CN104945615A - Fluorine-containing acryl compound, method for making the same, curable composition and substrate - Google Patents
Fluorine-containing acryl compound, method for making the same, curable composition and substrate Download PDFInfo
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- CN104945615A CN104945615A CN201510146322.1A CN201510146322A CN104945615A CN 104945615 A CN104945615 A CN 104945615A CN 201510146322 A CN201510146322 A CN 201510146322A CN 104945615 A CN104945615 A CN 104945615A
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Abstract
The invention provides a fluorine-containing acryl compound exhibiting excellent solubility and capable of being easily synthesized, a method for making the same, a curable composition including the same, and a substrate including a curing envelope. The fluorine-containing acryl compound is described in an equation (1) [Rf1-Z1]a-Q1-[CH2-CHR1-Z2-CHR2-OR3]b and an equation (2) [R3O-CHR2-Z2-CHR1-CH2]b-Q2-Z1-Rf2-Z1-Q2-[CH2-CHR1-Z2-CHR2-OR3]b. Rf1 represents a one-valence perfluoropolyether group with the molecular being 400-20000; Rf2 represents a two-valence perfluoropolyether group with the molecular being 400-20000; Z1 represents a two-valence hydroxy group including O, N and Si; Q1 represents an (a+b)-valence linking group including Si; Q1 represents a (b+1)-valence linking group including Si; Z2 represents a two-valence hydroxy group including O and N; R1 represents H or a one-valence hydroxy group; R2 represents a one-valence hydroxy group; Z2 and R1 can form a cyclic structure through combination; Z2 and R2 can also form a cyclic structure through combination; R1 and R2 can form a cyclic structure including Z2; a and b range from 1 to 10; R3 represents H or a one-valence organic group, wherein the one-valence organic group may include O and N, and includes an acryloyl group or an alpha substituent acryloyl group; and R3 represents more than one one-valence organic groups mentioned above.
Description
Technical field
The present invention relates to fluorine-containing based compound and manufacture method thereof, comprise the solidification compound of this compound and there is the base material of solidification tunicle of said composition.
Background technology
So far, as the means on the surface of protection resin-formed body etc., generally have employed hard coat process widely.Its for the surface of formed body formed hard curing resin layer (hard coat) and make its be difficult to damage.As forming the material of hard coat, employing heat-curing resin, ultraviolet or electronic beam solidified resin more and there is the resin of function of both.
On the other hand, utilize the expansion in field, the trend of high additive value along with synthetic resin, the requirement for the multifunction of curing resin layer (hard coat) is surging, as one of them, requires to give didirtresistance to hard coat.It is by giving the character such as water-repellancy, grease proofness to the surface of hard coat, even if thus make to be difficult to stain or stain also can easily remove.
As the method for hard coat being given to didirtresistance, employ the method in the hard coating surface coating once formed and/or fixing fluorine-containing stain control agent widely, for by adding fluorine-containing solidified nature composition to curable resin composition before solidification, make it be coated with solidification, thus the method for simultaneously carrying out the formation of hard coat and the imparting of didirtresistance is also studied.Such as, illustrated in Unexamined Patent 6-211945 publication (patent documentation 1) by adding fluoroalkyl base ester in the curable resin composition of acrylic acid series, making it solidify and impart the manufacture of the hard coat of didirtresistance.
The present inventor, as the fluorine cpd can giving didirtresistance to such curable resin composition, carry out various exploitation, such as, propose by fluorine-containing alcohol compound is matched with heat-curing resin in JP 2013-237824 publication (patent documentation 2) and give the method for didirtresistance.In addition, the present inventor, such as, JP 2010-53114 publication (patent documentation 3), JP 2010-138112 publication (patent documentation 4), the photo curable fluorine cpd shown in JP 2010-285501 publication (patent documentation 5) are proposed.As synthesis these can the method for fluorine cpd of photocuring, make fluorine-containing alcohol and acrylic acid halide, method excellence that the acrylic compounds with isocyanate group reacts.
In recent years, requirement for the multifunction of the fluorine-containing based compound synthesized by fluorine-containing alcohol compound and fluorine-containing alcohol for the purpose of the cooperation in such curable resin is surging, is strongly required the fluorine-containing based compound that solvability is excellent, can easily synthesize.
Prior art document
Patent documentation
[patent documentation 1] Unexamined Patent 6-211945 publication
[patent documentation 2] JP 2013-237824 publication
[patent documentation 3] JP 2010-53114 publication
[patent documentation 4] JP 2010-138112 publication
[patent documentation 5] JP 2010-285501 publication
Summary of the invention
The problem that invention will solve
The present invention completes in view of above-mentioned practical situation, and object is to provide that solvability is excellent, the fluorine-containing based compound that can easily synthesize and manufacture method thereof, comprise the solidification compound of this compound and have the base material of solidification tunicle of said composition.
For solving the means of problem
The present inventor, as such fluorine-containing based compound, in JP 2010-53114 publication (patent documentation 3), JP 2010-138112 publication (patent documentation 4), JP 2010-285501 publication (patent documentation 5) etc., propose the alkylol cpd that makes end have a unsaturated link(age) by hydrosilylation and the method for holo-fluorine polyester addition with multiple Si-H group, particularly, exemplified with using imported following primary alconol, tertiary alcohol end compound as intermediate.
-CH
2CH
2CH
2OH
-CH
2CH
2CH
2OCH
2CH
2OH
[changing 1]
Wherein, employ to have imported-CH
2when the fluorine-containing alcohol compound of the primary alconol end of OH type is as intermediate; sometimes due to heating, rheological parameters' change with time and easy thickening; solvability reduces; on the other hand; when tertiary alcohol end, compared with the situation of primary alconol, be difficult to deliquescent reduction occurs; but because of the difference of condition, speed of response when sometimes importing acryl becomes extremely slow.In particular for the reaction of isocyanate compound with acryl; in recent years; due to the worry for toxicity; the high tin series catalysts of catalyst activity is used to become difficulty; transfer to safer but the titanium system that catalyst activity is low, zirconium system etc. catalyzer; but for the employing tertiary alcohol of these catalyzer and the reaction of isocyanic ester, speed of response is tended to extremely slow.
Therefore, the novel fluorine-containing based compound showing stable solvability, can easily synthesize is needed.
The present inventor studies to achieve these goals further repeatedly, found that, makes following general formula (3) or (4)
[Rf
1-Z
1]
a-Q
1-[H]
b(3)
[H]
b-Q
2-Z
1-Rf
2-Z
1-Q
2-[H]
b(4)
(in formula, Rf
1for the holo-fluorine polyester of 1 valency of molecular weight 400 ~ 20,000 be made up of perfluoroalkyl and the Sauerstoffatom of carbon number 1 ~ 6, Rf
2for the holo-fluorine polyester of the divalent of molecular weight 400 ~ 20,000 be made up of perfluorinated alkylidene and the Sauerstoffatom of carbon number 1 ~ 6, Z
1be the alkyl of the divalent of Han the Sauerstoffatom of carbon number 1 ~ 20, nitrogen-atoms and Siliciumatom independently, midway can contain ring texture.Q
1the connection base comprising at least (a+b) individual Siliciumatom (a+b) valency, Q
2independently for comprising at least the connection base of (b+1) valency of (b+1) individual Siliciumatom.A is the integer of 1 ~ 10, and b is the integer of 1 ~ 10 independently.A the Z bracketed with []
1with b H all respectively with Q
1or Q
2silicon atom bonding in structure.)
Shown fluorochemicals and following general formula (5)
CH
2＝CR
1-Z
2-CHR
2-OH (5)
(in formula, Z
2be the alkyl of Han the Sauerstoffatom of carbon number 1 ~ 200 and the divalent of nitrogen-atoms independently, midway can contain ring texture.R
1be the alkyl of 1 valency of hydrogen atom or carbon number 1 ~ 8 independently, R
2be the alkyl of 1 valency of carbon number 1 ~ 8 independently, Z
2with R
1and/or Z
2with R
2can combine respectively and with and R
1, R
2in conjunction with carbon atom form ring texture together, in addition, R
1with R
2can in conjunction with and formed containing Z together with the carbon atom separately to combine
2ring texture.)
