CN100368486C - Active energy ray curable coating composition and molded product having coating film made of cured product of said composition - Google Patents
Active energy ray curable coating composition and molded product having coating film made of cured product of said composition Download PDFInfo
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- CN100368486C CN100368486C CNB200380102990XA CN200380102990A CN100368486C CN 100368486 C CN100368486 C CN 100368486C CN B200380102990X A CNB200380102990X A CN B200380102990XA CN 200380102990 A CN200380102990 A CN 200380102990A CN 100368486 C CN100368486 C CN 100368486C
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Abstract
To provide a coating composition which forms a coating film having excellent fingerprint removability and having favorable abrasion resistance and transparency, and a molded product having a coating film made of a cured product of the composition. An active energy ray curable coating composition comprising an active energy ray curable polymerizable monomer (A), a water and oil repellency-imparting agent (B) and an active energy ray polymerization initiator (C), wherein the water and oil repellency-imparting agent (B) contains a water and oil repellency-imparting agent (B-T) having a moiety (b-1) exerting water and oil repellency, an active energy ray curable functional group (b-2) and a moiety (b-3) excellent in compatibility with the polymerizable monomer (A) and a molded product having a coating film made of a cured product of the composition. Active energy ray curable coating composition contains a water and oil repellency-imparting agent (B) and molded product having coating film made of cured product of said composition.
Description
Technical field
The present invention relates to active energy ray-curing coating composition, its activated energy-ray irradiation and solidifying produces transparent filming, its excelling in abrasion resistance, and it is good particularly to be attached to the removal of surperficial fingerprint for the anti-activity that lipid is polluted.The invention still further relates on the substrate surface of glass or plastics by filming that the cured article of this coating composition is formed, can grow the molding of the wearability of basic exhibit excellent, removing property of fingerprint that didirtresistance that lipid is polluted is particularly good.
Background technology
Through the opening features of the metal sheet of mirror finish and unorganic glass system array window, disk array cabinet, automobile, antireflection film, optics colour filter, optical lens, liquid-crystal display, CRT monitor, projection TV, plasma display, EL indicating meter, CD etc., environment according to its placement, usually by finger class dirts such as fingerprint, sebum, sweat, makeup adhere to, in a single day such lipid dirt adhere to, just be not easy to remove, the optics of particularly having antireflection film, the dirt that adheres to is noticeable, thereby goes wrong.Therefore,, all technology have been proposed, even have the stain-proofing layer that the lipid dirt is difficult to adhere to the performance of also wiping easily in the formation of the surface of optics as solving the means that these lipid dirts adhere to the problem of generation.Have in the optics of stain-proofing layer on the surface, be positioned at outermost stain-proofing layer, its surface portion is easy to generate scar when wiping.
The open communique 2002-248703 communique of Japan special permission is to make the cured article layer of coating molding have wearability, oilness, uses and has added silicone compound or the fluorochemicals coating composition as lubricant.Yet the affinity of silicone compound that above-mentioned communique exemplifies and fluorochemicals and matrix resin is low, separates out from the surface of matrix resin easily when coating, easily damages the transparency of covering part, existing problems.And, can not manifest sufficient didirtresistance as lubricant interpolation silicone compound.
The open flat 11-293159 communique of communique of Japan's special permission has disclosed the hard coating agent that contains fluorochemical surfactant that is used for optical recording media.Yet the hard coat wearability that contains this fluorochemical surfactant is not enough, for obtaining didirtresistance, cross-linking type fluorine-containing tensio-active agent and 2 kinds of fluorochemical surfactants of non-crosslinked type fluorochemical surfactant must be arranged.
The open communique 2000-191668 communique of Japan's special permission has been put down in writing and has been contained end through the oxygenatedchemicals of urethane bonds bonded alkoxyl silicone alkyl structure and the didirtresistance composition of mineral compound or organic compound particulate composition.Yet this didirtresistance composition, because the layer of being made up of mineral compound such as silicon-dioxide will obtain adhesivity by the contained organoalkoxysilane combination of said composition, when there is not inorganic compound layer in substrate surface, even can obtain didirtresistance for the moment, but there is the problem that can not manifest long-term didirtresistance.And this didirtresistance composition also only with didirtresistance as purpose, do not have physical strength, surface portion more easily produces scar.Therefore in the time of must having physical strength such as wearability at substrate surface, substrate surface must be provided with hard coat, and the operation complicated problems that becomes is arranged.
The present invention is for solving the problem points of above-mentioned conventional art, purpose provides at all processed base materials, particularly can form excelling in abrasion resistance and good on the substrate surface of glass, metal or plastics, particularly the coating composition of the transparent coating of the fingerprint of the long-term exhibit excellent property removed to the didirtresistance of lipid dirt.The purpose of this invention is to provide glass of filming or plastics system molding that its outside surface is made up of the cured article of coating composition.
Summary of the invention
The invention provides active energy ray-curing coating composition, it is with respect to the polymerizable monomer of active energy ray solidified nature (A) 100 mass parts, contains the coating composition of the active energy ray polymerization starter (C) of the water and oil repellent agent (B) of 0.01～10 mass parts and 0.1～10 mass parts; It is characterized in that, above-mentioned polymerizable monomer (A) contains the following multi-functional polymerizable monomer (a-1) more than or equal to 20 quality %: be the monomer that the polymerizability functional group that is selected from acryl and methacryloyl more than 2 or 2 is arranged in the molecule in the total mass of contained this polymerizable monomer (A) of above-mentioned coating composition; Above-mentioned water and oil repellent agent (B) contains the position (b-1) that manifests water and oil-resistant, active energy ray solidified nature functional group (b-2) and by the water and oil repellent agent (B-T) at the position (b-3) of at least 1 formation of part that is selected from following formula (1)～(4) expression,
-R
3-... formula (1)
-(CH
2CH
2O)
x-... formula (2)
-(CH
2CH (CH
3) O)
y-... formula (3)
-(C (=O) C
uH
2uO)
t-... formula (4)
(R in the formula
3Be the alkylidene group of carbonatoms 6～20, x and y are 5～100 integers, and u is 3～5 integer, and t is 1～20 integer).
The present invention 1 coating composition is because water and oil repellent agent (B-T) has the intermiscibility of appropriateness, the transparency that water and oil repellent agent when coating substrate surface (B-T) is filmed before can not damaging curing at the film coated surface segregation to other compositions of said composition.Thereafter, when solidifying with the active energy ray irradiation, active energy ray solidified nature functional group in the water and oil repellent agent (B-T) combines with the resin matrix in the said composition and is fixed, thereby the film coated surface water and oil-resistant that the cured article of said composition is formed is good, and the fingerprint of exhibit excellent is removed property for a long time.
The position (b-1) that manifests above-mentioned water and oil-resistant in the above-mentioned water and oil repellent agent (B-T) better has at least 1 in the part shown in following formula (5)～(9),
C
kF
2k+1-... formula (5)
-(CF
2CF
2O)
p-... formula (6)
-(CF
2CF (CF
3) O)
q-... formula (7)
-(CF
2CF
2CF
2O)
r-... formula (8)
-(CF
2O)
s-... formula (9)
(in the formula, k is 1～16 integer, and p, q, r and s are 1～100 integers).
In the above-mentioned water and oil repellent agent (B-T), better there is part shown in following formula (10) or the following formula (11) at the position (b-1) that manifests above-mentioned water and oil-resistant,
R
f(OC
3F
6)
n-O-(CF
2)
m-(CH
2)
L-O-... formula (10)
R
f(OC
2F
4)
e-O-(CF
2)
g-(CH
2)
h-O-... formula (11)
(R in the formula
fBe the Polyfluoroalkyl (including the Polyfluoroalkyl of Sauerstoffatom) of carbonatoms 1～16, n is 1～50 integer, and e is 1～50 integer, and m and L are 0～3 integers, and g and h are 0～3 integers, 6 〉=m+L＞0,6 〉=g+h＞0).
Coating composition of the present invention better with respect to above-mentioned polymerizable monomer (A) 100 mass parts, also contains the colloidal silica (D) of 1～500 mass parts.
Above-mentioned colloidal silica (D) better is the silane compound that contains sulfydryl (S1) that is incorporated into Siliciumatom with the organic radical with sulfydryl and water-disintegrable base or hydroxyl, the silane compound that contains (methyl) acryl (S2) that perhaps has the organic radical of (methyl) acryl and water-disintegrable base or hydroxyl to be incorporated into Siliciumatom carry out surface modification and the modification colloidal silica.
The above-mentioned silane compound (S1) that contains sulfydryl better is the compound of following formula (12) expression,
HS-R
1-SiR
2 fR
5 3-fFormula (12)
(in the formula, R
1Be the divalent alkyl, R
2Be hydroxyl or water-disintegrable base, R
5Be 1 valency alkyl, f is 1～3 integer).
Above-mentioned containing, the silane compound (S2) of (methyl) acryloxy better was the compound of following formula (13) expression,
CH
2=C (R
3)-R
7-SiR
2 fR
5 3-fFormula (13)
(in the formula, R
6Be hydrogen atom or methyl, R
7Be the divalent alkyl, R
2Be hydroxyl or water-disintegrable base, R
5Be 1 valency alkyl, f is 1～3 integer).
The invention provides active energy ray-curing coating composition, it is the coating composition of filming through solidifying to form, it is characterized in that, film coated surface after the curing and the contact angle initial stage between the oleic acid are more than or equal to 60 degree, spend more than or equal to 55 after the humidity test, the haze value of filming after the above-mentioned curing is smaller or equal to 3%, and Taber (Taber) wearing test (abrasion wheels: CS-10F in ISO 9352 regulations, single isolated wheel loading 500g, 500 change) before and after the variation of the haze value of filming after the above-mentioned curing smaller or equal to 10%.
The present invention 2 coating composition, the water and oil-resistant that solidifies the back film coated surface is good, and can manifest its good water and oil-resistant for a long time.And the transparency, the wearability of filming after solidifying are also good.
Above-mentioned coating composition better contains active energy ray solidified nature polymerizable monomer (A).
The aforesaid coating composition of coating characteristic after the curing better is to contain above-mentioned (A), (B) and coating composition (C).
And, the invention provides the molding of filming that has thick 0.1～50 μ m that forms by the cured article of above-mentioned coating composition at the substrate surface of glass or plastics.
Embodiment
The present invention 1 coating composition (hereinafter to be referred as " coating composition 1 ") is with respect to active energy ray solidified nature polymerizable monomer (A) 100 mass parts, contains the active energy ray-curing coating composition of water and oil repellent agent (B) 0.01～10 mass parts and active energy ray polymerization starter (C) 0.1～10 mass parts.
In the coating composition 1; active energy ray solidified nature polymerizable monomer (A) (to call polymerizable monomer (A) in the following text) is in the presence of following active energy ray polymerization starter (C); the irradiation of activated energy-ray and the monomer of initiated polymerization specifically comprise having in 1 molecule more than 2 as the acryl of polymerizability functional group or the multi-functional polymerizable monomer (a-1) of methacryloyl (hereinafter referred to as monomer (a-1) with other polymerizable monomers headed by the following simple function polymerizable monomer (a-2).But do not comprise the compound that meets following water and oil repellent agent (B).In the following description, acryl and methacryloyl are referred to as (methyl) acryl.
In the coating composition 1, monomer (a-1) is equivalent to the described multi-functional compounds of 0013-0052 section (a) in the open flat 10-81839 communique of communique of Japan's special permission.But promptly be the multi-functional polymerizable monomer that has in 1 molecule more than 2 as (methyl) acryl of the polymerizability functional group of active energy ray initiated polymerization.
In the coating composition 1, from manifesting the viewpoint that highly abrasion-resistant decreases property, as monomer (a-1), better be that 3 above polymerizability functional groups are arranged in the molecule, the molecular weight of each functional group is below 120.As the monomer that satisfies such condition (a-1), can enumerate following compound:
Be the polyester of tetramethylolmethane or polypentaerythritol and (methyl) acrylic acid resultant of reaction, and (methyl) acryl more than 3 is arranged, be more preferably 4～20 multi-functional compounds.Specifically can enumerate trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate.
On the other hand; what intramolecularly had a urethane bonds contains (methyl) acryl compound (calling the acrylamido ethyl formate in the following text); this urethane bonds is with the effect of its hydrogen bond; as the work of simulation cross-linking set; even the molecular weight of each functional group is not less than and above-mentionedly also may manifests sufficiently high wearability, can use satisfactorily.Satisfy the monomer (a-1) of such condition, following compound is better:
Be tetramethylolmethane or polypentaerythritol and polyisocyanates, (methyl) vinylformic acid hydroxyalkyl acrylate resultant of reaction the acrylamido ethyl formate and (methyl) acryl more than 3 arranged, be more preferably 4～20 multi-functional compounds.
