containing the methyl isobutyl ketone solution of 50 quality % fluoropolymer property resins (5).Measure the molecular weight of the fluoropolymer property resin (5) of gained with GPC (polystyrene conversion molecular weight), the number of results average molecular weight is 1500, and weight-average molecular weight is 4100.In addition, the fluorine-containing rate of fluoropolymer property resin (5) is 11 quality %, and polymerizability unsaturated group equivalent is 500g/eq.
(comparative example 1)
In glass flask with whipping appts, TM, cooling tube, dropper, add MIBK 68.8 mass parts as solvent, and under stream of nitrogen gas, stir on one side, be warming up to 105 ℃ on one side.Then; The have compound (A-2-1), the 28.8 mass parts 2-hydroxyethyl methacrylates that gather (perfluorinated alkylidene ether) chain of gained in the synthetic example 1 of 40 mass parts are dissolved in the monomer solution that forms in the 82.6 mass parts MIBKs, are dissolved in these the 3 kinds of dropping liquids of polymerization starter solution that form in the 55.1 mass parts MIBKs as 10.3 mass parts tert-butyl hydroperoxide-2-ethylhexanoate of polymerization starter and are contained in respectively in each Dropping feeder; And flask interior is remained on 105 ℃ on one side, Yi Bian side by side dripped with 2 hours.After drip finishing, stirred 5 hours, under reduced pressure heat up in a steamer 169.3 mass parts solvents then, obtain polymkeric substance (P ') solution at 105 ℃.
Then; In the polymkeric substance of above-mentioned gained (P ') solution; Adding is as p methoxy phenol 0.1 mass parts of stopper, as stannous octoate 0.03 mass parts of urethane catalyzer; Under air draught, begin to stir, on one side and remain on 60 ℃, Yi Bian with 1 hour dropping 2-acryloxy ethyl isocyanate 31.2 mass parts.After dripping end, after 2 hours, be warming up to 80 ℃ 60 ℃ of stirrings; Stirred 10 hours; Disappearance by IR spectrometry affirmation NCO adds MIBK 54.6 mass parts again, obtains containing the methyl isobutyl ketone solution of 50 quality % fluoropolymer property resins (6).Measure the molecular weight of the fluoropolymer property resin (6) of gained with GPC (polystyrene conversion molecular weight), the number of results average molecular weight is 2200, and weight-average molecular weight is 6500.In addition, the fluorine-containing rate of fluoropolymer property resin (6) is 22 quality %, and free-radical polymerised unsaturated group equivalent is 456g/eq.
For fluoropolymer property resin (1)～(6) of gained in the foregoing description 1～5 and the comparative example 1, characteristic values such as its molecular weight gather and are shown in table 1.
[table 1]
Figure BSA00000588122000341
(embodiment 6)
[modulation of the base resin composition of active energy ray-curable composition]
(Dainippon Ink Chemicals makes " UNIDIC17-806 " with the ultraviolet hardening urethane acrylate resin; Resinous principle is the butylacetate solution of 80 quality %) 125 mass parts, as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater (BASF Amada Co., Ltd. makes " IRGACURE184 ") 5 mass parts, toluene 54 mass parts as solvent, 2-propyl alcohol 28 mass parts, ETHYLE ACETATE 28 mass parts, propylene glycol monomethyl ether 28 mass parts are mixed and dissolving, obtain the base resin composition of active energy ray-curable composition.
[modulation of active energy ray-curable composition and the making of cured coating film]
In base resin composition 268 mass parts of above-mentioned gained; Adding is as solution 2 mass parts that contain the fluorine-containing curable resins of 50 quality % (1) (for resinous principle is 1 mass parts) of gained among the embodiment 1 of fluorochemical surfactant; And uniform mixing, obtain active energy ray-curable composition.Then, use rod to be coated with machine No.13, this active energy ray-curable composition is coated on the polyethylene terephthalate that thickness is 188 μ m (PET) film, put into then in 60 ℃ the drying machine 5 minutes, make solvent evaporates.Then, (under nitrogen atmosphere, high pressure mercury vapour lamp, ultraviolet irradiation amount are 2kJ/m with ultraviolet curing device 2) to the dried coating irradiation ultraviolet radiation, obtain cured coating film.
[evaluation of didirtresistance]
By the following water and the contact angle of n-dodecane, estimate the didirtresistance on the cured coating film surface of above-mentioned gained.
[measurement of contact angle of water and n-dodecane]
Use contact angle determination device (consonance interface science Co., Ltd.'s system " MODEL CA-W150 "), to the contact angle of cured coating film surface measurements water and n-dodecane.
[evaluation of the didirtresistance after wearing and tearing are handled]
As the evaluation of antifouling persistence, cured coating film surface and the above-mentioned measurement of contact angle of likewise carrying out water and n-dodecane handled for wearing and tearing.In addition, wearing and tearing are handled and are to use reciprocal wear testing machine (new eastern science Co., Ltd.'s system " HEIDON Tribogear TYPE:30S "), and non-woven fabrics (Asahi Chemical Ind's system " BEMCOT S ") is installed on anchor clamps, with 1.72N/cm 2Load wear and tear repeatedly and carry out for 5000 times.
[highly basic of cured coating film is handled]
With the cured coating film of above-mentioned gained, heating to the potassium hydroxide aqueous solution of 70 ℃ 2.0mol/L dipping 1 minute, after the washing,, carry out highly basic and handle 100 ℃ of dryings 3 minutes.
[evaluation of scuff resistance]
Use the reciprocal wear testing machine TYPE:30S of Tribogear HEIDON (new eastern science Co., Ltd. system); And be used on the circular clamp that diameter is 27mm and BONSTARNo be installed, the wear testing machine (500g/cm of 0000 (manufacturing of Japanese Steel Wool (ス チ one Le ウ one Le) Co., Ltd.) 2Loading), weares and teares repeatedly 30 times, carry out this test.Number goes out the bar number of the scar that has on the film coated surface after the test, and according to following benchmark evaluation scuff resistance.
A: the bar number of scar is less than 5.
B: the bar number of scar is less than 10.
C: the bar number of scar is more than 10 and less than 50.
D: the bar number of scar is more than 50.
(embodiment 7～10)
Fluorine-containing curable resin (2)～(5) of gained replace the fluorine-containing curable resin (1) used among the embodiment 6 in using embodiment 2～5 respectively; Operate equally with embodiment 6, carry out the modulation of active energy ray-curable composition, the making of cured coating film, the evaluation of didirtresistance and the evaluation of scuff resistance.
(comparative example 2)
The fluorine-containing curable resin (6) of gained replaces the fluorine-containing curable resin (1) used among the embodiment 6 in using comparative example 1; Operate equally with embodiment 6, carry out the modulation of active energy ray-curable composition, the making of cured coating film, the evaluation of didirtresistance and the evaluation of scuff resistance.
(comparative example 3)
Except in embodiment 6 do not add any material in the base resin composition of synthetic active energy ray-curable composition and embodiment 6 operates equally, be cured the making of filming, the evaluation of didirtresistance and the evaluation of scuff resistance.
Said determination and evaluation result are shown in table 2.
[table 2]
Figure BSA00000588122000361
Hence one can see that; Added cured coating film as the active energy ray-curable composition of the embodiment 6～10 of fluoropolymer property resin (1)～(5) of gained among the embodiment 1 and 2 of fluoropolymer property resin of the present invention; The contact angle of its water and n-dodecane is high, and has excellent didirtresistance.Can know that in addition even after wearing and tearing are handled, the contact angle of water and n-dodecane does not reduce greatly yet, antifouling persistence is also higher.Can know that further it has excellent scuff resistance.
Can know on the other hand; Use the comparative example 2 of the fluoropolymer property resin of making in the comparative example 1 (6) that does not have adamantyl; The contact angle of its water and n-dodecane is high; And have excellent didirtresistance, but the water after wearing and tearing are handled and the contact angle of n-dodecane reduce greatly, antifouling persistence is not enough.In addition, scuff resistance is also not enough.
And can know that do not add the comparative example 3 of additive, the contact angle of its water and n-dodecane is low, and didirtresistance is not enough.In addition, scuff resistance is also not enough.