The fluorine-containing alcohol compound with secondary alcohol end that the shown alcohol containing terminal unsaturation group carries out hydrosilylation reactions and obtains is compared with the fluorochemicals of primary alconol end, the thickening that heating, rheological parameters' change with time cause is few, with employ tertiary alcohol end fluorochemicals situation compared with speed of response enough fast, also find: make this fluorine-containing alcohol compound and following formula (6) and/or (7)
CH
2＝CR
4COX (6)
CH
2＝CR
4COOCH
2CH
2-N＝C＝O (7)
(in formula, R
4for hydrogen atom or methyl, X is halogen atom.)
The following general formula (1) that shown compound reacts and obtains or (2)
[changing 2]
[Rf
1-Z
1]
a-Q
1-[CH
2-CHR
1-Z
2-CHR
2-OR
3]
b(1)
[R
3O-CHR
2-Z
2-CHR
1-CH
2]
b-Q
2-Z
1-Rf
2_Z
1-Q
2-[CH
2-CHR
1-Z
2-CHR
2-OR
3]
b(2)
(in formula, Rf
1, Rf
2, Z
1, Z
2, Q
1, Q
2, R
1, R
2, a, b be described above.R
3be hydrogen atom or the organic radical with 1 valency of acryl or α substituted acryl that can contain Sauerstoffatom and nitrogen-atoms independently of one another, but, R
3on average there is the organic radical of at least 1 above-mentioned 1 valency in the molecule.)
Shown fluorine-containing based compound shows stable solvability, and speed of response during synthesis is enough fast, meets above-mentioned requirements, completes the present invention.
Therefore, the invention provides following fluorine-containing based compound, its manufacture method and solidification compound and base material.
[1] the fluorine-containing based compound represented by following general formula (1) or (2).
[changing 3]
[Rf
1-Z
1]
a-Q
1-[CH
2-CHR
1-Z
2-CHR
2-OR
3]
b(1)
[R
3O-CHR
2-Z
2-CHR
1-CH
2]
b-Q
2-Z
1-Rf
2-Z
1-Q
2-[CH
2-CHR
1-Z
2-CHR
2-OR
3]
b(2)
(in formula, Rf
1for the holo-fluorine polyester of 1 valency of molecular weight 400 ~ 20,000 be made up of perfluoroalkyl and the Sauerstoffatom of carbon number 1 ~ 6, Rf
2for the holo-fluorine polyester of the divalent of molecular weight 400 ~ 20,000 be made up of perfluorinated alkylidene and the Sauerstoffatom of carbon number 1 ~ 6, Z
1be the alkyl of the divalent of Han the Sauerstoffatom of carbon number 1 ~ 20, nitrogen-atoms and Siliciumatom independently, midway can contain ring texture.Q
1for comprising at least the connection base of (a+b) valency of (a+b) individual Siliciumatom, Q
2independently for comprising at least the connection base of (b+1) valency of (b+1) individual Siliciumatom.Z
2be the alkyl of Han the Sauerstoffatom of carbon number 1 ~ 200 and the divalent of nitrogen-atoms independently, midway can contain ring texture.R
1be the alkyl of 1 valency of hydrogen atom or carbon number 1 ~ 8 independently, R
2be the alkyl of 1 valency of carbon number 1 ~ 8 independently, Z
2with R
1and/or Z
2with R
2can combine respectively and with and R
1, R
2in conjunction with carbon atom form ring texture together, in addition, R
1with R
2can in conjunction with and formed containing Z together with the carbon atom separately to combine
2ring texture.A is the integer of 1 ~ 10, and b is the integer of 1 ~ 10 independently.R
3be hydrogen atom or the organic radical with 1 valency of acryl or α substituted acryl that can contain Sauerstoffatom and nitrogen-atoms independently of one another, wherein, R
3on average there is the organic radical of at least 1 above-mentioned 1 valency in the molecule.)
[2] the fluorine-containing based compound described in [1], wherein, the following formula in general formula (1) and (2)
-Z
2-CHR
2-OR
3
Shown group is following formula
-Z
3-OCH
2CH(CH
3)-OR
3
(in formula, R
3same as described above.Z
3for the alkyl of Han the Sauerstoffatom of carbon number 1 ~ 199 and the divalent of nitrogen-atoms, midway can form ring texture, in addition, and adjacent R
1with Z
3can in conjunction with and with and R
1in conjunction with carbon atom form ring texture together.)
Shown group.
[3] the fluorine-containing based compound described in [2], wherein, the following formula in general formula (1) and (2)
-Z
2-CHR
2-OR
3
Shown group is following formula
-CH
2-[OC
3H
6]
n-OCH
2CH(CH
3)-OR
3
(in formula, R
3same as described above.N is the integer of 0 ~ 64.)
Shown group.
[4] the fluorine-containing based compound described in any one of [1] ~ [3], it is represented by following general formula (8) or (9).
[changing 4]
[Rf
1-Z
1]
a-Q
1-[CH
2CH
2CH
2[OC
3H
6]
nOCH
2CH(CH
3)OCOCR
4＝CH
2]
b(8)
Rf
2-{Z
1-Q
2-[CH
2CH
2CH
2[OC
3H
6]
nOCH
2CH(CH
3)OCONHCH
2CH
2OCOCR
4＝CH
2]
b}
2
(9)
(in formula, Rf
1, Rf
2, Q
1, Q
2, Z
1, a, b as previously mentioned, n is the integer of 0 ~ 64, R
4for hydrogen atom or methyl.)
[5] the fluorine-containing based compound described in any one of [1] ~ [4], wherein, Rf
1for being selected from the structure of following formula (i), (ii), (iii),
CF
3O-(CF
2O)
p-(CF
2CF
2O)
q-CF
2- (i)
(in formula, p is the integer of 0 ~ 400, and q is the integer of 0 ~ 170, and p+q is the integer of 2 ~ 400.)
F[CF(CF
3)CF
2O]
r-CF(CF
3)- (ii)
(in formula, r is the integer of 1 ~ 120.)
F[CF
2CF
2CF
2O]
s-CF
2CF
2- (iii)
(in formula, s is the integer of 1 ~ 120.)
Rf
2for being selected from the structure of following formula (iv), (v),
-CF
2O-(CF
2O)
p-(CF
2CF
2O)
q-CF
2- (iv)
(in formula, p is the integer of 0 ~ 400, and q is the integer of 0 ~ 170, and p+q is the integer of 2 ~ 400.)
[changing 5]
-CF(CF
3)-[OCF
2CF(CF
3)]
t-OCF
2CF
2O-[CF(CF
3)CF
2O]
u-CF(CF
3)- (v)
(in formula, t+u is the integer of 2 ~ 120.)
Q
1be selected from following formula (vi) ~ (ix),
[changing 6]
(in formula, a, b are the integer of 1 ~ 10 independently of one another, and c is the integer of 1 ~ 5.The arrangement of each unit is random, bonding end and a the Z bracketed with [] of (a+b) individual each unit etc.
1with b CH
2in any one group combine.T is the connection base of (a+b) valency, is following formula (x) ~ (xiv)
[changing 7]
Any one.)
Q
2be selected from following formula (xv) ~ (xviii),
[changing 8]
(in formula, b is the integer of 1 ~ 10, and c is the integer of 1 ~ 5.The arrangement of each unit is random, the bonding end of (b+1) individual each unit etc. and Z
1with b the CH bracketed with []
2any one group combine.
T ' is following formula (xix) ~ (xxiii)
[changing 9]
Any one.)
Z
1be selected from following formula
-CH
2CH
2-
-CH
2CH
2CH
2-
-CH
2CH
2CH
2CH
2-
-CH
2OCH
2CH
2-
-CH
2OCH
2CH
2CH
2-
[changing 10]
[6] the fluorine-containing based compound described in any one of [1] ~ [5], wherein, formula (1) or the fluorine-containing based compound shown in (2) are any one in following formula (A1) ~ (A3).
[changing 11]
(in formula, Rf ' is-CF
2o (CF
2o)
p1(CF
2cF
2o)
q1cF
2-, p1, q1 are the numbers meeting q1/p1=0.8 ~ 1.5, q1+p1=5 ~ 80.R1 is the integer of 2 ~ 100 separately.N1 is the integer of 0 ~ 30 independently of one another.)