Be poly-(methyl) acrylate of hydroxyl of tetramethylolmethane or polypentaerythritol and polyisocyanates reaction product the acrylamido ethyl formate and have more than 3, be more preferably the multi-functional compounds of 4～20 (methyl) acryls.
The 1st coating composition can contain monomer (a-1) polymerizable monomer in addition as polymerizable monomer (A).As monomer (a-1) polymerizable monomer (A) in addition, the simple function polymerizable monomer (the following monomer (a-2) that also claims) of 1 (methyl) acryl is arranged in available 1 molecule or the compound of the polymerizability functional group beyond (methyl) acryl more than 1 is arranged.Yet, the polymerizability functional group beyond (methyl) acryl, the solidified nature of a lot of activated energy-rays is not enough, or is difficult to obtain, so better with monomer (a-2) as monomer (a-1) polymerizable monomer (A) in addition.
As monomer (a-2), can enumerate by general formula CH
2=C (R
4) COOC
zH
2z+1(R
4Be hydrogen atom or methyl, z is 1～13 integer, C
zH
2z+1Can be linear chain structure, also can be branched structure) expression following compounds: (methyl) alkyl acrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid butoxy ethyl ester, (methyl) vinylformic acid butanediol ester, butoxy triethylene glycol list (methyl) acrylate, (methyl) vinylformic acid t-butyl amino ethyl ester, (methyl) vinylformic acid 3-chloro-2-hydroxy propyl ester, (methyl) 2 cyanoethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 2,3-dibromo propyl ester, (methyl) vinylformic acid two cyclopentenes esters, (methyl) vinylformic acid N, N-diethylamino ethyl ester, (methyl) vinylformic acid N, the N-dimethylamino ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-(2-ethoxy ethoxy) ethyl ester, (methyl) 2-EHA, glycerine (methyl) acrylate, (methyl) glycidyl acrylate, (methyl) vinylformic acid 17 fluorine esters in the last of the ten Heavenly stems, (methyl) vinylformic acid 2-hydroxy methacrylate, chlorination 2-hydroxyl-3-(methyl) acryloyl-oxy oxypropyl trimethyl ammonium, (methyl) vinylformic acid 2-hydroxy propyl ester, γ-(methyl) acryloyl-oxy propyl trimethoxy silicane, (methyl) vinylformic acid 2-methoxyl group ethyl ester, methoxyl group Diethylene Glycol (methyl) acrylate, methoxyl group triethylene glycol (methyl) acrylate, methoxyl group TEG (methyl) acrylate, methoxyl group dipropylene glycol (methyl) acrylate, methoxylation ring triolefin in the last of the ten Heavenly stems (methyl) acrylate, morpholine (methyl) acrylate, Nonylphenoxy polyoxyethylene glycol (methyl) acrylate, Nonylphenoxy polypropylene glycol (methyl) acrylate, (methyl) vinylformic acid octafluoro pentyl ester, phenoxy group hydroxypropyl (methyl) acrylate, (methyl) vinylformic acid phenoxy ethyl, phenoxy group Diethylene Glycol (methyl) acrylate, phenoxy group TEG (methyl) acrylate, phenoxy group six ethylene glycol (methyl) acrylate, phenoxy group (methyl) acrylate, polypropylene glycol (methyl) acrylate, 2-sodium sulfonate oxyethyl group (methyl) acrylate, (methyl) vinylformic acid tetrafluoro propyl ester, (methyl) vinylformic acid tetrahydrofuran (THF) methyl esters, (methyl) vinylformic acid trifluoro ethyl ester, vinyl-acetic ester, the N-caprolactam, the N-vinyl pyrrolidone, (methyl) vinylformic acid dicyclopentadienyl ester, isobornyl acrylate etc.
In the total mass of the polymerizable monomer (A) that coating composition 1 is contained, monomer (a-1) is 20～100 quality %.In the contained polymerizable monomer (A) of coating composition 1, in this scope, good by the wearability of filming of forming of the cured article of coating composition 1 (following also claim to solidify after film) as the ratio of monomer (a-1).Monomer (a-1) is more preferably 50～100 quality %, and good especially is 70～100 quality %.
Water and oil repellent agent in the coating composition 1 (B) comprises the water and oil repellent agent (B-T) of following explanation and other following water and oil repellent agents.Coating composition of the present invention with respect to polymerizable monomer (A) 100 mass parts, contains such water and oil repellent agent (B) 0.01～10 mass parts, is preferably and contains 0.1～5.0 mass parts.The amount of water and oil repellent agent (B) is as in this scope, and the water and oil-resistant and the wearability of filming after the curing are good.Less than 0.01 mass parts, the water and oil-resistant of filming after the curing is poor as water and oil repellent agent (B).On the other hand, surpass 10 mass parts as water and oil repellent agent (B), it is plasticized to film after the curing, and wearability descends, transparent variation.
Water and oil repellent agent (B-T) is to have the position (b-1) that manifests water and oil-resistant, active energy ray solidified nature functional group (b-2) in 1 molecule simultaneously and by the compound at the position (b-3) of at least one formation in the part of following formula (1)～(4) expression.
-R
3-... formula (1)
-(CH
2CH
2O)
x-... formula (2)
-(CH
2CH (CH
3) O)
y-... formula (3)
-(C (=O) C
uH
2uO)
t-... formula (4)
(R in the formula
3Be the alkylidene group of carbonatoms 6～20, x and y are 5～100 integers, and u is 3～5 integer, and t is 1～20 integer).
In the water and oil repellent agent (B-T), the position (b-1) (the following position (b-1) that claims sometimes) that manifests water and oil-resistant is meant usually the position of the fluorine-containing organic radical formation of fluorochemicals as water-resisting agent or oil-proofing agent (for example multipolymer of the single polymers of the polymerizable monomer of (methyl) esters of acrylic acid polyfluorinated alkyl of polyfluorinated alkyl or it and polymerizable monomers such as other acrylate, maleic anhydride, chloroprene, divinyl, methyl vinyl ketone, fluorochemical polyether compound, fluorosilicone compound etc.).
In the above-mentioned water and oil repellent agent (B-T), position (b-1) better has at least 1 in the part that is selected from following (5)～(9) expression;
C
kF
2k+1-... formula (5)
-(CF
2CF
2O)
p-... formula (6)
-(CF
2CF (CF
3) O)
q-... formula (7)
-(CF
2CF
2CF
2O)
r-... formula (8)
-(CF
2O)
s-... formula (9)
(in the formula, k is 1～16 integer, and p, q, r and s are 1～100 integers).
The part of following formula (5) is a perfluoroalkyl, and its carbonatoms k better is 1～16.In this scope, this group crystallinity is poor as carbon atom, and the transparency of filming after the curing can not damaged.
The part of following formula (6) is an expression ptfe ring oxirane unit, and the part of formula (7) and (8) is expression Propylene oxide hexafluoride unit, and the part of formula (9) is the difluoro methylene unit.P, q, r and the s of the expression polymerization degree better are below 100.In above-mentioned scope, the coating waterproofing grease proofness after the curing is good as p, q, r and s, the fingerprint of the long-term exhibit excellent property removed.P, q, r and s are more preferably 1～80 integer.
In the water and oil repellent agent (B-T), position (b-1) can have any 1 in the part of above-mentioned formula (5)～(9), also can have more than 2 at same intramolecularly.
In the water and oil repellent agent (B-T), position (b-1) better has the part shown in the following formula (10);
R
f(OC
3F
6)
n-O-(CF
2)
m-(CH
2)
L-O-... formula (10)
(in the formula, R
fBe the Polyfluoroalkyl (including the Polyfluoroalkyl of Sauerstoffatom) of carbonatoms 1～16, n is 1～50 integer, and m and L are 0～3 the integers that satisfies the condition of following formula relation, 6 〉=m+L＞0);
In the formula 10, OC
3F
6Refer to OCF
2CF
2CF
2Or OCF (CF
3) CF
2
Polyfluoroalkyl (R
f) be meant the base that the hydrogen atom more than 2 of alkyl is replaced by fluorine atom.R
fBase better is a linear chain structure, also branched structure can be arranged, and the occasion of branched structure is being arranged, and component is present in R
fThe short chain that the terminal portions of base and terminal portions are carbonatoms 1～4 is better.
R
fCarbonatoms better be 1～8.As R
fThe base carbonatoms in this scope, R
fThe crystallinity of base is relatively poor, and that films after the curing is transparent good.
R
fBase can contain other halogen atoms beyond the fluorine atom.Other halogen atoms better are hydrogen atoms, and R
fBetween C-C, can insert etheric oxygen atom, ester bond, sulfoamido or thioether sulphur atom in the base.
R
fNumber of fluorine atoms in the base is with [(R
fNumber of fluorine atoms in the base)/(with R
fContained number of hydrogen atoms in the identical corresponding alkyl of base carbonatoms)] * during 100 (%) expression, more fortunately more than 60%, especially fortunately more than 80%.
In addition, R
fBase better be the base (being perfluoroalkyl) that replaced by fluorine atom of whole hydrogen atoms of alkyl or endways part the group of perfluoroalkyl is arranged.
As R
fThe object lesson of base can be enumerated following base.
CF
3-, C
2F
5-, C
3F
7-[comprise CF
3(CF
2)
2-, (CF
3)
2The group of Structural Isomerisms such as CF-], C
4F
9-[comprise CF
3(CF
2)
3-, (CF
3)
2CFCF
2-, (CF
3)
3C-or CF
3CF
2(CF
3) group of Structural Isomerism such as CF-], C
5F
11-[as CF
3(CF
2)
4-], C
6F
13-[as CF
3(CF
2)
5-], C
7F
15-[as CF
3(CF
2)
6-], C
8F
17-[as CF
3(CF
2)
7-], C
9F
19-[as CF
3(CF
2)
8-], C
10F
21-[as CF
3(CF
2)
9-], C
12F
25-[as CF
3(CF
2)
11-], C
14F
29-[as CF
3(CF
2)
13-], C
16F
33[as CF
3(CF
2)
15-], Cl (CF
2)
v-, H (CF
2)
v-(v is 1～16 integer), (CF
3)
2CF (CF
2)
w-(w is 1～13 integer) etc.
R
fBase is the concrete example of occasion that inserts the base of etheric oxygen atom, ester bond, sulfoamido or thioether carbon atom between C-C, can exemplify following base.
CF
3(CF
2)
4OCF(CF
3)-、
F[CF(CF
3)CF
2O]
GCF(CF
3)CF
2CF
2-、
F[CF(CF
3)CF
2O]
HCF(CF
3)-、
F[CF(CF
3)CF
2O]
HCF
2CF
2-、
F(CF
2CF
2CF
2O)
HCF
2CF
2-、
F(CF
2CF
2O)
HCF
2CF
2-、
F(CF
2)
5SCF(CF
3)-、
F[CF(CF
3)CF
2S]
GCF(CF
3)CF
2CF
2-、
F[CF(CF
3)CF
2S]
HCF(CF
3)-、
F[CF(CF
3)CF
2S]
HCF
2CF
2-、
F(CF
2CF
2CF
2S)
HCF
2CF
2-、
F(CF
2CF
2S)
JCF
2CF
2-
(G is 1～3 integer, and H is 1～4 integer, and J is 1～7 integer) etc.
In coating composition 1, at above-mentioned illustrative R
fIn the base, better also be CF
3-, C
2F
5-, C
3F
7-.As R
fBe these groups, raw material is easy to get when the position of synthesis type (10), also synthetic easily this position, therefore better.
In the water and oil repellent agent (B-T), position (b-1) better contains the part shown in the following formula (11);
R
f(OC
2F
4)
e-O-(CF
2)
g-(CH
2)
h-O-... formula (11)
(in the formula, R
fIt is the Polyfluoroalkyl (comprise the Polyfluoroalkyl that contains Sauerstoffatom, e is 1～50 integer, and g and h are 0～3 the integers that satisfies the condition of following formula relation, 6 〉=g+h＞0) of carbonatoms 1～16
R in the formula (II)
f, and to the R in the formula (10)
fWhat illustrate is identical.
Coating composition 1, as water and oil repellent agent (B-T), can be also with the multiple water and oil repellent agent (B-T) that different sites (b-1) arranged.