Claims (7)

1. a fluoropolymer property resin is characterized in that, this resin is the polymkeric substance that makes polymerizability polymerization of unsaturated monomers gained, and in the structure of said polymkeric substance, has and gather (perfluorinated alkylidene ether) chain, adamantyl and polymerizability unsaturated group.
2. fluoropolymer property resin as claimed in claim 1; It obtains through making compound (C) and polymkeric substance (P1) reaction; Said polymkeric substance (P1) obtains through gathering (perfluorinated alkylidene ether) chain to have and carrying out copolymerization at the polymerizability unsaturated monomer (B1) that its two end has the compound (A) of polymerizability unsaturated group and has an adamantyl that has reactive functional group (b1) as necessary monomer component, and said compound (C) contains with respect to said functional group (b1) and has reactive functional group (c) and polymerizability unsaturated group.
3. fluoropolymer property resin as claimed in claim 1; It obtains with polymkeric substance (P2) reaction through making the compound (C) more than a kind; Said polymkeric substance (P2) through gather (perfluorinated alkylidene ether) chain to have and have the compound (A) of polymerizability unsaturated group at its two end, the polymerizability unsaturated monomer (B2) and the polymerizability unsaturated monomer (B3) with reactive functional group (b3) that have the polymerizability unsaturated monomer (B1) of the adamantyl that has reactive functional group (b1) or have an adamantyl of reactive functional group be not with (b1) carry out copolymerization as necessary monomer component and obtain, said compound (C) contains with respect to said functional group (b1) or said functional group (b3) and has reactive functional group (c) and polymerizability unsaturated group.
4. like claim 2 or 3 described fluoropolymer property resins; Wherein, Said monomer (B1) or the reactive functional group (b1) that (B2) is had or (b3) for to be selected from least a functional group in hydroxyl, NCO, epoxy group(ing), carboxyl, acid halide group and the anhydride group, and the functional group (c) that had of said compound (C) has with said reactive functional group (b1) or reactivity (b3) and is selected from least a functional group in hydroxyl, NCO, epoxy group(ing), carboxyl, acid halide group and the anhydride group.
5. an active energy ray-curable composition is characterized in that, contains each described fluoropolymer property resin of claim 1～4 and active energy ray curable resin (D) or active energy ray-curable monomer (E).
6. a cured article is characterized in that, through each described fluoropolymer property resin of claim 1～4 or the described active energy ray-curable composition of claim 5 are coated on the base material, and the irradiation active energy beam is solidified to form it.
7. article is characterized in that, have the cured coating film of each described fluoropolymer property resin of claim 1～4 or the described active energy ray-curable composition of claim 5.
CN201110303253.2A 2010-09-30 2011-09-29 Fluoropolymer resin, the active energy ray-curable composition using it and cured article thereof Active CN102532432B (en)

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