[7] manufacture method of the fluorine-containing based compound described in any one of [1] ~ [6], is characterized in that, makes following general formula (3) or (4)
[Rf
1-Z
1]
a-Q
1-[H]
b(3)
[H]
b-Q
2-Z
1-Rf
2-Z
1-Q
2-[H]
b(4)
(in formula, Q
1, Q
2, Rf
1, Rf
2, Z
1, a, b as previously mentioned, a the Z bracketed with []
1with b H all respectively with Q
1or Q
2siliciumatom in structure combines.)
Shown fluorochemicals and following general formula (5)
CH
2＝CR
1-Z
2-CHR
2-OH (5)
(in formula, R
1, R
2, Z
2as previously mentioned.)
The shown alcohol containing terminal unsaturation group carries out fluorine-containing alcohol compound that hydrosilylation reactions obtains and following formula (6) and/or (7)
CH
2＝CR
4COX (6)
CH
2＝CR
4COOCH
2CH
2-N＝C＝O (7)
(in formula, R
4for hydrogen atom or methyl, X is halogen atom.)
Shown compound reaction.
[8] manufacture method described in [7], wherein, formula (3) or the compound shown in (4) are selected from following (B-1) ~ (B-8),
[changing 12]
[changing 13]
(in formula, Rf ' is-CF
2o (CF
2o)
p1(CF
2cF
2o)
q1cF
2-, p1, q1 are the numbers meeting q1/p1=0.8 ~ 1.5, q1+p1=5 ~ 80.R1 is the integer of 2 ~ 100 separately.)
The alcohol containing terminal unsaturation group of formula (5) is selected from following formula,
CH
2＝CH-CH
2-OCH
2CH(CH
3)-OH
CH
2＝CH-CH
2-(OC
3H
6)
2-OCH
2CH(CH
3)-OH
CH
2＝CH-CH
2-(OC
3H
6)
4-OCH
2CH(CH
3)-OH
CH
2＝CH-CH
2-(OC
3H
6)
9-OCH
2CH(CH
3)-OH
[changing 14]
[9] solidification compound, is characterized in that, comprises [1] ~ fluorine-containing the based compound described in any one of [6].
[10] solidification compound described in [9] is coated with and the base material making it solidify at substrate surface.
The effect of invention
Fluorine-containing based compound of the present invention, owing to showing stable solvability, speed of response during synthesis is enough fast, easily can synthesize, therefore can be used as giving the additive of didirtresistance to thermohardening type resin combination or ultraviolet curing resin being given to the antifoulant additive etc. of didirtresistance.
Embodiment
Fluorine-containing based compound of the present invention is represented by following general formula (1) or (2).
[changing 15]
[Rf
1-Z
1]
a-Q
1-[CH
2-CHR
1-Z
2-CHR
2-OR
3]
b(1)
[R
3O-CHR
2-Z
2-CHR
1-CH
2]
b-Q
2-Z
1-Rf
2_Z
1-Q
2-[CH
Z-CHR
1-Z
2-CHR
2-OR
3]
b(2)
In above-mentioned formula (1), (2), Rf
1the holo-fluorine polyester of 1 valency of the molecular weight 400 ~ 20,000 be made up of the perfluoroalkyl of carbon number 1 ~ 6 and Sauerstoffatom, Rf
2the holo-fluorine polyester of the divalent of the molecular weight 400 ~ 20,000 be made up of the perfluorinated alkylidene of carbon number 1 ~ 6 and Sauerstoffatom, Rf
1, Rf
2particularly preferably there is the structure of following carbon number 1 ~ 3 as main repeating unit.
-CF
2O-
-CF
2CF
2O-
-CF(CF
3)CF
2O-
-CF
2CF
2CF
2O-
These structures can be the homopolymer of any one or random, the block polymer that are made up of multiple structure.
As the Rf with such structure
1preferred example, such as following structure can be enumerated.
CF
3O-(CF
2O)
p-(CF
2CF
2O)
q-CF
2-
(in formula, p is the integer of 0 ~ 400, preferably 0 ~ 200, and q is the integer of 0 ~ 170, preferably 0 ~ 100, and p+q is the integer of 2 ~ 400, preferably 3 ~ 300.)
F[CF(CF
3)CF
2O]
r-CF(CF
3)-
(in formula, r is the integer of 1 ~ 120, preferably 1 ~ 80.)
F[CF
2CF
2CF
2O]
s-CF
2CF
2-
(in formula, s is the integer of 1 ~ 120, preferably 1 ~ 80.)
In addition, as Rf
2preferred example, such as following structure can be enumerated.
-CF
2O-(CF
2O)
p-(CF
2CF
2O)
q-CF
2-
(in formula, p is the integer of 0 ~ 400, preferably 0 ~ 200, and q is the integer of 0 ~ 170, preferably 0 ~ 100, and p+q is the integer of 2 ~ 400, preferably 3 ~ 300.)
-CF(CF
3)-[OCF
2CF(CF
3)]
t-OCF
2CF
2O-[CF(CF
3)CF
2O]
u-CF(CF
3)-
(in formula, t+u is the integer of 2 ~ 120, preferably 4 ~ 100.)
For these Rf
1, Rf
2the molecular weight of group, the number-average molecular weight of this structure division is included in 400 ~ 20 respectively, 000, preferably 800 ~ 10, in the scope of 000, is not particularly limited for its molecular weight distribution.Should illustrate, in the present invention, molecular weight be by based on
1h-NMR and
19the number-average molecular weight that the end structure of F-NMR and the ratio of backbone structure calculate.
Above-mentioned Rf
1and Rf
2bonding end all and Z
1in conjunction with.Z
1for carbon number 1 ~ 20, preferably 2 ~ 16, the alkyl that can contain the divalent of Sauerstoffatom, nitrogen-atoms and Siliciumatom, midway can contain ring texture.As Z
1particularly preferred structure, following structure can be enumerated.
-CH
2CH
2-
-CH
2CH
2CH
2-
-CH
2CH
2CH
2CH
2-
-CH
2OCH
2CH
2-
-CH
2OCH
2CH
2CH
2-
[changing 17]
In above-mentioned formula (1), (2), a and b is the integer of 1 ~ 10 independently of one another, is preferably the integer of 1 ~ 8, is more preferably the integer of 1 ~ 4.
In above-mentioned formula (1), Q
1for comprising at least the connection base of (a+b) valency of (a+b) individual Siliciumatom, ring texture can be formed.As such Q
1preferred example, can enumerate there is (a+b) individual Si atom separately siloxane structure, do not replace or the connection base of (a+b) valency that the silicon alkylen structures of halogen substiuted, silicon arylidene structure or these combination of more than two kinds are formed.As particularly preferred structure, particularly, following structure is shown.
Wherein, a with b is identical with a, the b of above-mentioned formula (1), is the integer of 1 ~ 10 independently of one another, is preferably the integer of 1 ~ 8, is more preferably the integer of 1 ~ 4.C is the integer of 1 ~ 5, is preferably the integer of 3 ~ 5.The arrangement of each unit is random, bonding end and a the Z bracketed with [] of each unit that (a+b) is individual etc.
1with b CH
2in any one group bonding.
[changing 18]
Wherein, T is the connection base of (a+b) valency, can illustrate such as following group.
[changing 19]
In above-mentioned formula (2), Q
2for comprising at least the connection base of (b+1) valency of (b+1) individual Siliciumatom, ring texture can be formed.As such Q
2preferred example, can enumerate there is (b+1) individual Si atom separately siloxane structure, do not replace or the connection base of (b+1) valency that the silicon alkylen structures of halogen substiuted, silicon arylidene structure or these combination of more than two kinds are formed.As particularly preferred structure, particularly, following structure is shown.
Wherein, b is identical with the b of above-mentioned formula (2), is the integer of 1 ~ 10 independently, is preferably the integer of 1 ~ 8, is more preferably the integer of 1 ~ 4.C is the integer of 1 ~ 5, is preferably the integer of 1 ~ 3.The arrangement of each unit is random, the bonding end of each unit that (b+1) is individual etc. and Z
1with b the CH bracketed with []
2any one group bonding.
[changing 20]
Wherein, T ' is the connection base of (b+1) valency, can illustrate such as following group.
[changing 21]
In above-mentioned formula (1), (2), Z
2for carbon number 1 ~ 200, preferably 2 ~ 80, can containing the alkyl of the divalent of Sauerstoffatom and nitrogen-atoms, midway can contain ring texture.As Z
2preferred structure, following structure can be enumerated.