In the water and oil repellent agent (B-T); active energy ray solidified nature functional group (b-2) (the following functional group (b-2) that claims sometimes) so long as the functional group that free radical reaction arranged all can, specifically can exemplify (methyl) acryl, allyl group, vinyl, vinyl ether group, halogen, sulfydryl etc.Consider that from the stability of free radical reaction and formed chemical bond (methyl) acryl is good especially.
Water and oil repellent agent (B-T), owing to contain functional group (b-2), when solidifying in the activated energy-ray irradiation of coating composition 1, curing reaction also takes place in functional group (b-2), and with polymerizable monomer (A) covalent attachment of the resinous principle that constitutes coating composition 1.Therefore, water and oil repellent agent (B-T) combines through covalent linkage with filming after the cured article of coating composition 1 promptly solidifies, and water and oil repellent agent (B-T) is fixed on the film coated surface exists.Therefore water and oil repellent agent (B-T) can be from film coated surface dissipation, so better.And water and oil repellent agent (B-T) is owing to be incorporated into this and film, the water and oil repellent agent that the film coated surface after the curing can long-term exhibit excellent, and good fingerprint is removed performance and is continued for a long time.
Water and oil repellent agent (B-T) can have some in the top illustrative functional group as functional group (b-2), perhaps at same intramolecularly functional group more than 2 kinds can be arranged.And coating composition 1 as water and oil repellent agent (B-T), can and have the water and oil repellent agent (B-T) of different functional groups (b-2) with several.
Water and oil repellent agent (B-T) at least 1 position (b-3) (the following position (b-3) that claims sometimes) in the part arranged shown in the formula of being selected from (1)～(4), have the function that manifests with the intermiscibility of polymerizable monomer (A).
-R
3-... formula (1)
-(CH
2CH
2O)
x-... formula (2)
-(CH
2CH (CH
3) O)
y-... formula (3)
-(C (=O) C
uH
2uO)
t-... formula (4) m
(R in the formula
3Be the alkylidene group of carbonatoms 6～20, x and y are 5～100 integers, and u is 3～5 integer, and t is 1～20 integer).
Water and oil repellent agent (B-T) manifests the position (b-1) of water and oil-resistant, because the affinity of the resin matrix that forms with polymerizable monomer (A) is low, when coating composition solidifies, ooze out on the resin matrix surface easily, the tendency of the transparency of filming after the easy infringement curing is arranged.
Have the water and oil repellent agent (B-T) at the good position (b-3) of intermiscibility with polymerizable monomer (A),, polymerizable monomer (A) is also had the intermiscibility of appropriateness even when selecting the low position (b-1) of affinity with polymerizable monomer (A).
Coating composition 1 is because water and oil repellent agent (B-T) has the intermiscibility of appropriateness to polymerizable monomer (A), when coating composition 1 is coated substrate surface, water and oil repellent agent (B-T) can not damage the transparency of filming before solidifying at this film coated surface segregation.Therefore do not damage the transparency of filming after the curing yet.
The part of above-mentioned formula (1) is that carbonatoms is 6～20 the alkylidene group that straight or branched is arranged.As carbonatoms in this scope, water and oil repellent agent (B-T) has the intermiscibility of appropriateness to polymerizable monomer (A), and crystallinity that should base is relatively poor, and the transparency of filming after therefore solidifying and the water and oil-resistant of this film coated surface are good, and fingerprint that can long-term exhibit excellent is removed property., low as carbonatoms to the intermiscibility of polymerizable monomer (A) below 5, solidify the preceding transparency of filming so can damage.This means and to damage the transparency of filming after the curing.This basic crystallinity grow on the other hand, surpasses 20, owing to also can damage the transparency of filming after the curing as carbonatoms.
The part representative ring oxirane unit of above-mentioned formula (2).The x of the expression polymerization degree is 5～100, is preferably 5～80.In this scope, water and oil repellent agent (B-T) has appropriate intermiscibility to polymerizable monomer (A) as x, so the water and oil-resistant of the transparency of filming after solidifying and this film coated surface is good, and the property of the fingerprint of exhibit excellent removal for a long time.Below 4, the intermiscibility step-down of water and oil repellent agent (B-T) damages the transparency of filming after solidifying as x.On the other hand, surpass 100 as x, then the intermiscibility of water and oil repellent agent (B-T) is too high, and water and oil repellent agent (B-T) is difficult separates out in film coated surface, can not fully manifest the water and oil-resistant of filming after the curing.
The part of above-mentioned formula (3) is represented propylene oxide units.The y of the expression polymerization degree is 5-100, is preferably 5-80.If y is in this scope, water and oil repellent agent (B-T) has the intermiscibility of appropriateness to polymerizable monomer (A), so the water and oil-resistant of the transparency of filming after solidifying and this film coated surface is good, and the fingerprint property removed of the long-term exhibit excellent of energy.If y is below 4, the intermiscibility step-down of water and oil repellent agent (B-T) damages the transparency of filming after solidifying.On the other hand, if y surpasses 100, then the intermiscibility of water and oil repellent agent (B-T) is too high, and water and oil repellent agent (B-T) is difficult at the film coated surface segregation, can not manifest the water and oil-resistant of filming after the curing.
The part of above-mentioned formula (4), the unit that expression is obtained by lactone open loop body.The consideration that is easy to get calmly, this basic carbonatoms better is 3～5.And the t of the expression polymerization degree better is below 20.In this scope, this basic crystallinity is only strong as t, and that films after the curing is transparent good.
Water and oil repellent agent (B-T) can have some as position (b-3) in the part of above-mentioned formula (1)～(4), and the part more than 2 kinds perhaps can be arranged in a part.And coating composition 1 can and with several water and oil repellent agents (B-T) that different positions (b-3) arranged as water and oil repellent agent (B-T).
The combining form at each position is not particularly limited in the water and oil repellent agent (B-T).The combining form at each position specifically can be enumerated following example in the water and oil repellent agent (B-T).
1. straight chain type: be that position (b-1), position (b-3) and functional group (b-2) are with straight chain shape successive type.Hereinafter referred to as straight chain type.
In this straight chain type, as the starting compound that forms position (b-1), better use and contain position (b-1) and the terminal compound that is become hydroxyl, the end that better can exemplify above-mentioned formula (10) or above-mentioned formula (11) is become the compound of hydroxyl, and perhaps end becomes the poly-epoxy HFC-236fa of hydroxyl etc.
This class has on the hydroxyl of end of position (b-1) and the terminal compound that becomes hydroxyl, by making monomer polymerizations with it such as oxyethane as position (b-3), propylene oxide, lactone, can be adjacent to make up position (b-3) with position (b-1).Perhaps also can with as polymkeric substance such as the polyoxyethylene glycol of position (b-3), polypropylene glycols with two functional isocyanate etc. through urethane bonds in the position (b-1) continuously.The chemical structure of the starting compound at also with good grounds formation position (b-1), the acidity of terminal hydroxyl is too high sometimes, and monomeric polymerizations such as oxyethane, propylene oxide, lactone can not be carried out smoothly.At this moment, in the presence of catalyzer, make decarboxylation of ethylene carbonate ester and addition, can insert oxyethane Unit 1, the acidity of terminal hydroxyl is reduced, but also monomer polymerization such as ethane via epoxyethane, propylene oxide, lactone and make up position (b-3).
By such operation, the end of position (b-3) is a hydroxyl.In addition; import the method for functional group (b-2) (for example (methyl) acryl); the method that can exemplify method that usefulness (methyl) vinylformic acid, (methyl) acrylate chloride etc. import through ester bond, import through urethane bonds with 2-(methyl) propionyl acetoacetic ester isocyanic ester, the method that imports with urethane bonds through two functional isocyanate with (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester etc.
Also can exemplify compound with end quilt (methyl) acryl modification of polymkeric substance such as polyoxyethylene glycol, polypropylene glycol; and the terminal hydroxyl of position (b-1) between; through urethane bonds, be adjacent to once in order the method for position (b-3) and functional group (b-2) continuously with two functional isocyanate etc. with position (b-1).
2. copoly type: the free-radical polymerised macromonomer of preparing that the free-radical polymerised macromonomer at position (b-1) is arranged and position (b-3) being arranged can make these macromonomer copolymerization.Can be different again in the gained multipolymer go into functional group (b-2).Hereinafter referred to as copoly type.
As the macromonomer that contains position (b-1), the end that specifically can exemplify above-mentioned formula (10) or above-mentioned (11) is by the monomer of (methyl) acryl modification, (methyl) acrylic acid fluorine-containing alkyl ester etc.
As the macromonomer that contains position (b-3), the end of ring-opening polymerization polymer that an end that specifically can exemplify polymkeric substance such as polyoxyethylene glycol, polypropylene glycol becomes the monomer of (methyl) acryl, (methyl) acrylic acid alkyl ester, lactone is by the monomer of (methyl) acryl modification etc.
Its terminal method that imports after the above-mentioned two class macromonomer copolymerization can be enumerated by functional group (b-2).Can exemplify usefulness (methyl) vinylformic acid, (methyl) acrylate chloride etc. through (methyl) acryls of the above-mentioned 2 kinds of macromonomers of ester bond method of importing of a terminal hydroxyl of addition not, the method that imports through urethane bonds with 2-methyl-vinylformic acid ethyl isocyanate.
Perhaps also can exemplify and make (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-pyruvic alcohol, (methyl) vinylformic acid 4-hydroxyl butyl ester etc., the method for using method that (methyl) vinylformic acid, (methyl) acrylate chloride etc. import through ester bond thereafter, importing with 2-methacrylic acid ethyl isocyanate with above-mentioned two class macromonomer copolymerization.
In above-mentioned straight chain type and the above-mentioned copoly type, better all be that functional group (b-2) is adjacent with position (b-3) and combine.This be since functional group (b-2) during with adjacent combination the in position (b-3), follow adjacent with position (b-1) carry out in conjunction with the time compare, the dividing a word with a hyphen at the end of a line property of surface of position (b-1) uprises, the water and oil-resistant that solidifies back film coated surface is good.
Water and oil repellent agent (B) can contain the known in addition water and oil repellent agent of above-mentioned water and oil repellent agent (B-T).The known water and oil repellent agent of this class can exemplify fluoro-resin such as tetrafluoroethylene, vinylidene fluoride, use fluorochemicals that perfluoroalkyl is arranged etc. fluorine-containing water and oil repellent agent, use the silicone water and oil repellent agent that has siloxane bond, side chain that the organopolysiloxane of alkyl such as methyl, ethyl, propyl group or fluoroalkyl is arranged on the main chain, with the wax class water and oil repellent agent of beeswax and paraffin etc., with the water and oil repellent agent of the metallic salt of the salt of salt, aluminium and the lipid acid of zirconium and lipid acid.But in the known water and oil repellent agent, do not contain the compound that meets above-mentioned water and oil repellent agent (B-T) in this specification sheets.Containing the occasion of these known water and oil repellent agents, total mass 100 mass parts with respect to water and oil repellent agent (B) better contain below 30 mass parts.
Coating composition 1 contains active energy ray polymerization starter (C) 0.1～10 mass parts with respect to polymerizable monomer (A) 100 mass parts except that above-mentioned composition.In this scope, solidified nature is enough as the amount of active energy ray polymerization starter (C), and all active energy ray polymerization starters (C) all decompose during curing, so better.
Here the active energy ray polymerization starter of saying (C) extensively comprises known Photoepolymerizationinitiater initiater.
The concrete example of known Photoepolymerizationinitiater initiater has aryl ketones Photoepolymerizationinitiater initiater (as phenyl methyl ketone class, Benzophenones, alkylamino Benzophenones, benzil class, bitter almond oil camphor class, benzoin ethers, benzil dimethyl ketal class, benzoylbenzoic acid ester class, α-acyl group oxime ester class etc.), sulfur-bearing Photoepolymerizationinitiater initiater (as sulfide-based, thioxanthene ketone etc.), other Photoepolymerizationinitiater initiaters of acylphosphine oxide class (as acyl group diaryl phosphine oxide etc.).These Photoepolymerizationinitiater initiaters can be also with more than 2 kinds.And Photoepolymerizationinitiater initiater can be used in combination with photosensitizerss such as amines.Concrete Photoepolymerizationinitiater initiater for example has following compound, but is not limited to these.