-CH
2CH
2-
-CH
2CH
2CH
2-
-CH
2CH
2CH
2CH
2-
-CH
2[OC
2H
4]
d[OC
3H
6]
e[OC
4H
8]
f-
-CH
2[OC
2H
4]
d[OC
3H
6]
e[OC
4H
8]
fOCH
2-
Wherein, d is the integer of 0 ~ 99, and e is the integer of 0 ~ 66, and f is the integer of 0 ~ 50, adds up to and meets carbon number less than 200.The arrangement of repeating unit, has nothing to do with kind, is random.In addition, each repeating unit can not be monomer but the mixture of isomer.
As Z
2, as particularly preferred structure, can enumerate following structure, wherein, preferred e is the structure of 1 ~ 30.
-CH
2[OC
3H
6]
eOCH
2-
In above-mentioned formula (1), (2), R
1for the alkyl of 1 valency of hydrogen atom or carbon number 1 ~ 8, preferably 1 ~ 6, R
2for the alkyl of 1 valency of carbon number 1 ~ 8, preferably 1 ~ 6, as the alkyl of 1 valency, particularly, the aralkyl etc. such as the aryl such as the thiazolinyls such as the cycloalkyl such as alkyl, cyclohexyl, vinyl, allyl group, propenyl, phenyl, tolyl, xylyl, benzyl, phenylethyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, octyl group can be enumerated.As R
1, be preferably hydrogen atom and methyl, as R
2, preferable methyl.
In addition, Z
2with R
1and/or Z
2with R
2can combine separately and with and R
1, R
2in conjunction with carbon atom form ring texture together, in addition, R
1with R
2can in conjunction with and formed containing Z together with the carbon atom separately to combine
2ring texture.
As Z
2with R
1or Z
2with R
2in conjunction with the example defining ring texture, following structure can be enumerated.Further, bonding end and OH and CHR
1or CHR
2and CH
2bonding.
[changing 22]
In addition, as R
1with R
2in conjunction with and formed containing Z together with the carbon atom separately to combine
2the example of ring texture, following structure can be enumerated.Should illustrate, bonding end represented by dashed line and OH and CHR
1or CHR
2and CH
2in conjunction with.
[changing 23]
In above-mentioned formula (1), (2), R
3be hydrogen atom or the 1 valency organic group with acryl or α substituted acryl that can contain Sauerstoffatom and nitrogen-atoms independently of one another.As 1 valency organic group, preferably at end, there is at least 1, the group of preferably 1 ~ 5 acryl or α substituted acryl, as this substituting group, methyl, ethyl, F, CF can be enumerated
3, Cl, Br etc.In addition, way can have amido linkage, ehter bond, ester bond etc. in the structure.
As such structure, such as following structure can be enumerated.
CH
2＝CHCO-
CH
2＝C(CH
3)CO-
CH
2＝C(C
2H
5)CO-
CH
2＝CFCO-
CH
2＝CClCO-
CH
2＝CBrCO-
CH
2＝C(CF
3)CO-
CH
2＝CHCOOCH
2CH
2-NHCO-
CH
2＝C(CH
3)COOCH
2CH
2-NHCO-
CH
2＝C(CH
3)COOCH
2CH
2OCH
2CH
2-NHCO-
(CH
2＝CHCOOCH
2CH
2)
2C(CH
3)-NHCO-
Wherein, be particularly preferably
CH
2＝CHCOOCH
2CH
2-NHCO-
CH
2＝C(CH
3)COOCH
2CH
2-NHCO-。
Wherein, R
3a part can be hydrogen atom, but be not all hydrogen atom, in a part, average packet is containing the aforesaid propylene acyl group of more than 1 and/or α substituted acryl.
-Z in above-mentioned formula (1), (2)
2-CHR
2-OR
3shown group, is preferably following formula
-Z
3-OCH
2CH(CH
3)-OR
3
Shown group.
Wherein, Z
3for carbon number 1 ~ 199, preferably 1 ~ 60, can containing the alkyl of the divalent of Sauerstoffatom and nitrogen-atoms, midway can form ring texture, in addition, adjacent R
1with Z
3can in conjunction with and with and R
1in conjunction with carbon atom form ring texture together.As Z
3preferred structure, following structure can be enumerated.
-CH
2[OC
2H
4]
d[OC
3H
6]
e[OC
4H
8]
f-
(in formula, d, e, f are same as described above.The arrangement of repeating unit, has nothing to do with kind, is random.In addition, each repeating unit can not be monomer, but the mixture of isomer.)
As Z
3, as particularly preferred structure, can enumerate following structure, wherein, preferred e is the structure of 1 ~ 30.
-CH
2[OC
3H
6]
e-
In addition ,-the Z in general formula (1), (2)
2-CHR
2-OR
3shown group is more preferably following formula
-CH
2-[OC
3H
6]
n-OCH
2CH(CH
3)-OR
3
(wherein, n be 0 ~ 64, the integer of preferably 0 ~ 40, more preferably 1 ~ 30.) shown in group.
As the fluorine-containing based compound shown in above-mentioned formula (1), (2), preferred following general formula (8), the compound shown in (9).
[changing 24]
[Rf
1-Z
1]
a-Q
1-[CH
2CH
2CH
2[OC
3H
6]
nOCH
2CH(CH
3)OCOCR
4＝CH
2]
b(8)
Rf
2-{Z
1-Q
2-[CH
2CH
2CH
2[OC
3H
6]
nOCH
2CH(CH
3)OCONHCH
2CH
2OCOCR
4＝CH
2]
b}
2
(9)
(in formula, Rf
1, Rf
2, Q
1, Q
2, Z
1, a, b, n be described above, R
4for hydrogen atom or methyl.)
As the fluorine-containing based compound shown in above-mentioned formula (1), (2), more specifically, following shown compound can be illustrated.
[changing 25]
[changing 26]
[changing 27]
(in formula, Rf ' is-CF
2o (CF
2o)
p1(CF
2cF
2o)
q1cF
2-, p1, q1 are the numbers meeting q1/p1=0.8 ~ 1.5, q1+p1=5 ~ 80.R1 is the integer of 2 ~ 100, preferably 2 ~ 50 separately.N1 is the integer of 0 ~ 30, preferably 1 ~ 15 independently of one another.)
Such general formula (1) or the fluorine-containing based compound shown in (2), to its synthesis method, there is no particular restriction, such as, first, by making following general formula (3) or (4)
[Rf
1-Z
1]
a-Q
1-[H]
b(3)
[H]
b-Q
2-Z
1-Rf
2-Z
1-Q
2-[H]
b(4)
(in formula, Rf
1, Rf
2, Z
1, Q
1, Q
2, a, b be same as described above, a the Z bracketed with []
1with b H all respective and Q
1or Q
2silicon atom bonding in structure.)
The shown perfluoroalkyl polyether compound with multifunctional Si-H group and following general formula (5)
CH
2＝CR
1-Z
2-CHR
2-OH (5)
(in formula, R
1, R
2, Z
2same as described above.)
The shown alcohol (having the compound of thiazolinyl and secondary alcohol in molecule) containing terminal unsaturation group carries out hydrosilylation reactions, thus can obtain the fluorine-containing alcohol compound as intermediate.
Wherein, as the perfluoroalkyl polyether compound with multifunctional Si-H group shown in above-mentioned formula (3), (4), following shown compound can be illustrated.
[changing 28]
[changing 29]
[changing 30]
[changing 31]
(in formula, Rf ', r1 are same as described above.)
In addition, as the alcohol containing terminal unsaturation group shown in above-mentioned formula (5), the alcohol shown in following general formula (a) can be illustrated.
CH
2＝CR
1-Z
3-OCH
2CH(CH
3)-OH (a)
(in formula, R
1, Z
3same as described above.)
As the alcohol containing terminal unsaturation group shown in above-mentioned formula (a), the alcohol shown in preferred following general formula (b).
CH
2＝CH-CH
2-[OC
3H
6]
n-OCH
2CH(CH
3)-OH (b)
(in formula, n is same as described above.)
As the alcohol containing terminal unsaturation group shown in above-mentioned formula (5), particularly, following shown alcohol can be illustrated.
CH
2＝CH-CH
2-OCH
2CH(CH
3)-OH
CH
2＝CH-CH
2-(OC
3H
6)
2-OCH
2CH(CH
3)-OH
CH
2＝CH-CH
2-(OC
3H
6)
4-OCH
2CH(CH
3)-OH
CH
2＝CH-CH
2-(OC
3H
6)
9-OCH
2CH(CH
3)-OH
[changing 32]
This hydrosilylation (addition) is reacted, preferably, the alcohol containing terminal unsaturation group shown in the perfluoroalkyl polyether compound with multifunctional Si-H group shown in formula (3) or (4) and formula (5) is mixed, under the addition reaction catalyst of platinum metals system exists, carry out reaction at temperature of reaction 50 ~ 150 DEG C, preferably 60 ~ 120 DEG C 1 minute ~ 48 hours, especially 10 minute ~ 12 hours.If temperature of reaction is too low, sometimes react when reacting and not carrying out fully and stop, if too high, the temperature sometimes caused due to the reaction heat of hydrosilylation rises, and can not control reaction, and the decomposition etc. of bumping, raw material occurs.
In this case, by the perfluoroalkyl polyether compound with multifunctional Si-H group shown in formula (3) or (4) and the reaction ratio by the alcohol containing terminal unsaturation group shown in formula (5), relative to the total mole number of the H bracketed by the use [] with the perfluoroalkyl polyether compound of multifunctional Si-H group shown in formula (3) or (4), preferably use 0.5 ~ 5.0 times mole, especially 0.9 ~ 2.0 times mole by shown in formula (5) containing terminal unsaturation group alcohol terminal unsaturation group and make it react.By formula (5) if shown in very few in contrast containing the alcohol of terminal unsaturation group, then be difficult to the fluorine-containing alcohol compound obtaining having high resolution, if more than it too much, the homogeneity of reaction soln reduces, speed of response becomes unstable, and in the degree only increasing remaining unreacted alcohol, strictly controls the conditions such as heating, decompression, extraction when reacting the removing of the alcohol containing terminal unsaturation group shown in laggard line (5).
Addition reaction catalyst can use the compound such as comprising the platinum metals such as platinum, rhodium or palladium.Wherein preferably comprise the compound of platinum, chlordene platinum (IV) sour hexahydrate, platinum carbonyl ethylene ylmethyl complex compound, platinum-divinyl tetramethyl disiloxane complex compound, platinum-cyclovinylmethylsiloxane complex compound, platinum-octanal/octanol complex can be used or be carried on the platinum of gac.
The use level of addition reaction catalyst, relative to by the perfluoroalkyl polyether compound with multifunctional Si-H group shown in formula (3) or (4), preferably contained amount of metal is 0.1 ~ 5,000 quality ppm, is more preferably 1 ~ 1,000 quality ppm.
Also can implement even if above-mentioned addition reaction does not exist solvent, but useable solvents dilution as required.Now, diluting solvent can utilize the general widely used organic solvents such as toluene, dimethylbenzene, octane-iso, preferred boiling point is more than the temperature of reaction of target, and do not hinder reaction, the compound of the formula (1) that reaction generates afterwards or (2) is solvable under above-mentioned temperature of reaction.As such solvent, preference as the solvent of the part fluorine richness such as fluorine richness ether series solvent such as fluorine richness aromatic hydrocarbons series solvent, methyl perfluorobutyl ether such as hexafluoro m-xylene, trifluoromethylbenzene, particularly preferably hexafluoro m-xylene.
When using solvent, its usage quantity, relative to by perfluoroalkyl polyether compound 100 mass parts with multifunctional Si-H group shown in formula (3) or (4), is preferably 5 ~ 2,000 mass parts, is more preferably 50 ~ 500 mass parts.If fewer than it, the effect of the dilution that solvent produces is weak, if many, extent of dilution excessively raises, and sometimes causes the reduction of speed of response.
After reaction terminates, preferred employing decompression is heated up in a steamer except the known methods such as, extractions, absorption are by the alcohol containing terminal unsaturation group shown in unreacted formula (5), diluting solvent removing, but the reaction mixture containing these also can directly use in ensuing reaction.
As the fluorine-containing alcohol compound obtained like this, following shown compound can be illustrated.[changing 33]
[changing 34]
[changing 35]
(in formula, r1, n1, Rf ' same as described above.)
Next, by importing acryl in fluorine-containing alcohol compound obtained above, fluorine-containing based compound can be obtained.As method acryl being imported fluorine-containing alcohol compound; can enumerate for one and react with the acryloyl halide shown in following formula (6) and form the method for ester; another can enumerate the method for reacting with the isocyanate compound containing acryl shown in following formula (7); adopt these methods, the fluorine-containing based compound of target of the present invention can be obtained.
CH
2＝CR
4COX (6)
CH
2＝CR
4COOCH
2CH
2-N＝C＝O (7)
(in formula, R
4for hydrogen atom or methyl, X is the halogen atoms such as fluorine atom, chlorine atom, bromine atoms.)
Wherein, as the acryloyl halide shown in formula (6), following shown compound can be enumerated.
CH
2＝CHCOX
CH
2＝CCH
3COX
(in formula, X is same as described above.)
Particularly preferably acrylate chloride, methacrylic chloride.
In addition, as the isocyanate compound containing acryl shown in formula (7), following shown compound can be enumerated.
CH
2＝CHCOOCH
2CH
2-N＝C＝O
CH
2＝CCH
3COOCH
2CH
2-N＝C＝O
These acryloyl halides or the isocyanate compound containing acryl; can relative to the total of the amount of hydroxyl groups of fluorine-containing alcohol compound; load wait mole more than and make it react; make whole hydroxyl reaction; also can relative to fluorine-containing alcohol compound 1 mole; the acryl of average importing more than 1 mole, by making hydroxyl excessive, does not make unreacted acryloyl halide or the isocyanate compound containing acryl remain.Particularly; fluorine-containing alcohol compound amount in reaction system is designated as x mole; when the total of the amount of hydroxyl groups of fluorine-containing alcohol compound is designated as y mole; preferred acryloyl halide or the isocyanate compound containing acryl are more than x mole less than 2y mole, are particularly preferably more than 0.6y mole less than 1.3y mole.When fewer than 0.6y mole, all do not import the possibility rising that the fluorine-containing alcohol compound of acryl is remaining, likely the solvability of resultant reduces.If than more than 1.3y mole, the residue removal of unreacted acryloyl halide or the isocyanate compound containing acryl becomes difficulty.
These reactions, can react with suitable solvent cut as required.As such solvent, as long as not with the hydroxyl of fluorine-containing alcohol compound, the halogen atom of acryloyl halide, the solvent of the isocyanic ester radical reaction of the isocyanate compound containing acryl, then can use with no particular limitation, particularly, toluene can be enumerated, dimethylbenzene, the hydrocarbon system solvents such as octane-iso, tetrahydrofuran (THF), Di Iso Propyl Ether, the ether series solvents such as dibutyl ether, acetone, methyl ethyl ketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), the ketone series solvents such as pimelinketone, hexafluoro m-xylene, the fluorine richness aromatic hydrocarbons series solvents such as trifluoromethylbenzene, the fluorine richness ether series solvents etc. such as methyl perfluorobutyl ether.The known method removings such as this solvent can adopt decompression to heat up in a steamer to remove after the reaction, also can use in intended applications as diluting soln as former state.
In addition, during reaction, stopper can be added as required.As stopper, there is no particular restriction, can use the stopper of the stopper being typically used as acrylic compounds.Particularly, quinhydrones, Hydroquinone monomethylether, 4-tert-butyl catechol, butylated hydroxytoluene etc. can be enumerated.
When fluorine-containing alcohol compound and acryloyl halide are reacted, particularly preferably make acrylate chloride, methacrylic chloride react, generate ester.This ester formation reaction, while undertaken above-mentioned reaction intermediate (fluorine-containing alcohol compound), antacid mix and blend limit acryloyl halide instillation.Antacid can use triethylamine, pyridine, urea etc.
For instillation, the temperature of reaction mixture is maintained 0 ~ 35 DEG C, last 20 ~ 60 minutes and carry out.Then, further Keep agitation 30 minutes ~ 10 hours.React after terminating, remove by the employings such as unreacted acryloyl halide, the salt generated by reaction and reaction solvent are heated up in a steamer, adsorb, filter method removings such as cleaning, fluorine-containing based compound of the present invention can be obtained.