4-phenoxy group Er Lvyixianben, 4-tertiary butyl Er Lvyixianben, 4-tertiary butyl tribromo-acetyl benzene, diethoxy phenyl methyl ketone, 2-hydroxy-2-methyl-1-phenyl third-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone, 1-(4-dodecylphenyl)-2-methyl-prop-1-ketone, 1-{4-(2-hydroxyl-oxethyl) phenyl }-2-hydroxy-2-methyl third-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-{ 4-(methylthio group) phenyl }-2-morpholinyl third-1-ketone.
Benzil; bitter almond oil camphor; benzoin methylether; ethoxybenzoin; benzoin iso-propylether; the bitter almond oil camphor ethyl isobutyl ether; the benzil dimethyl ketal; benzophenone; benzoylbenzoic acid; the benzoylbenzoic acid methyl esters; 4-phenyl benzophenone; hydroxy benzophenone; propylene acidylate benzophenone; 3; 3 '-dimethyl-4-methoxyl group benzophenone; 3; 3 '; 4; 4 '-four (t-butylperoxy carbonyl) benzophenone; 9; the 10-phenanthrenequione; camphorquinone; dibenzosuberone; 2-ethyl-anthraquinone; 4 '; 4 " diethyl isophthaloyl benzene; (1-phenyl-1,2-propanedione-2-(o-ethoxy carbonyl) oxime); α-acyl group oxime ester; oxoethanoic acid aminomethyl phenyl ester.
4-benzoyl-4 '-methyldiphenyl base sulphur, thioxanthone, 2-clopenthixal ketone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-two clopenthixal ketones, 2,4-diethyl thioxanthone, 2,4-di-isopropyl thioxanthone, 2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide, benzoyl diphenyl phosphine oxide, 2,6-dimethyl benzene formyl diphenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide.
Coating composition 1 also can contain as required and is selected from more than one the functional additive that UV light absorber, photostabilizer, oxidation inhibitor, thermopolymerization prevent agent, levelling agent, defoamer, tackifier, anti-sedimentation agent, pigment (organic coloring pigment, mineral dye), illuminating colour, infrared absorbent, white dyes, dispersion agent, electrically conductive particles, anti-live agent, antifogging agent, coupling agent.
UV light absorber better is usually as the benzotriazole category UV light absorber of synthetic resins UV light absorber, Benzophenones UV light absorber, salicylic acid UV light absorber, phenyl triazines UV light absorber etc.Specifically can exemplify the compound of the open 0078 section record of the flat 11-268196 communique of communique of Japan's special permission.Because coating composition 1 contains multi-functional polymerizable monomer (a-1), good especially is 2-{2-hydroxyl-5-(2-acryloxy ethyl) phenyl } benzotriazole, 3-(3-benzotriazole-4-hydroxyl-5-tert-butyl-phenyl) propionic acid 2-hydroxy-3-methyl acryloxy propyl ester equimolecular contain the compound of optical polymerism functional group.
Photostabilizer better is the hindered amine light stabilizer that is used as the synthetic resins photostabilizer usually.Specifically can exemplify the compound of the open 0080 section record of the flat 11-268196 communique of communique of Japan's special permission.
Good especially among the present invention is N-methyl-4-methacryloxy-2,2,6, and the compound of polymerizability functional group is arranged in the 6-tetramethyl piperidine equimolecular.
Oxidation inhibitor can enumerate 2,6-di-t-butyl-Hinered phenols antioxidants such as p-cresylol, phosphoric acid kind antioxidants such as triphenylphosphate etc.Prevent that as thermopolymerization agent from can exemplify hydroquinone monomethyl ether etc.And, can exemplify silicone resin class levelling agent, crylic acid resin levelling agent etc. as levelling agent.
As defoamer, can exemplify silicone resin defoamers such as polydimethylsiloxane etc.And can exemplify polymethylmethacrylate base polymer, hydrogenated castor oil compounds, fatty acyl amide compound etc. as tackifier.
Organic coloring pigment can exemplify fused polycycle class pigment dyestuff, phthalocyanines pigment dyestuff etc.Mineral dye, it is black etc. to exemplify titanium dioxide, cobalt oxide, chrome vermillion, titanium.Illuminating colour can exemplify organic solvent solubility azo metalloid complex compound dyestuff, organic solvent soluble phthalocyanine class dyestuff etc.
Infrared absorbent can exemplify polymethine class, phthalocyanines, metal complex class, ammonium class, diimine class (diimonium), anthraquinone class, two mercapto metalloid complex compound classes, naphthoquinones class, indoles phenol, azo class, triarylmethane compounds etc.
Electrically conductive particles can exemplify metal powders such as zinc, aluminium, nickel, iron phosphide, antimony rubber cement type stannic oxide etc.
Anti-live agent can exemplify non-class subclass anti-live agent, cationic anti-live agent, cloudy class subclass anti-live agent etc.
Coupling agent can exemplify silane coupling agent, titanate coupling agent etc.
In order further to improve the wearability of filming after solidifying, can in coating composition 1, cooperate colloidal silica (D).Colloidal silica (D) is the ultramicron that is dispersed in the silicic anhydride in the dispersion medium with colloidal, and dispersion medium is not particularly limited, but better be water, lower alcohols, cellosolve class etc.Concrete dispersion medium can exemplify water, methyl alcohol, ethanol, Virahol, propyl carbinol, ethylene glycol, ethylene glycol-methyl ether, glycol-ether, ethylene glycol-ether, propylene glycol-methyl ether-acetic ester, N,N-DIMETHYLACETAMIDE, toluene, dimethylbenzene, ritalin, vinyl acetic monomer, amyl acetate-n, acetone etc.
The median size of colloidal silica (D) is not particularly limited, and for manifesting the high transparent of filming after the curing, better is 1～1000nm, and good especially is 1～200nm, and especially 1～50nm is better.
Be to improve the dispersion stabilization of colloidal silica (D), also the hydrolyzate modified particle of available water-disintegrable silane compound surface and using.Here " use the hydrolyzate modified surface " and be the hydrolyzate physics of silane compound or Chemical bond in the state of the part or all of silanol base on colloidal silica particles surface, be meant to make the surface property modification therefrom.Also comprise the condensation reaction of the thing that is hydrolyzed and same bonded silicon dioxide granule.This surface modification, part or all hydrolysis of water-disintegrable base that can be by in the presence of silicon dioxide granule, making silane compound or hydrolysis takes place and condensation reaction and carrying out easily.
Water-disintegrable silane compound better is to contain the silane compound that water-disintegrable bases such as the organic radical of functional groups such as (methyl) acryl, amino, epoxy group(ing), sulfydryl and alkoxyl group or hydroxyl are incorporated into Siliciumatom.Water-disintegrable base in this specification sheets, be meant with Siliciumatom bonded part in can hydrolysis base.Can exemplify 3-(methyl) acryloxy propyl trimethoxy silicane, 2-(methyl) acryloxy ethyl trimethoxy silane, 3-(methyl) acryloxy propyl-triethoxysilicane, 2-(methyl) acryloxy ethyl triethoxysilane, the 3-aminopropyltriethoxywerene werene, the 3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, the 3-glycidoxypropyltrime,hoxysilane, 3-sulfydryl propyl trimethoxy silicane etc.
As water-disintegrable silane compound, contain the silane compound that contains sulfydryl (S1) that the organic radical of sulfydryl and water-disintegrable base or hydroxyl are incorporated into Siliciumatom, because reactive high, more satisfactory with polymerizable monomer (A).The silane compound (S1) that contains sulfydryl better is the compound of following formula (12) expression.
HS-R
1-SiR
2 fR
5 3-fFormula (12)
(in the formula, R
1Be the divalent alkyl, R
2Be hydroxyl or water-disintegrable base, R
5Be 1 valency alkyl, f is 1～3 integer).
In the formula (12), R
1Better be the alkylidene group of carbonatoms 2～6, good especially is that carbonatoms is 3 alkylidene group.R
5Better be the alkyl of carbonatoms below 4, good especially is methyl and ethyl.R
2Better be water-disintegrable base, be more preferably halogen or the alkoxyl group of carbonatoms below 4, good especially is the alkoxyl group of carbonatoms below 4.Halogen atom better is a chlorine or bromine.As alkoxyl group, methoxyl group and oxyethyl group are water-disintegrable good, so better.F better is 2 or 3.
Below list the typical example of the silane compound that contains sulfydryl of formula (12) expression.Wherein OMe, OEt, OPr represent methoxyl group, oxyethyl group, positive propoxy respectively.
HS-CH
2CH
2CH
2-Si(OMe)
3、HS-CH
2CH
2CH
2-Si(OEt)
3、HS-CH
2CH
2CH
2-Si(OPr)
3、HS-CH
2CH
2CH
2-SiMe(OMe)
2、HS-CH
2CH
2CH
2-SiMe(OEt)
2、HS-CH
2CH
2CH
2-SiMe(OPr)
2、HS-CH
2CH
2CH
2-SiMe
2(OMe)、HS-CH
2CH
2CH
2-SiMe
2(OEt)，HS-CH
2CH
2CH
2-SiMe
2(OPr)、HS-CH
2CH
2CH
2-SiCl
3、HS-CH
2CH
2CH
2-SiBr
3、HS-CH
2CH
2CH
2-SiMeCl
2、HS-CH
2CH
2CH
2-SiMeBr
2、HS-CH
2CH
2CH
2-SiMe
2Cl、HS-CH
2CH
2CH
2-SiMe
2Br。
As water-disintegrable silane compound; there are the organic radical of (methyl) acryl and water-disintegrable base or hydroxyl to be incorporated into the silane compound that contains (methyl) acryl (S2) of Siliciumatom; because with the reactive height of polymerizable monomer (A), and its bonded good stability, more satisfactory.As the silane compound that contains (methyl) acryl (S2), better be the compound of following formula (13) expression;
CH
2=C (R
6)-R
7-SiR
2 fR
5 3-fFormula (13)
(R in the formula
6Be hydrogen atom or methyl, R
7Be the divalent alkyl, R
2Be hydroxyl or water-disintegrable base, R
5Be 1 valency alkyl, f is 1～3 integer).
R in the formula (13)
1Better be the alkylidene group of carbonatoms 2～6, good especially is the alkylidene group of carbon atom 3.R
5Better be the alkyl of carbonatoms below 4, good especially is methyl and ethyl.R
2Better be water-disintegrable base, be more preferably halogen or the alkoxyl group of carbonatoms below 4, good especially is the alkoxyl group of carbonatoms below 4.Halogen better is a chlorine or bromine.As alkoxyl group, methoxyl group and oxyethyl group are water-disintegrable good, so better.F better is 2 or 3.
The typical example of the silane compound that contains (methyl) acryl (S2) that following illustration following formula is represented.
CH
2＝C(R
6)-CH
2CH
2CH
2-Si(OMe)
3、CH
2＝C(R
6)-CH
2CH
2CH
2-Si(OEt)
3、CH
2＝C(R
6)-CH
2CH
2CH
2-Si(OPr)
3、CH
2＝C(R
6)-CH
2CH
2CH
2-SiMe(OMe)
2、CH
2＝C(R
6)-CH
2CH
2CH
2-SiMe(OEt)
2、CH
2＝C(R
6)-CH
2CH
2CH
2-SiMe(OPr)
2、CH
2＝C(R
6)-CH
2CH
2CH
2-SiMe
2(OMe)、CH
2＝C(R
6)-CH
2CH
2CH
2-SiMe
2(OEt)、CH
2＝C(R
6)-CH
2CH
2CH
2-SiMe
2(OPr)、CH
2＝C(R
6)-CH
2CH
2CH
2-SiCl
3、CH
2＝C(R
6)-CH
2CH
2CH
2-SiBr
3、CH
2＝C(R
6)-CH
2CH
2CH
2-SiMeCl
2、CH
2＝C(R
6)-CH
2CH
2CH
2-SiMeBr
2、CH
2＝C(R
6)-CH
2CH
2CH
2-SiMe
2Cl、CH
2＝C(R
6)-CH
2CH
2CH
2-SiMe
2Br。
Cooperate the occasion of colloidal silica (D), its use level (solids component) is preferably 0.1 mass parts-500 mass parts with respect to polymerizable monomer (A) 100 mass parts, is more preferably 1 mass parts-300 mass parts, and good especially is 10 mass parts-200 mass parts.As in this scope, the sufficient wearability of having filmed after the curing, difficult labour is given birth to muddyly, and applies external force and is difficult to produce crack etc.