In addition, when reaction stops, the alkylol cpd such as methyl alcohol, ethanol can be added in system, by unreacted acryloyl halide esterification.The esters of acrylic acid generated can adopt and remove same method with unreacted acryloyl halide and remove, and also can use when remaining.
When fluorine-containing alcohol compound and the reaction of isocyanate compound containing acryl, fluorine-containing alcohol compound is stirred as required with the isocyanate compound containing acryl together with solvent, reacts.
In this reaction, in order to increase the speed of reaction, suitable catalyzer can be added.As catalyzer, such as dibutyltin diacetate can be illustrated, dibutyl tin laurate, two sad dibutyl tins, two acetic acid dioctyl tins, tin dilaurate dioctyl tin, two sad dioctyl tins, the tin alkyl ester cpds such as two stannous octoates, tetraisopropoxy titanium, four titanium n-butoxide, four (2-ethyl hexyl oxy) titanium, two (methyl ethyl diketone) titanium of dipropoxy, titanic acid ester or the titanium chelate compounds such as isopropoxy ethohexadiol titanium, four methyl ethyl diketone zirconiums, three butoxy single acetyl acetone zirconiums, two (methyl aceto acetate) zirconium of only son's oxygen ethylacetoacetone, two (methyl aceto acetate) zirconium of dibutoxy, four methyl ethyl diketone zirconiums, zirconium chelate compound etc.These are not limited to its a kind, can use as 2 kinds or its above mixture, particularly preferably on the use of the low titanium compound of the impact of environment, zirconium compounds.
By relative to reactant total mass, add these catalyzer of 0.01 ~ 2 quality %, preferably 0.05 ~ 1 quality %, speed of response can be made to increase.React to carry out at the temperature of 0 ~ 120 DEG C, preferably 10 ~ 70 DEG C 1 minute ~ 500 hours, preferably 10 minute ~ 48 hours.If temperature of reaction is too low, speed of response is excessively slack-off sometimes, if temperature of reaction is too high, likely as the polymerization of side reaction generation acryl.
After reaction terminates, methods such as removing by the employings such as unreacted isocyanate compound and reaction solvent being heated up in a steamer, adsorbing, filtration is cleaned removes, and can obtain fluorine-containing based compound of the present invention.
In addition, when reaction stops, the alkylol cpd such as methyl alcohol, ethanol can be added in system, form urethane bond with unreacted isocyanate compound.The urethane acrylate class generated can adopt the method same with unreacted isocyanate compound to remove, and also can use when remaining.
The embodiment of another way of the present invention is the solidification compound of the fluorine-containing based compound (A) obtained comprised as described above, as this solidification compound, especially, preferably utilizes active energy ray and solidifies.(A) composition also can make it solidify individually, such as, by coordinating with the active energy ray-curable composition (B) beyond (A) composition, when maintaining the characteristic as the cured article of (B) composition such as hardness, the antifouling properties of the excellence of (A) composition generation can be given from the teeth outwards.
The active energy ray-curable composition of suitable (B) composition used in the present invention, as long as can mix with (A) composition, solidification, can use any composition, be particularly preferably esters of acrylic acid, can enumerate and such as comprise 1,6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, isocyanuric acid ethylene-oxide-modified two (methyl) acrylate, isocyanuric acid EO modification three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, glycerine three (methyl) acrylate, tricresyl phosphate (methyl) acryloyloxyethyl ester, hydrogen phthalate-(2,2,2-tri--(methyl) acryloyloxymethyl) ethyl ester, glycerine three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, two (TriMethylolPropane(TMP)) four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, (methyl) acrylic compounds of sorbyl alcohol six (methyl) acrylate etc. 2 ~ 6 official energy, the oxyethane of these (methyl) acrylic compounds, propylene oxide, Epicholorohydrin, lipid acid, alkyl-modified product, make the Epoxy Acrylates that epoxy resin and vinylformic acid addition obtain, the composition of the multipolymer of (methyl) acryl etc. has been imported with the side chain at acrylate copolymer.
In addition, the product that urethane acrylate class, (methyl) acrylate making to have hydroxyl and polyisocyanates also can be used to react and obtain, make the polyester of polyisocyanates and end glycol with have hydroxyl (methyl) acrylate reactions and obtain product, make excessive vulcabond and polyol reaction and the polyisocyanates that obtains and (methyl) acrylate reactions with hydroxyl and the product that obtains.Wherein, the urethane acrylate class preferably making (methyl) acrylate with hydroxyl selected from (methyl) vinylformic acid 2-hydroxy methacrylate, methacrylic acid 2-hydroxyl-3-acryloxy propyl ester and pentaerythritol triacrylate react with the polyisocyanates selected from hexamethylene diisocyanate, isophorone diisocyanate, Xylene Diisocyanate and diphenylmethanediisocyanate.Above-claimed cpd can be used alone, and also two or more may be used.In addition, in order to regulate the physical property of composition, the esters of acrylic acid of 1 official's energy can be coordinated.
In addition, solidification compound of the present invention, by containing Photoepolymerizationinitiater initiater as (C) composition, the solidification compound utilizing ultraviolet curing can be become.
(C) Photoepolymerizationinitiater initiater of composition, as long as acrylic compounds can be made to solidify by uviolizing, is then not particularly limited, and preferably, can enumerate such as methyl phenyl ketone, benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-ketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, 2,4,6-trimethylbenzoy-dipheny-phosphine oxide, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 1,2-octadione-1-[4-(thiophenyl)-2-(o-benzoyl oximes)], ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-ethanoyl oxime), 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl] phenyl }-2-methyl-propan-1-ketone etc., can be used alone, also two or more may be used.
In solidification compound of the present invention, the use level of each composition, suitably can determine according to the solvability of required water-repellancy, grease proofness, composition, condition of cure etc., to the compounding ratio of (A) composition, (B) composition, (C) composition, there is no particular restriction, such as, (B) use level of composition, relative to (A) composition 100 mass parts, preferably 1 ~ 10,000 mass parts, be more preferably 5 ~ 1,000 mass parts, be particularly preferably 10 ~ 200 mass parts.In addition, when using (C) composition, the use level of (C) composition, when counting 100 mass parts by the total amount of (A) composition, (B) composition, preferably 0.1 ~ 10 mass parts, is particularly preferably 0.5 ~ 5 mass parts.
Further, coordinated the hard paint of above-mentioned (B) composition and (C) composition by the various product of each Company.Solidification compound of the present invention can be the product that with the addition of (A) composition in the hard paint of such commercially available product.As the hard paint of commercially available product, can enumerate such as waste river chemical industry (strain) “ ビ ー system セ ッ ト ", bridge chemical industry (strain) “ ユ ー PVC ッ Network ", オ リ ジ Application is (strain) " UV コ ー ト " electrically, カ シ ュ ー (strain) " カ シ ュ ー UV ", JSR (strain) " デ ソ ラ イ ト ", to refine large day industry (strain) " セ イ カ ビ ー system ", Japan's synthetic chemistry (strain) " purple light ", Teng Cang changes into (strain) " Off ジ Ha ー De ", Mitsubishi レ イ ヨ Application (strain) " ダ イ ヤ ビ ー system ", Musashi coating (strain) " ウ Le ト ラ バ イ Application " etc.
[other additives]
In solidification compound of the present invention, in addition, according to object, organic solvent, stopper, static inhibitor, defoamer, viscosity modifier, resistance to photostabilizer, heat-resisting stabilizing agent, antioxidant, tensio-active agent, tinting material and filler etc. also can be coordinated.In addition, even when using the hard paint of commercially available product as mentioned above, also organic solvent, stopper, static inhibitor, defoamer, viscosity modifier, resistance to photostabilizer, heat-resisting stabilizing agent, antioxidant, tensio-active agent, tinting material and filler etc. can be coordinated according to object.
As organic solvent, the alcohols such as 1-propyl alcohol, 2-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, Pyranton can be enumerated; The ketones such as methyl propyl ketone, metacetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone; The ethers such as dipropyl ether, dibutyl ether, phenylmethylether, diox, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether; The ester classes etc. such as propyl acetate, N-BUTYL ACETATE, cyclohexyl acetate.Above-mentioned solvent can be used alone a kind, also can be used in combination by two or more.
To the usage quantity of solvent, there is no particular restriction, relative to total 100 mass parts of (A) ~ (C) composition, preferably 50 ~ 10,000 mass parts, particularly preferably 100 ~ 1,000 mass parts.