For the coating that improves coating composition, with the adhesivity of substrate surface, in coating composition 1, can further cooperate organic solvent, if organic solvent does not have the solubility problem of polymerizable monomer (A), water and oil repellent agent (B), active energy ray polymerization starter (C), colloidal silica (D), other additives, be not particularly limited, that can satisfy above-mentioned performance can.Also can be also with the organic solvent more than 2 kinds.The usage quantity of organic solvent is with respect to polymerizable monomer (A), and quality better is below 100 times, and is good especially below 50 times.
Lower alcohols such as organic solvent can exemplify, ethanol, butanols, Virahol, ethers such as ketones such as methyl iso-butyl ketone (MIBK), methyl ethyl ketone, acetone, two alkane, diethylene glycol dimethyl ether, tetrahydrofuran (THF), methyl tertiary butyl ether, organic solvents such as cellosolve class such as methyl glycol, glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetic ester.In addition, also can use ester classes such as n-butyl acetate, isoamyl acetate, Diethylene Glycol monoacetate, more fluoride hexane, polyfluoro methylcyclohexane, polyfluoro-1, the perfluor aliphatic hydrocarbon of carbonatomss 5～12 such as 3-dimethyl cyclohexane, halogenated hydrocarbons such as polyfluoro aromatic hydrocarbon, polyfluoro aliphatic hydrocarbon such as two (trifluoromethyl) benzene, hydro carbons such as toluene, dimethylbenzene, hexane etc.These organic solvents also can mix use more than 2 kinds.
The occasion that contains organic solvent in the coating composition 1 better is that the kind of the base material of filming according to formation is selected suitable organic solvent.For example base material is when being prepared by the low aromatic polycarbonate resin of solvent resistance, better uses the solvent low to the aromatic polycarbonate resin solvability, and more suitable is lower alcohols, cellosolve class, ester class, ethers and their mixture etc.
Coating composition 1 usefulness pickling process, spin-coating method, flow coat method, spraying method, rod are coated with methods such as method, engraved roll coating method, rolling method, spread coating, airblade coating method and are coated on glass or the plastic base material, in the occasion of the composition that contains organic solvent after drying, use its curing with the active energy ray irradiation.
Active energy ray can exemplify ultraviolet ray, electron rays, X line, radioactive rays and high frequency radiation etc., and the ultraviolet ray of wavelength 180～500nm is particularly advantageous aspect economy.
UV irradiation equipment such as xenon lamp, low pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, carbon arc lamp, tengsten lamp, electron beam irradiation device, roentgen radiation x device, high frequency generating apparatus etc. can be used in the active energy ray source.
The irradiation time of active energy ray can suitably change according to conditions such as the kind of polymerizable monomer (A), the kind of active energy ray polymerization starter (C), the thickness of filming, active energy ray sources.Usually can achieve the goal with irradiation in 0.1～60 second.For making curing reaction complete, also can after the active energy ray irradiation, carry out heat treated again.
The thickness of filming can adopt all thickness as requested.Usually better be filming of 0.1～50 μ m thickness, it is good especially to form filming of 0.2～20 μ m thickness.In this scope, wearability is abundant as coating thickness, and the curing of the depths of filming is also abundant, so better.Best coating thickness is 0.3～10 μ m.
Filming after the curing, the transparency is good, and its surface abrasion resistance, water and oil-resistant are good, and fingerprint that can long-term exhibit excellent is removed property.Therefore, this is filmed to the lipid dirt didirtresistance excellence of fingerprint, sebum, sweat, makeup etc., and such lipid dirt difficulty adheres to, and wipes away easily even adhere to also.
The fingerprint property removed of the exhibit excellent of filming after coating composition 1 solidifies, think that it be the reasons are as follows:
(to call " fingerprint " in the following text) that is commonly referred to fingerprint and is attached to surfaces such as optics is to be attached to the sweat of finger tip and sebum composition to be attached to this surface with the form with the apperance transfer printing of fingerprint.
Can think, filming after the curing because its surface waterproofing grease proofness is good, even " fingerprint " is attached to this film coated surface, this film coated surface is also repelled " fingerprint " contained moisture and sebum composition, " fingerprint " is not close to this film coated surface, carries the state of holding globular moisture and sebum composition and form this film coated surface.Therefore this sebum becomes to grade and is wiped away easily.So the fingerprint property removed is good.
Coating composition 2 of the present invention (to call " coating composition 2 " in the following text) is the active energy ray-curing coating composition of filming through being solidified to form, and it is characterized in that having following properties.
Film coated surface after the curing to the oleic contact angle initial stage 60 the degree more than, and after the humidity test 55 the degree more than.
The haze value of filming after the curing is below 3%.
The variation of the haze value of filming after solidifying before and after the Taber wearing test (abrasion wheels: CS-10F, single isolated wheel loading 500g, 500 change) of ISO9352 regulation is below 10%.
Coating composition 2 has above-mentioned characteristic, so the film coated surface water and oil-resistant after solidifying is good, and the water and oil-resistant of the long-term exhibit excellent of energy.The present invention is equipped with drop (being specially water and oleic acid drop) with the film coated surface after solidifying state to the contact angle of this drop as the water and oil-resistant index.Coating composition 2 by the curing of the program determination shown in the following embodiment after the contact angle of film coated surface as follows.
Solidify the contact angle of back film coated surface
Water: more than 85 degree, more than better 90 degree, better 95 degree above (initial stage), 80 degree above (after the humidity test)
Oleic acid: 60 degree, more than better 65 degree, better 70 degree above (initial stage), 55 degree above (after the humidity test)
And, coating composition 2, because above-mentioned characteristic is arranged, the transparency of filming after the curing is also good.
Among the present invention with haze value as the index of transparency of filming after solidifying.The haze value of filming after coating composition 2 solidifies is defined as the haze value of filming of the thickness 1.2 μ m that form on the polycarbonate substrate of thick 3mm.Coating composition 2, the haze value of filming after the curing are below 3%, more fortunately below 1%, better below 0.5%.
And coating composition 2 is owing to there is above-mentioned characteristic, and the wearability of the film coated surface after the curing is also good.Among the present invention during with the Taber wearing test of implementing ISO 9352 regulations (abrasion wheels: CS-10F, single isolated wheel loading 500g, 500 change) before and after the test variation of this haze value of filming as the wearability index of the film coated surface after solidifying.Coating composition 2, the variation of this haze value of filming after the curing are below 10%, more fortunately below 8%, better below 6%.
Coating composition 2 is owing to there is above-mentioned characteristic, and the surface lubrication of the film coated surface after the curing is also good.Use the index of the kinetic friction coefficient of the film coated surface of pressing the program determination shown in the following embodiment among the present invention as the surface lubrication of the film coated surface after solidifying.Specifically, initial stage kinetic friction coefficient of filming after coating composition 2 solidifies and the kinetic friction coefficient after the humidity test are all below 0.1.
Coating composition 2 is active energy ray-curing coating compositions, comprises that many kinds contain the composition of above-mentioned characteristic.
Coating composition 2 better is to comprise above-mentioned active energy ray solidified nature polymerizable monomer (A), promptly multi-functional polymerizable monomer (a-1) and/or simple function polymerizable monomer (a-2) etc.Here the content ratio of (a-1) is arbitrarily in the polymerizable monomer (A), better is to be 20～100 quality % in the total mass of polymerizable monomer (A), is more preferably 40～100 quality %, and good especially scope is 70～100 quality %.
The form that coating composition 2 is good especially is above-mentioned coating composition 1.
Coating composition 1 of the present invention and 2 is applicable to that it is good to form its transparency, wearability and water and oil-resistant as the glass of optics or the surface of plastic base material, and the cured coating film of the fingerprint of the long-term exhibit excellent property removed.
The material of the plastic basis material of filming as formation, better being the plastic material that the transparency is arranged, the plastic material of wearability difference, specifically is aromatic polycarbonate resin, plexiglass, Polymethacrylimide resin, polystyrene resin, polyvinyl chloride (PVC) RESINS, unsaturated polyester resin, polyolefin resin, ABS resin, MS (methyl methacrylate-vinylbenzene) resin etc.
＜embodiment 〉
Followingly the present invention is described, but the present invention is not limited by they according to embodiment (example 1～3,5～8,11,13,15～18) and comparative example (example 4,9,10,12,14,19).In each example, the mensuration of various rerum naturas and evaluation are undertaken by method shown below, and its result represents with table 4.With the sheet of the transparent aromatic adoption carbonate resin system of thickness 3mm (100mm * 100mm) as base material.
[contact angle]
With automatic contact angle meter (DSA10D02: German Network Le ス corporate system), form the drop of 3 μ L at needle point, make film coated surface of its contact sample make drop in drying regime (20 ℃, relative humidity 65%).Contact angle is defined as liquid and the angle that the tangent line of the fluid surface of solid point of contact is become with solid surface, is the angle that comprises liquid one side.Liquid uses distilled water and oleic acid respectively.Sample after initial stage sample and the humidity test (60 ℃, the moist environment of relative humidity 95% kept 500 hours down) is measured contact angle.
[fingerprint removal]
(ベ Application コ Star ト M-3: Asahi Kasei Corporation's system) wiping is attached to the fingerprint of the film coated surface of sample, and the difficulty or ease of its wiping are carried out visual judgement with Mierocrystalline cellulose system non-woven fabrics.By the sample after initial stage sample and the humidity test (60 ℃, the moist environment of relative humidity 95% kept 500 hours down) assess sample.
Determinating reference is as follows.
Zero: fingerprint can be wiped fully
*: fingerprint can not be wiped fully
[transparency]
Sample is filmed,, calculate its mean value (initial stage haze value) with the mist degree (%) at 4 positions of turbidometer mensuration.
[wearability]
According to the Taber wearing test of ISO 9352 regulation, will place on the sample film coated surface with 2 CS-10F abrasion wheels of the state of 500g weight combination respectively, rotation 500 is changeed.Measure the haze value carry out after the wearing test with turbidometer.Mist degree is determined at 4 positions of abrasion wheels circular trackway to carry out, and measures mean value.Wearability is with value (%) expression of (haze value after wearing test is carried out)-(initial stage haze value).
[surface lubrication]
To above-mentioned initial stage sample and to the sample behind the wet test, the kinetic friction coefficient of working sample film coated surface is under the following conditions, measure to make load level move necessary slide plate weight (g), by " by weight/load and " obtain kinetic friction coefficient.
Testing table: Mierocrystalline cellulose system non-woven fabrics (ベ Application コ Star ト, Asahi Kasei Corporation's system)
Load: 500g (contact area 50mm * 100mm)
Miles of relative movement: 20mm
Translational speed: 10mm/ branch
Testing circumstance: 25 ℃, relative humidity 45%
[binding property]
In the film coated surface of sample with razor in length and breadth to crack, each stroke 11 road, 1mm forms 100 at interval, makes commercially available cellotape (ニ チ バ Application Co., Ltd. system) fine bonding,, does not peel off and residual checker number (individual) expression when peeling off fast along 90 degree directions then with filming.
The raw material that uses among the embodiment etc. is described below.
" starting compound "
1) polymerizable monomer (A):
A-1: the reaction of the Dipentaerythritol polyacrylic ester of hydroxyl and hexamethylene diisocyanate and per molecule average propylene acyl group number be 15, the acrylamido ethyl formate of molecular weight 2300.
A-2: dipentaerythritol acrylate.
A-3: isobornyl acrylate.
2) active energy ray polymerization starter (C)
C-1:2-methyl isophthalic acid-(4-thiotolene base)-2-morpholinyl-third-1-ketone
3) colloidal silica (D)
D-1: in glycol-ether decentralized colloidal silica (dioxide-containing silica 30 quality %, median size 11nm) 100 mass parts, add 3-sulfydryl propyl trimethoxy silicane 2.5 mass parts, heated and stirred is after 5 hours under 80 ℃, nitrogen gas stream, under room temperature aging 12 hours and the surface colloidal silica of the hydrolytic condensate of the silane compound that contains sulfydryl is arranged.
D-2: in propylene glycol-methyl ether acetate decentralized colloidal silica (dioxide-containing silica 30 quality %, average diameter grain 11nm) 100 mass parts; add 3-methacryloxypropyl trimethoxy silane 2.5 mass parts; in 50 ℃ stir 3 hours after, aged at room temperature 12 hours and the surface colloidal silica of the hydrolytic condensate of the silane compound that contains methacryloyl is arranged.
[water and oil repellent agent (B-T)]
The number-average molecular weight of the following stated is to ooze the dish chromatography with gel to make the numerical value that reference material is measured with polystyrene.
B-1: in the 300mL four neck flasks that agitator and prolong are housed, add the four isobutoxy titaniums of 80mg, the C of 100g
3F
7(OCF
2CF
2CF
2)
20O (CF
2)
2CH
2The 6-caprolactone of OH (ダ イ キ Application industrial system, デ system Na system SA, number-average molecular weight 4000) and 10g, in 150 ℃ of heating 5 hours, the 6-caprolactone open loop adds and is formed in C
3F
7(OCF
2CF
2CF
2)
20O (CF
2)
2CH
2The white waxy compound of the end of OH.Number-average molecular weight 4400, the polymerization degree of caprolactone is about 3.5.
Then; compound cool to room temperature with gained; add 2 of the hexafluoro m-xylene of 50g and 60mg; the 6-toluene di-tert-butyl phenol; stir the 2-methacryloxyethyl isocyanic ester that adds 6.0g after 30 minutes; in room temperature restir 24 hours, terminal by the hexafluoro m-xylene solution of the water and oil repellent agent of methacryloyl modification (B-1) (solids component 70 quality %).(B-1) number-average molecular weight is 4550.
B-2: in the 300mL four neck flasks that agitator is housed, add the above-mentioned C of 100g
3F
7(OCF
2CF
2CF
2)
20O (CF
2)
2CH
22 of the dibutyl tin laurate of OH, 50mg and 250mg, the 6-toluene di-tert-butyl phenol after 30 minutes, adds the 2-methacryloxyethyl isocyanic ester of 3.6g in stirring at room.Room temperature restir 24 hours, terminal by the water and oil repellent agent of methacryloyl modification (B-2).(B-2) number-average molecular weight is 4150.
B-3: in the 300mL four neck flasks that agitator and prolong are housed; add 2 of 600mg; 2 '-the hexafluoro m-xylene of n-dodecyl mercaptan, 90g N-BUTYL ACETATE and the 90g of azo two (2-methyl propionitrile), 740mg; in stirring at room after 15 minutes; an end of poly(propylene oxide) that adds the above-mentioned water and oil repellent agent (B-2) of 45g and 15g is by the macromonomer of acryl modification (the system Block レ of Nof Corp. Application マ-AP-800, CH
2=CHCOO-(CH
2CH (CH
3) O)
y-H, y 13, hydroxyl value=66.8), clean the back with nitrogen and carried out polymerization in 18 hours in 70 ℃ of stirrings, get reaction product.
The result gets the polymkeric substance of number-average molecular weight 10000.Then with gained reaction product cool to room temperature; the dibutyl tin laurate and the 100mg 2 that add 50mg; the 6-toluene di-tert-butyl phenol; in stirring at room after 30 minutes; the 2-methacryloxyethyl isocyanic ester that adds 2.27g; in room temperature restir 24 hours, in the polymerized unit of multipolymer poly-propylene oxide end by the N-BUTYL ACETATE solution of the water and oil repellent agent of methacryloyl modification (B-3) (the about 25 quality % of solid component concentration).(B-3) number-average molecular weight is 10460.
B-4: in the 300mL four neck flasks that agitator and condenser are housed, add 600mg 2,2 '-azo two (2-methyl propionitrile), 740mg n-dodecyl mercaptan and 180g N-BUTYL ACETATE, in stirring at room after 15 minutes, add the above-mentioned water and oil repellent agent of 35g (B-2), 20g stearyl acrylate ester and 5g vinylformic acid 2-hydroxy methacrylate, clean the back with nitrogen and carried out polymerization in 18 hours, get reaction product in 70 ℃ of stirrings.
The result gets the polymkeric substance of number-average molecular weight 25000.Then with the reaction product cool to room temperature of gained; add 50mg dibutyl tin laurate and 100mg 2; the 6-toluene di-tert-butyl phenol; the 2-methacryloxyethyl isocyanic ester that adds 6.61g in stirring at room after 30 minutes; in room temperature restir 24 hours, the polymerized unit inner propene acid 2-hydroxy methacrylate end of multipolymer by the N-BUTYL ACETATE solution of the water and oil repellent agent of methacryloyl modification (B-4) (the about 25 quality % of solid component concentration).(B-4) number-average molecular weight is 27800.
B-5: in the 300mL four neck flasks that agitator and prolong are housed, add 2 of 600mg, 2 '-azo two (2-methyl propionitrile), 740mg n-dodecyl mercaptan and 180g N-BUTYL ACETATE, in stirring at room after 15 minutes, add the ester modified 6-caprolactone of above-mentioned water and oil repellent agent of 45g (B-2) and 15g unsaturated fatty acids hydroxyalkyl (ダ イ セ Le chemical company system, the polymerization degree=2 of プ ラ Network セ Le FA2D, caprolactone), carry out polymerization in 18 hours with nitrogen cleaning back in 70 ℃ of stirrings and get reaction product.
The result gets the polymkeric substance of number-average molecular weight 35000.Then with the reaction product cool to room temperature of gained; add 2 of the dibutyl tin laurate of 50mg and 100mg; the 6-toluene di-tert-butyl phenol; in stirring at room after 30 minutes; the 2-methacryloxyethyl isocyanic ester that adds 6.69g; in room temperature restir 24 hours, the ester modified 6-caprolactone end of the unsaturated fatty acids hydroxyalkyl of polymerized unit of multipolymer by the N-BUTYL ACETATE solution of the water and oil repellent agent of methacryloyl modification (B-5) (the about 25 quality % of solid component concentration).(B-5) number-average molecular weight is 39000.
B-6: above-mentioned C
3F
7(OCF
2CF
2CF
2)
20O (CF
2)
2CH
2OH is not with the water and oil repellent agent of radiation-hardenable functional group (b-2) and position (b-3).
B-7: in the 300mL four neck flasks that agitator and prolong are housed, add polyfluoro polyethylene oxide (ソ Le ベ イ ソ レ Network シ ス corporate system, trade(brand)name Off オ Application Block リ Application Z-dol 1000, HOCH that 80mg four isobutoxy titaniums, 100g have two terminal hydroxyls
2(CF
2CF
2O)
p(CF
2O)
sCF
2CF
2CH
2OH, molecular-weight average 1000) and the 25g 6-caprolactone, in 150 ℃ of heating 5 hours, get the white waxy compound of two ends of polyfluoro polyethylene oxide.Number-average molecular weight is 1250, about 1.1 of the polymerization degree of each terminal caprolactone.
With the compound cool to room temperature of gained, add 1 of 67g then, 2 of two (trifluoromethyl) benzene of 3-and 60mg, the 6-toluene di-tert-butyl phenol stirred after 30 minutes, added the 2-methacryloxyethyl isocyanic ester of 31.0g, in room temperature restir 24 hours, reaction is finished.Then, in 40 ℃ of pressure reducing and steaming solvents 1, two (trifluoromethyl) benzene of 3-get terminal by the water and oil repellent agent of methacryloyl modification (B-7).(B-7) number-average molecular weight is 1560.
Compound M (the CF of the raw material of B-8～B-13
3O (CF
2CF
2O)
pCF
2CH
2OH, p 7.3) synthetic
Following tetramethylsilane is called for short TMS, CClF
2CF
2CHClF claims AK-225, CCl
2FCClF
2Be called R-113.
Operation 1) with commercially available polyoxyethylene glycol-methyl ether (CH
3O (CH
2CH
2O)
P+1H, p 7.3) (25g) and AK-225 (20g), NaF (1.2g), pyridine (1.6g) put in the flask, interior temperature remains on below 10 ℃, vigorous stirring makes nitrogen bubble simultaneously.Temperature is changed 3.0 hours simultaneously therein and is dripped FCOCF (CF below 5 ℃ in keeping
3) OCF
2CF (CF
3) OCF
2CF
2CF
3(46.6g).After drip finishing, stirred 12 hours in 50 ℃, stirring at room 24 hours, reclaim thick liquid then.With thick liquid filtration under diminished pressure, reclaim liquid then and used Vacuumdrier (50 ℃, 667Pa) dry 12 hours again.Be dissolved in the thick liquid of gained among the AK-225 of 100ml this moment, with 1000ml saturated sodium bicarbonate aqueous solution washing 3 times, reclaims organic phase.In reclaiming organic phase, add sal epsom (1.0g) again, stirred 12 hours.Thereafter sal epsom is removed in pressure filtration, steams with vaporizer and removes AK-225, is cooled to room temperature and gets liquid polymers 56.1g.
1H-NMR,
19The result that F-NMR analyzes confirms that resulting polymers is CH
3O (CH
2CH
2O)
P+1COCF (CF
3) OCF
2CF (CF
3) OCF
2CF
2CF
3The compound of (the p meaning is the same) expression.
Operation 2) in the potheater of 500mL heat-proof corrosion-resistant nickel-base alloy system, adds R-113 (1560g), stir, in 25 ℃ of insulations.Water cooler, the NaF grain packing layer of 20 ℃ of maintenances is set and keeps 20 ℃ water cooler in the series connection of potheater gas outlet.And the liquid Returning pipe of potheater is sent phlegma back to from the water cooler of-20 ℃ of maintenances in setting.Blast nitrogen after 1.0 hours, blasted 1 hour with flow velocity 24.8L/h with the fluorine gas (to call 10% fluorine gas in the following text) of nitrogen dilution to 10%.
Blast 10% fluorine gas with identical flow velocity then, the resultant (27.5g) of changing 30 hours injection process 1 gained simultaneously is dissolved in the solution of R-113 (1350g).
Then blast 10% fluorine gas, inject R-113 solution 12mL simultaneously with identical flow velocity.At this moment, interior temperature is become 40 ℃.Inject the R-113 solution (6mL) that is dissolved with 1wt% benzene then.Blast fluorine gas again after 1.0 hours, blasted nitrogen 1.0 hours.
After reaction finishes, desolventize, be cooled to room temperature and get liquid resultant 45.4g through vacuum-drying (60 ℃, 6.0 hours) steaming.The results verification that NMR analyzes be operation 1 gained resultant the hydrogen atom sum 99.9% by fluorine atom replace with CF
3O (CF
2CF
2O)
P+1COCF (CF
3) OCF
2CF (CF
3) OCF
2CF
2CF
3The compound of expression.
Operation 3) be added with the 300mL round-bottomed flask of stirring piece, fully replace with nitrogen, add methyl alcohol (36g), NaF (5.6g) and AK-225 (50g) drip the resultant (43.5g) of operation 2 gained, then in the room temperature bubbling, and vigorous stirring simultaneously.The eggplant type flask outlet seals with nitrogen.
Vacuum pump was set in prolong after 8 hours, makes to keep decompression in the system, steam and remove excessive methanol and byproduct of reaction.After 24 hours, be cooled to room temperature and get liquid resultant 26.8g.
Analytical results confirm whole ester groups of operation 2 gained resultants become methyl esters with CF
3O (CF
2CF
2O)
pCF
2COOCH
3The compound of expression is main resultant.
Operation 4) is added with the 300mL round-bottomed flask of stirring piece, fully replaces with nitrogen.Add 2-propyl alcohol (30g), AK-225 (50.0g) and NaBH
4(4.1g), operation 3 gained resultants (26.2g) are dripped with AK-225 (30g) dilution back.Thereafter in the room temperature vigorous stirring, the round-bottomed flask outlet seals with nitrogen.
Vacuum pump was set in prolong after 8 hours, makes to keep decompression in the system, steaming desolventizes.Add AK-225 (100g) after 24 hours, drip 0.2N hydrochloric acid (500g) while stirring.Dripping the back continues to stir 6 hours.Thereafter, organic phase makes two separate reclaim organic phase with distilled water (500g) washing 3 times.In the organic phase that reclaims, add sal epsom (1.0g) again, stirred 12 hours.Thereafter, sal epsom is removed in pressure filtration, steams with vaporizer and removes AK-225, is cooled to room temperature and gets liquid polymers 24.8g.
Analytical results confirm that whole ester groups of operation 3 gained resultants are reduced with CF
3O (CF
2CF
2O)
pCF
2CH
2The compound that OH represents is main the generation.
B-8: in the 300mL four neck flasks that agitator and prolong are housed, add the four isobutoxy titaniums of 80mg, the compound M of 100g and the 6-caprolactone of 25g, in 150 ℃ of heating 5 hours, get the white wax shape water and oil repellent agent (B-8) that the 6-caprolactone open loop adds the end that is formed in the polyfluoro polyethylene oxide.(B-8) molecular weight is 1250, and the polymerization number of degrees of caprolactone are about 2.2.