In addition, as stopper, static inhibitor, defoamer, viscosity modifier, resistance to photostabilizer, heat-resisting stabilizing agent, antioxidant, tensio-active agent, tinting material and filler, known material can be used with no particular limitation in the scope not damaging object of the present invention.
The curing of solidification compound of the present invention is not particularly limited, such as, when containing (B) composition, active energy ray can be adopted to make it solidify, when also containing the Photoepolymerizationinitiater initiater of (C) composition, ultraviolet can be adopted to make it solidify.
As previously discussed, if solidification compound of the present invention, then the consistency becoming the solidified nature composition of hard coating composition and fluorine-containing based compound is good, can utilize ultraviolet isoreactivity energy line curing, can form didirtresistance, the solidification compound of the curing resin layer of excellent scratch resistance.
In addition, in the present invention, provide above-mentioned solidification compound of the present invention in surface coated and the base material making it solidify.As mentioned above, if use solidification compound of the present invention, the solidification tunicle (curing resin layer) with excellent surface property can be formed on the surface of base material.Especially, can be used for giving water-repellancy, grease proofness, didirtresistance to the surface of acrylic acid series hard coat.Thereby, it is possible to contamination base material being given to the generations such as people's fat, the makeup such as fingerprint, sebum, sweat is difficult to attachment, and the hard coating surface that erasing property is also excellent.Therefore, solidification compound of the present invention can provide for likely human contact, the coated film on the surface of base material (article) stain by people's fat, makeup etc. or protective membrane.
Housing, the Wristwatch-type glasses type wearable computer of the various equipment that the hand that the solidification tunicle (curing resin layer) using solidification compound of the present invention to be formed can be used as the employments such as Tablet PC, notebook PC, mobile telephone smart mobile phone etc. portable (communication) intelligent terminal, digital media player, e-book carries, liquid-crystal display, plasma display, organic EL (electroluminescent) indicating meter, back side projection type indicating meter, fluorescent display tube (VFD), the field emission projected display, CRT, to surface such as the display operating equipment of the picture of the various flat-panel monitors such as system indicating meter and TV etc., automobile exterior, piano, the finish plate of furniture, the stone surface for building such as marble, lavatory, bathtub, vanity tops etc. are around the decorative building material of water, artistic products displaying protective glass, show window, display stands, photo frame front cover, wrist-watch, automotive glazings, train, the window glass of flyer etc., car headlamp, the glass system that taillight etc. are transparent or transparent plastics system (acrylic acid series, polycarbonate etc.) parts, the coated film of various reflection mirror components etc. and surface protection film.
Especially, can be used as contact panel display etc. and there are the various equipment that the finger of employment or palm carry out the display input device of the operation on picture, such as Tablet PC, notebook PC, mobile telephone, portable (communication) intelligent terminal, digital media player, e-book, digital frame, game machine, digital camera, Digital Video, the Nvgtl aids of automobile use etc., automatic cash transaction apparatus, cash dispenser, vending machine, Digital ID (electronic bill-board), security system terminal, POS terminal, the various controller such as telepilot, the surface protection film of the display input devices such as car-mounted device panel switch etc.
In addition, the solidification tunicle formed by solidification compound of the present invention also can be used as the optical recording medium such as photomagneto disk, CD; The surface protection tunicle of the optics optical devices such as eyeglass lens, prism, lens, pellicle, polaroid, optical filter, biconvex lens, Fresnel lens, antireflective coating, optical fiber, opticcoupler.
Embodiment
Synthesis example, embodiment and comparative example are below shown, the present invention is specifically described, but the present invention does not limit by following embodiment.
[synthesis example 1]
Following formula is loaded in the 1L four-hole boiling flask with reflux and whipping appts
[changing 36]
Single terminal allylic ether (containing ratio 100% of Nippon Yushi (Co., Ltd.) ユ ニ Le ー Block MA-35, molecular weight 639, secondary alcohol) 89g (allyl base unit weight 0.0016mol/g), the hexafluoro m-xylene 300g of shown compound (I) 200g (Si-H value 0.00061mol/g), polypropylene glycol, heated and stirred is until 90 DEG C under nitrogen atmosphere.Drop into platinum/1 wherein, the toluene solution 0.442g of 3-divinyl-tetramethyl disiloxane complex compound is (in Pt simple substance, containing 1.1 × 10
-6mol), under the state that interior temperature is maintained more than 90 DEG C, continue stirring 4 hours, adopt
1h-NMR confirms to disappear from the allyl group of raw material, the peak of Si-H group.Next, in the flask of 5L with whipping appts, load hexane 3L, instill the above-mentioned reaction soln of cool to room temperature while stirring, and then stir 1 hour.Stir stop after, leave standstill 2 hours, the hexane layer decant on upper strata is removed, with vaporizer from the throw out obtained by remaining solvent remove, obtain translucent faint yellow high thick liquid by compound (II) 272g shown in following formula.
[changing 37]
By compound (II)
1h-NMR chemical shift is shown in table 1.
[table 1]
[synthesis example 2]
リ ナ ロ ー Le オ キ シ De (ピ ラ ノ イ De) (3-hydroxyl-2 is employed except replacing ユ ニ ル ー Block MA-35,2,6-trimethylammonium-6-vinyl tetrahydropyrans) beyond 22g, similarly to Example 1, obtain translucent faint yellow high thick liquid by compound (III) 201g shown in following formula.
By compound (III)
1h-NMR chemical shift is shown in table 2.
[table 2]
[synthesis example 3]
Under dry nitrogen atmosphere, in 2, the 000mL there-necked flasks with reflux and whipping appts, drop into following formula
CH
2＝CH-CH
2-O-CH
2-Rf’-CH
2-O-CH
2-CH＝CH
2
Rf’：-CF
2(OCF
2CF
2)
q(OCF
2)
pOCF
2-
(q/p＝0.9、p+q≒45)
Shown PFPE 500g [0.125mol] and hexafluoro m-xylene 700g and tetramethyl-ring tetrasiloxane 361g [1.50mol], is heated to 90 DEG C while stirring.Drop into platinum/1 wherein, the toluene solution 0.442g of 3-divinyl-tetramethyl disiloxane complex compound is (in Pt simple substance, containing 1.1 × 10
-6mol), under the state that interior temperature is maintained more than 90 DEG C, stirring 4 hours is continued.With
1after H-NMR confirms that the allyl group of raw material disappears, solvent and the decompression of excessive tetramethyl-ring tetrasiloxane are heated up in a steamer and removes.Then, carry out activated carbon treatment, obtain by water white aqueous compound (IV) 498g shown in following formula.
[changing 39]
Rf’：-CF
2(OCF
2CF
2)
q(OCF
2)
pOCF
2-
(q/p＝0.9、p+q≒45)
Under dry air atmosphere, relative to compound obtained above (IV) 50.0g [Si-H group amount 0.0669mol], by the toluene solution 0.0442g of five propylene glycol mono allyl ether 27.5g [0.0789mol], the hexafluoro m-xylene 50.0g and Platinic chloride/vinylsiloxane complex compound with secondary alcohol end (in Pt monomer, containing 1.1 × 10
-7mol) mix, stir 4 hours at 100 DEG C.With
1after H-NMR and IR confirms that Si-H group disappears, by reaction soln cool to room temperature.Next, in the flask of 2L with whipping appts, load hexane 500mL, instill the above-mentioned reaction soln of cool to room temperature while stirring, then stir 1 hour.Stir stop after leave standstill 2 hours, the hexane layer decant on upper strata is removed, with vaporizer from the throw out obtained by remaining solvent remove, obtain translucent faint yellow high thick liquid by compound (V) 45.1g shown in following formula.
[changing 40]
Rf’：-CF
2(OCF
2CF
2)
q(OCF
2)
pOCF
2-
(q/p＝0.9、p+q≒45)
By compound (V)
1h-NMR chemical shift is shown in table 3.
[table 3]
[synthesis example 4]
Under dry air atmosphere, by the toluene solution 0.0442g of compound (IV) 50.0g [Si-H group amount 0.0669mol] of synthesis example 3,2-allyloxyethanol 7.05g [allyl base unit weight 0.0690mol], hexafluoro m-xylene 50.0g and Platinic chloride/vinylsiloxane complex compound (in Pt simple substance, containing 1.1 × 10
-7mol) mix, stir 4 hours at 100 DEG C.With
1after H-NMR and IR confirms that Si-H group disappears, solvent and the decompression of superfluous 2-allyloxyethanol are heated up in a steamer and removes, carry out activated carbon treatment, obtain compound (VI) 55.2g being contained PFPE by the liquid of the pale yellow transparent shown in following formula.