B-9: in the 300mL four neck flasks that agitator and prolong are housed, add 1 of 125g water and oil repellent agent (B-8) and 60g, 2 of two (trifluoromethyl) benzene of 3-and 60mg, the 6-toluene di-tert-butyl phenol, stir after 30 minutes, the 2-methacryloxyethyl isocyanic ester that adds 15.5g again in stirring at room 24 hours, finishes reaction.Thereafter in 40 ℃, decompression is steamed down and is desolventized 1, and two (trifluoromethyl) benzene of 3-get terminal by the water and oil repellent agent of methacryloyl modification (B-9).(B-9) molecular weight is 1400.
B-10: in the 300mL four neck flasks that agitator is housed; add 2 of 100g compound M and 60mg; the 6-toluene di-tert-butyl phenol; stir after 30 minutes; the 2-methacryloxyethyl isocyanic ester that adds 31.0g; in room temperature restir 24 hours, terminal by the water and oil repellent agent of methacryloyl modification (B-10).(B-1)) number-average molecular weight is 1160.
B-11: in the 300mL four neck flasks that agitator and prolong are housed; add 2 of 600mg; 2 '-azo two (2-methyl propionitrile), 740mg n-dodecyl mercaptans, 90g N-BUTYL ACETATE and 90g 1; two (trifluoromethyl) benzene of 3-; in stirring at room 15 minutes; an end that adds above-mentioned water and oil repellent agent of 45g (B-10) and 15g poly(propylene oxide) then is by the macromonomer of acryl modification (Nof Corp.'s system, Block レ Application マ-AP-800, CH
2=CHCOO-(CH
2CH (CH
3) O)
y-H, y 13, hydroxyl value=66.8),, get resultant of reaction with carrying out polymerization in 18 hours in 70 ℃ of stirrings after the nitrogen purge.
Its result obtains the multipolymer of number-average molecular weight 10000.Then, the resultant of reaction cool to room temperature with gained adds 2 of 50mg dibutyl tin laurate and 100mg, the 6-toluene di-tert-butyl phenol, after 30 minutes, add the 2-methacrylic acyloxy ethyl isocyanate of 2.27g in stirring at room, again in stirring at room 24 hours.Reaction is finished.Steaming desolventizes 1 under 40 ℃ of decompressions then, two (trifluoromethyl) benzene of 3-, and the interior poly(propylene oxide) end of polymerized unit that gets multipolymer is by the water and oil repellent agent of methacryloyl modification (B-11).(B-11) number-average molecular weight is 10460.
B-12: in the 300mL four neck flasks that agitator and prolong are housed, add 2 of 600mg, 2 '-azo two (2-methyl propionitrile), 740mg n-dodecyl mercaptan and 180g N-BUTYL ACETATE, in stirring at room after 15 minutes, add the ester modified 6-caprolactone of above-mentioned water and oil repellent agent of 45g (B-10) and 15g unsaturated fatty acids hydroxyalkyl (ダ イ セ Le chemical company system, プ ラ Network セ Le FA2D, the polymerization degree of caprolactone=2), with carrying out polymerization in 18 hours in 70 ℃ of stirrings after the nitrogen purge, get resultant of reaction.
The result gets the multipolymer of number-average molecular weight 35000.Then, add 2 of 50mg dibutyl tin laurate and 100mg, the 6-toluene di-tert-butyl phenol with gained resultant of reaction cool to room temperature, in stirring at room after 30 minutes, the 2-methacryloxyethyl isocyanic ester that adds 6.69g in room temperature restir 24 hours, finishes reaction.Then; under 40 ℃ of decompressions, steam and desolventize 1; 3 a pair ofs (trifluoromethyl) benzene must the ester modified 6-caprolactone end of unsaturated fatty acids hydroxyalkyl be 39000 by the number-average molecular weight of the water and oil repellent agent of methacryloyl modification (B-12), (B-12) in the polymerized unit of multipolymer.
B-13: in the 300mL four neck flasks that agitator and prolong are housed, add 580mg Potassium monofluoride, 100g compound M and 9.12g carbonic acid ethylidene ester, in 160 ℃ of decarboxylations, heated simultaneously 40 hours, get 1 unit loop oxidative ethane and add the water white transparency oily compound that is formed in compound M end.
After the Potassium monofluoride filtering in the system, in the 300mL four neck flasks that agitator and prolong are housed, the 6-caprolactone that adds 80mg four isobutoxy titaniums and above-mentioned oily compound 109g and 25g, in 150 ℃ of heating 5 hours, get 6-caprolactone adds the end that is formed in compound M by 1 unit loop oxidative ethane open loop white waxy compound.Number-average molecular weight is 1400, and the polymerization degree of caprolactone is about 2.2.
Then add 1 of 60g, 2 of two (trifluoromethyl) benzene of 3-and 60mg, 6-dual-tert-butyl p-cresol stirred after 30 minutes, added the 2-methacryloxyethyl isocyanic ester of 15.5g, in room temperature restir 24 hours, made the reaction end.Thereafter steaming desolventizes 1 under 40 ℃ of decompressions, and two (trifluoromethyl) benzene of 3-get terminal by the water and oil repellent agent of methacryloyl modification (B-13).(B-13) number-average molecular weight is 1550.
B-14: the part of side chain is by C
8F
17CH
2CH
2Base metathetical dimethyl silicone oil (Asahi Glass corporate system, trade(brand)name " FLS 525 ").It is the water and oil repellent agent that does not have functional group (b-2) and position (b-3).
Table 1
| Water and oil repellent agent | Type | Structure |
| B-1 | Straight chain type | C 3F 7(OCF 2CF 2CF 2) nO(CF 2) 2CH 2O-(C(＝O)C 3H 18O) 2- CONHC 2H 4OCOC(CH 3)＝CH 2 n20，t3.5 |
| B-2 | No position (b-3) | C 3F 7(OCF 2CF 2CF 2) nO(CF 2) 2CH 2O-CONHC 2H 4OCOC(CH 3)＝CH 2 n20，t3.6 |
| B-3 | Copoly type | -[CH 2-C(CH 2)CO{P}] f-{GH 2-CHCO{Q}] f- f1.8.g3.0 {P}：C 3F 7(OCF 2CF 2CF 2) AO(CF 2) 2CH 2O-CONHC 2H 4O- {Q}：CH 2＝C(CH 3)COOC 2H 5NHCOO-(CH 2CH(CH 3)O) y- n20，y13 |
| B-4 | Copoly type | -[CH 2-C(CH 2)CO{P}] f-[CH 2-CHCO[Q]] g-[CH 2- CHCO{R}] h- f3.5，g25.6，h18.0 {P}：C 3F 7(OCF 2CF 2CF 2) RO(CF 2) 2CH 2O-CONHC 2H 4O- {Q}：C 18H 37O- {R}：CH 2＝C(CH 3)COOC 2H 6NHCOO-CH 2CH 2O- n20 |
| B-5 | Copoly type | -[CH 2-C(CH 3)CO{P}] f-[CH 2-CHCO{Q}] g- f6.3，g26.7 {P}：C 3F 7(OCF 2CF 2CF 2) pO(CF 2) 2CH 2O-CONHC 2H 4O- {O}：CH 2＝C(CH 3)COOC 2H 6NHCOO-(COC 5H 10-O) x-C 2H 4O- n20，X2 |
| B-6 | No functional group (b-2) position (b-3) | C 3F 7(OCF 2CF 2CF 2) nO(CF 2) 2CH 2OH n20 |
Table 2
| Water and oil repellent agent | Type | Structure |
| B-7 | Straight chain type | CH 2＝C(CH 3)COOC 2H 4NHCOO-(C(＝O)C 6H 10O) t- CH 2(CF 2CF 2O) p(CF 2O) aCF 2CF 2CH 2O-(C(＝O)C 6H 10O) t- CONHC 2H 4OCOC(CH 3)＝CH 2 t1.1 |
| B-8 | No functional group (b-2) | CF 3O(CF 2CF 2O) pCF 2CH 2O-(C(＝O)C 5H 10O) t-H p7.3，t2.2 |
| B-9 | Straight chain type | CF 3O(CF 2CF 2O) PCF 2CH 2O-(C(＝O)C 5H 10O) t- CONHC 2H 4OCOC(CH 3)＝CH 2 p7.3，t2.2 |
| B-10 | No position (b-3) | CF 3O(CF 2CF 2O) pCF 2CH 2O-CONHC 2H 4OCOC(CH 3)＝CH 2 p7.3 |
| B-11 | Copoly type | -[CH 2-C(CH 3)CO{P}] f-[CH 2-CHCO{O}] g- f6.5，g3.0 {P}：CF 3O(CF 2CF 2O) pCF 2CH 2O-CONHC 2H 4O- {O}：CH 2＝C(CH 3)COOC 2H 5NHCOO-(CH 2CH(CH 3)O) y- p7.3，y13 |
| B-12 | Copoly type | -[CH 2-C(CH 3)CO{P}] f-[CH 2-CHCO{O}] g- f22.6，g26.7 {P}；CF 3O(CF 2CF 2O)，CF 2CH 2O-CONHC 2H 4O- {Q}：CH 2＝C(CH 3)COOC 2H 5NHCOO-(COC 5H 10-O) x-C 2H 4O- p7.3，X2 |
| B-13 | Straight chain type | CF 3O(CF 2CF 2O) pCF 2CH 2O-CH 2CH 2O-(C(＝O)C 5H 10O) t- CONHC 2H 4OCOC(CH 3)＝CH 2 p7.3，t2.2 |
[example 1]
In the 300mL four neck flasks that agitator and prolong are housed, add 80g polymerizable monomer (A-1), 1.0g water and oil repellent agent (B-1), 4.0g active energy ray polymerization starter (C-1), prevent as thermopolymerization agent 1.0g hydroquinone monomethyl ether and as the 65.0g N-BUTYL ACETATE (AcBt) of organic solvent, under normal temperature and lucifuge state, stirred 1 hour, make its homogenization.Stir on one side then,, stirred 1 hour in normal temperature and lucifuge state again, make its homogenization Yi Bian slowly add 75.0g colloidal silica (D-1).
Then, add dibutyl ether (DBE), stirred 1 hour, get coating composition (Q1) at normal temperature and lucifuge state as the 65.0g of organic solvent.Then at substrate surface spin coating (2000rpm * 10 second) coating composition (Q1), in 90 ℃ Hotaircirculatingoven dry 1 minute, use high voltage mercury lamp (light quantity: 1200mJ/cm then
2, wavelength 300～390nm scope ultraviolet accumulated energy) make curing of coating.The result obtains having at substrate surface the sample 1 of the cured article layer (filming) of thickness 1.2 μ m.Measure and estimate above-mentioned projects with sample 1.The results are shown in Table 4.
[example 2～9,11～19]
Except the polymerizable monomer in the coating composition of example 1 (A), water and oil repellent agent (B), active energy ray polymerization starter (C), colloidal silica (D) and organic solvent being changed over kind shown in the table 3 and quantity (in the parantheses, the g of unit) in addition, with the example 1 same perparation of specimen 2～9,11～19, measure equally and estimate with example 1.
[example 10]
In the 300mL four neck flasks that agitator and prolong are housed, add 80g polymerizable monomer (A-1), 4.0g active energy ray polymerization starter (C-1), as the 1.0g hydroquinone monomethyl ether of stopper with as the 65.0g N-BUTYL ACETATE (AcBt) of organic solvent, stirred 1 hour in normal temperature and lucifuge state, make its homogenization.Stir on one side then,, stirred 1 hour in normal temperature and lucifuge state again, make its homogenization Yi Bian slowly add 75.0g colloidal silica (D-1).
Add 65.0g dibutyl ether (DBE) then, stirred 1 hour, get coating composition (Q10) in normal temperature and lucifuge state as organic solvent.Then with (Q10) spin coating (2000rpm * 10 second) at substrate surface, in 90 ℃ Hotaircirculatingoven dry 1 minute, use high voltage mercury lamp (light quantity: 1200mJ/cm then
2The ultraviolet accumulated energy of wavelength 300～390nm scope) makes curing of coating, form the cured article layer that solidifies the thickness 1.2 μ m that form by polymerizable monomer (A-1) at substrate surface.
Then, (B-1) is dissolved in acetone with the 1.0g water and oil repellent agent, the acetone soln spin coating (2000rpm * 10 second) that to be somebody's turn to do (B-1) then is in above-mentioned cured article laminar surface, in 90 ℃ Hotaircirculatingoven after dry 1 minute, with high voltage mercury lamp (light quantity: 1200mJ/cm
2, the ultraviolet accumulated energy of wavelength 300～390nm scope) and make curing of coating, form the thin solidified layer of water and oil repellent agent (B-1).The result obtains having formed the cured article layer that polymerizable monomer (A-1) solidifies the thickness 1.2 μ m that form at substrate surface, has formed the sample 10 of the thin cured article layer of water and oil repellent agent (B-1) at this cured article laminar surface.Carry out mensuration and the evaluation same with this sample 10 with example 1.
Table 3
| A | B | C | D | AcBt | DBE | |
| Example 1 | A-1：80g | B-1：1.0g | C-1：4.0g | D-1：75.0g | 65.0g | 65.0g |
| Example 2 | A-2：80g | B-1：1.0g | C-1：4.0g | D-1：75.0g | 55.0g | 65.0g |
| Example 3 | A-1：50g A-2：30g | B-1：1.0g | C-1：4.0g | D-1：75.0g | 65.0g | 65.0g |
| Example 4 | A-2：80g | B-2：1.0g | C-1：4.0g | D-1：75.0g | 65.0g | 65.0g |
| Example 5 | A-2：80g | B-3：1.0g | C-1：4.0g | D-1：76.0g | 65.0g | 65.0g |
| Example 6 | A-2：80g | B-4：1.0g | C-1：4.0g | D-1：75.0g | 65.0g | 65.0g |
| Example 7 | A-2：80g | B-5：1.0g | C-1：4.0g | D-1：75.0g | 65.0g | 65.0g |
| Example 8 | A-2：50g A-3：30g | B-1：1.0g | C-1：4.0g | Do not have | 65.0g | 65.0g |
| Example 9 | A-1：80g | B-6：1.0g | C-1：4.0g | D-1：75.0g | 65.0g | 65.0g |
| Example 10 | A-1：80g | B-1：1.0g | C-1：4.0g | D-1：75.0g | 65.0g | 65.0g |
| Example 11 | A-2：80g | B-7：0.3g | C-1：4.0g | 0-1：75.0g | 65.0g | 65.0g |
| Example 12 | A-2：80g | B-8：0.3g | C-1：4.0g | D-1：75.0g | 65.08 | 65.0g |
| Example 13 | A-2：80g | B-9：0.3g | C-1：4.0g | D-1：75.0g | 65.0g | 65.0g |
| Example 14 | A-1：60g A-3：20g | B-10：0.8g | C-1：4.0g | D-1：75.0g | 65.0g | 65.0g |
| Example 15 | A-1：60g A-3：20g | B-11：0.8g | C-1：4.0g | D-1：75.0g | 65.0g | 65.0g |
| Example 16 | A-1：60g A-3：20g | B-12：0.8g | C-1：4.0g | D-1：75.0g | 65.0g | 65.0g |
| Example 17 | A-2：80g | B-13：0.3g | C-1：4.0g | D-1：75.0g | 65.0g | 65.0g |
| Example 18 | A-2：80g | B-13：0.3g | C-1：4.0g | D-2：75.0g | 65.0g | 65.0g |
| Example 19 | A-1：60g A-3：20g | B-14：0.8g | C-1：4.0g | D-1：75.0g | 65.0g | 65.0g |
But example 10 is containing the cured article layer that has formed B on the solidified surface film of A, C, D.
Table 4
| Contact angle distilled water/oleic acid | (haze value, %) | Wearability (%) | Binding property (individual) | The fingerprint property removed | Surface lubrication | ||||
| Initial stage | After the humidity test | Initial stage | After the humidity test | Initial stage | After the humidity test | ||||
| Example 1 example 2 examples 3 examples 4 examples 5 examples 6 examples 7 examples 8 examples 9 examples 10 examples 11 examples 12 examples 13 examples 14 examples 15 examples 16 examples 17 examples 18 examples 19 | 110/76 112/73 110/74 103/74 111/75 108/76 107/74 109/73 109/70* 111/75 112/77 109/71 113/78 100/70 108/72 109/74 108/71 108/72 103/55 | 105/75 107/72 105/74 101/71 107/74 102/75 103/73 104/70 65/35 70/40 106/72 70/45 111/77 98/68 106/71 107/72 107/70 107/71 60/30 | 0.3 0.3 0.2 3.6 0.2 0.2 0.1 0.2 5.5 0.6 0.3 0.3 0.3 8.5 0.3 0.3 0.2 0.2 0.6 | 3.5 2.8 3.0 2.7 2.9 2.6 2.4 9.5 3.5 4.0 2.8 2.9 3.0 3.6 5.2 6.0 2.9 2.8 1.3 | 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 | ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × | ○ ○ ○ ○ ○ ○ ○ ○ × × ○ ○ ○ ○ ○ ○ ○ ○ × | 0.08 0.09 0.09 0.08 0.09 0.09 0.09 0.09 0.07 0.07 0.07 0.07 0.06 0.08 0.07 0.07 0.05 0.05 0.3 | 0.08 0.09 0.09 0.15 0.09 0.09 0.09 0.09 0.6 0.5 0.07 0.5 0.06 0.16 0.07 0.07 0.05 0.05 0.4 |
* film surface some places oily dirt free acid.
The possibility of＜industrial utilization 〉
The glass system of filming or plastic formed products that the surface has the solidfied material of coating composition of the present invention to form, soil resistance, particularly the soil resistance to lipid dirts such as fingerprint, sebum, sweat, cosmetic crystalline substances is good, and such lipid dirt is difficult to adhere to, and wipes away easily even adhere to also. And the mar proof of this formed products, the transparency are also good. Therefore be attached to the opticses such as the antireflection film that can throw into question in appearance, optics colour filter, optical lens, liquid crystal display, EL display, CD as the lipid dirt, very satisfied.
Claims (10)
1. active energy ray-curing coating composition, it is with respect to the polymerizable monomer of active energy ray solidified nature (A) 100 mass parts, contains the coating composition of the active energy ray polymerization starter (C) of the water and oil repellent agent (B) of 0.01～10 mass parts and 0.1～10 mass parts; It is characterized in that, above-mentioned polymerizable monomer (A) contains the following multi-functional polymerizable monomer (a-1) more than or equal to 20 quality %: be the monomer that the polymerizability functional group that is selected from acryl and methacryloyl more than 2 or 2 is arranged in the molecule in the total mass of contained this polymerizable monomer (A) of above-mentioned coating composition; Above-mentioned water and oil repellent agent (B) is to contain by being selected from shown in following formula (6)～(8) position (b-1) that having of at least 1 formation in the part manifest water and oil-resistant, active energy ray solidified nature functional group (b-2) and by the water and oil repellent agent (B-T) that is selected from the position (b-3) of at least 1 formation in the part shown in following formula (2)～(4)
-(CH
2CH
2O)
x-... formula (2)
-(CH
2CH (CH
8) O)
y-... formula (3)
-(C (=O) C
uH
2uO)
t-... formula (4)
X and y are 5～100 integers in the formula, and u is 3～5 integer, and t is 1～20 integer;
-(CF
2CF
2O)
p-... formula (6)
-(CF
2CF (CF
3) O)
q-... formula (7)
-(CF
2CF
2CF
2O)
r-... formula (8)
P, q, r are 1～100 integers in the formula.
2. coating composition according to claim 1 is characterized in that, in above-mentioned water and oil repellent agent (B-T), the part shown in following formula (10) or the following formula (11) is contained at the above-mentioned position (b-1) that manifests water and oil-resistant;
R
f(OC
3F
6)
n-O-(CF
2)
m-(CH
2)
L-O-... formula (10)
R
f(OC
2F
4)
e-O-(CF
2)
g-(CH
2)
h-O-... formula (11)
R in the formula
fBe the Polyfluoroalkyl of carbonatoms 1～16, include the Polyfluoroalkyl of Sauerstoffatom, n is 1～50 integer, and m and L are 0～3 integers, 6 〉=m+L＞0; E is 1～50 integer, and g and h are 0～3 integers, 6 〉=g+h＞0.
3. coating composition according to claim 1 is characterized in that, above-mentioned water and oil repellent agent (B-T) is represented by following formula:
CF
3O (CF
2CF
2O)
pCF
2CH
2O-CH
2CH
2O-(C (=O) C
5H
10O)
t-CONHC
2H
4OCOC (CH
3)=CH
2In the formula, p 7.3, t 2.2.
4. according to each described coating composition in the claim 1～3, it is characterized in that,, also contain the colloidal silica (D) of 0.1～500 mass parts with respect to the above-mentioned polymerizable monomer (A) of 100 mass parts.
5. coating composition according to claim 4, it is characterized in that, above-mentioned colloidal silica (D) be with the silane compound that contains sulfydryl (S1) that the organic radical that sulfydryl is arranged and water-disintegrable base or hydroxyl are incorporated into Siliciumatom carry out surface modification and the modification colloidal silica.
6. coating composition according to claim 5 is characterized in that, the above-mentioned silane compound (S1) that contains sulfydryl is the compound of following formula (12) expression;
HS-R
1-SiR
2 fR
5 3-fFormula (12)
R in the formula
1Be the divalent alkyl, R
2Be hydroxyl or water-disintegrable base, R
5Be 1 valency alkyl, f is 1～3 integer.
7. coating composition according to claim 4; it is characterized in that; above-mentioned colloidal silica (D), be with the silane compound that contains (methyl) acryl (S2) that organic radical that (methyl) acryl is arranged and water-disintegrable base or hydroxyl are incorporated into Siliciumatom carry out surface modification and the modification colloidal silica.
8. coating composition according to claim 7 is characterized in that, above-mentioned containing, the silane compound (S2) of (methyl) acryl was the compound of following formula (13) expression;
CH
2=C (R
6)-R
7-SiR
2 fR
5 3-fFormula (13)
R in the formula
6Be hydrogen atom or methyl, R
7Be the divalent alkyl, R
2Be hydroxyl or water-disintegrable base, R
5Be 1 valency alkyl, f is 1～3 integer.
9. coating composition according to claim 1, it is characterized in that, the contact angle initial stage of solidifying between back film coated surface and the oleic acid is spent more than or equal to 60, and spend more than or equal to 55 after the humidity test, the haze value of filming after the above-mentioned curing is smaller or equal to 3%, and the variation of the haze value of filming after the above-mentioned curing before and after the Taber wearing test (500 change for abrasion wheels: CS-10F, single isolated wheel loading 500g) of ISO 9352 regulations is smaller or equal to 10%.
10. molding is characterized in that, has filming of thickness 0.1～50 μ m that the cured article by each described coating composition in the claim 1～9 constitutes at the substrate surface of glass or plastics.
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|---|---|---|---|
| JP329119/2002 | 2002-11-13 | ||
| JP2002329119 | 2002-11-13 | ||
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| JP94994/2003 | 2003-03-31 |
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| CN2007103005350A Division CN101230215B (en) | 2002-11-13 | 2003-11-12 | Active energy ray-curing coating composition |
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| CN100368486C true CN100368486C (en) | 2008-02-13 |
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| JPH1060306A (en) * | 1996-08-13 | 1998-03-03 | Asahi Glass Co Ltd | Coating composition and its use |
| JPH10245419A (en) * | 1997-03-05 | 1998-09-14 | Fukuvi Chem Ind Co Ltd | Surface modification by fluorine-based photo-curable resin composition |
| JPH1110767A (en) * | 1997-06-25 | 1999-01-19 | Asahi Glass Co Ltd | Transparently coated molding and its manufacture |
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| JP2000309725A (en) * | 1999-04-27 | 2000-11-07 | Asahi Glass Co Ltd | Actinic-radiation-curable composition |
| JP2001288216A (en) * | 2000-04-06 | 2001-10-16 | Kanto Denka Kogyo Co Ltd | Fluorine containing copolymer containing double bonds and manufacturing method thereof |
| JP2002128845A (en) * | 2000-10-23 | 2002-05-09 | Shin Etsu Chem Co Ltd | Liquid radiation curable resin composition of, coating composition for optical fiber and optical fiber |
| US20020111391A1 (en) * | 2000-12-11 | 2002-08-15 | Asahi Glass Company, Limited | Curable composition, cured coating film and coated substrate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105008429A (en) * | 2013-03-05 | 2015-10-28 | 旭硝子株式会社 | Fluorine-containing ether compound, composition for forming hard coating layer, and article having hard coating layer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1711325A (en) | 2005-12-21 |
| JP2011026606A (en) | 2011-02-10 |
| CN101230215B (en) | 2010-10-20 |
| JP2004176054A (en) | 2004-06-24 |
| CN101230215A (en) | 2008-07-30 |
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