[changing 41]
Rf’：-CF
2(OCF
2CF
2)
q(OCF
2)
pOCF
2-
(q/p＝0.9、p+q≒45)
By compound (VI)
1h-NMR chemical shift is shown in table 4.
[table 4]
[synthesis example 5]
Employ except リ ナ ロ ー Le オ キ シ De (Off ラ ノ イ De) (2-(2-hydroxyl-2-propyl group)-5-methyl-5-vinyl tetrahydrofuran (THF)) 22g except replacing ユ ニ ル ー Block MA-35, similarly to Example 1, obtain translucent faint yellow high thick liquid by compound (VII) 198g shown in following formula.
[changing 42]
By compound (VII)
1h-NMR chemical shift is shown in table 5.
[table 5]
[embodiment 1,2 and comparative example 1]
To be respectively charged in the 100mL eggplant type flask of 2 mouthfuls with reflux and agitator for each compound 10.0g of the fluorine-containing alcohol compound (II) obtained in synthesis example, (III) and (VII) and methyl ethyl ketone 10.0g, 4-methoxyhydroquinon 0.01g, and then add the vinylformic acid 2-isocyanatoethyl of the amount shown in following table 6, under dry atmosphere, be heated to 40 DEG C.Next, add 10 quality % methyl ethyl ketone solution 0.2g of metatitanic acid four monooctyl ester wherein, at 40 DEG C, continue heating.For reaction soln, within every 12 hours, sample, carry out the mensuration of IR spectrum, confirm 2,280cm from isocyanate group
-1peak disappear time.Table 6 will be the results are shown in.
[table 6]
For the reaction solution of embodiment 1 and embodiment 2, after the peak of isocyanate groups disappears respectively after cool to room temperature, drop into hexane 100g, stir 1 hour.After stirring terminates, filter with filter paper, make component dissolves residual on filter paper with hexafluoro m-xylene, carrying out under 80 DEG C/0.13kPa reduces pressure to heat up in a steamer for 2 hours removes, and obtains the fluorine-containing based compound of target.
The compound of embodiment 1 is below shown.
[changing 43]
Output 9.2g
By the compound of embodiment 1
1h-NMR chemical shift is shown in table 7.
[table 7]
The compound of embodiment 2 is below shown.
[changing 44]
Output 8.5g
By the compound of embodiment 2
1h-NMR chemical shift is shown in table 8.
[table 8]
[embodiment 3,4 and comparative example 2,3]
The fluorine-containing alcohol compound (V) obtained in synthesis example and (VI) are loaded in glass dish, (V '), (VI ') will be designated as respectively at 100 DEG C/12 little samples heated at present under nitrogen atmosphere.
By for the fluorine-containing alcohol compound (V) obtained in synthesis example and (VI) and carried out each compound 10.0g of (V ') and (VI ') of heat treated and methyl ethyl ketone 10.0g, 4-methoxyhydroquinon 0.01g to them and be respectively charged in the 100mL eggplant type flask of 2 mouthfuls with reflux and agitator, and then add the vinylformic acid 2-isocyanatoethyl of the amount shown in following table 9, under dry atmosphere, be heated to 40 DEG C.Next, add 10 quality % methyl ethyl ketone solution 0.2g of metatitanic acid four monooctyl ester wherein, at 40 DEG C, continue heating.After 12 hours, each reaction soln is sampled, carry out the mensuration of IR spectrum, all confirm 2,280cm from isocyanate groups in all situations
-1the disappearance at peak.
For reaction solution, after the peak of isocyanate groups disappears after difference cool to room temperature, drop in hexane 100g, stir 1 hour.After stirring terminates, filter with filter paper, the component dissolves will filter paper remained with hexafluoro m-xylene, carrying out under 50 DEG C/0.13kPa reduces pressure to heat up in a steamer for 2 hours removes, and obtains the fluorine-containing based compound of target.
By the fluorine-containing based compound obtained and solution 5 mass parts and the diacrylate 1 that are diluted to 20 quality % by methyl iso-butyl ketone (MIBK), 6-hexylene glycol ester 100 mass parts mixes, and at room temperature leaves standstill after 1 hour, carries out visual confirmation, if do not produce muddiness, then for dissolving.These be the results are shown in table 9.
[table 9]
The compound of embodiment 3 and 4 is below shown.
[changing 45]
Rf’：-CF
2(OCF
2CF
2)
q(OCF
2)
pOCF
2-
(q/p＝0.9、p+q≒45)
By the compound of embodiment 3 and 4
1h-NMR chemical shift is shown in table 10.
[table 10]
[evaluation of the making of cured article and the didirtresistance on cured article surface]
Will as the embodiment 1 ~ 3 of (A) composition and compound 1 mass parts of comparative example 2,4 functional acrylates (mixing of EBECRYL 40 (ダ イ セ Le オ Le ネ Network ス society system) 100 mass parts, 1-hydroxycyclohexylphenylketone 3 mass parts as (C) composition and 2-propyl alcohol 142 mass parts as solvent, the modulation solidification compound as (B) composition.
Each composition of modulation is coated with (wet coating thickness 16.0 μm) with coiling rod No.7 on polycarbonate substrate.After carrying out the drying of 100 DEG C, 1 minute after coating, use delivering metal halide UV irradiating unit (パ Na ソ ニ ッ Network electrician system), by cumulative exposure 1,600mJ/cm in nitrogen atmosphere
2uviolizing to coated face, composition is solidified.The water contact angle of the cured film obtained, oleic acid contact angle, magic ink erasing property are measured, evaluated.In order to compare, for the sample not containing (A) composition, also carry out same evaluation as comparative example 4.Their result is shown in table 11.
(evaluation of measuring method)
1) water contact angle measurement
Use contact angle meter (republicanism interface science society DropMaster), the drop of 2 μ L is dripped in cured film, measures the contact angle after 1 second.Using the mean value of N=5 as measured value.
2) oleic acid contact angle determination
Use contact angle meter (republicanism interface science society DropMaster), the drop of 7 μ L is dripped in cured film, measures the contact angle after 1 second.Using the mean value of N=5 as measured value.
3) evaluation of magic ink erasing property
Describe straight line at cured film surface magic ink (ゼ Block ラ society Ha イ マ ッ キ mono-(registered trademark) boldface letter), evaluate its repulsion situation by visual observation.
[table 11]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 2 | Comparative example 4 | |
| Water contact angle (°) | 112 | 113 | 106 | 113 | 59 |
| Oleic acid contact angle (°) | 71 | 72 | 69 | 72 | 20 |
| Magic ink erasing property | Erasing | Erasing | Erasing | Erasing | Do not wipe |
Claims (10)
1. following general formula (1) or the fluorine-containing based compound shown in (2):
[Rf
1-Z
1]
a-Q
1-[CH
2-CHR
1-Z
2-CHR
2-OR
3]
b(1)
[R
3O-CHR
2-Z
2-CHR
1-CH
2]
b-Q
2-Z
1-Rf
2-Z
1-Q
2-[CH
2-CHE
1-Z
2-CHR
2-OR
3]
b(2)
In formula, Rf
1for the holo-fluorine polyester of 1 valency of molecular weight 400 ~ 20,000 be made up of perfluoroalkyl and the Sauerstoffatom of carbon number 1 ~ 6, Rf
2for the holo-fluorine polyester of the divalent of molecular weight 400 ~ 20,000 be made up of perfluorinated alkylidene and the Sauerstoffatom of carbon number 1 ~ 6, Z
1be the alkyl of the divalent of Han the Sauerstoffatom of carbon number 1 ~ 20, nitrogen-atoms and Siliciumatom independently, midway can contain ring texture; Q
1for comprising at least the connection base of (a+b) valency of (a+b) individual Siliciumatom, Q
2independently for comprising at least the connection base of (b+1) valency of (b+1) individual Siliciumatom; Z
2be the alkyl of Han the Sauerstoffatom of carbon number 1 ~ 200 and the divalent of nitrogen-atoms independently, midway can contain ring texture, R
1be the alkyl of 1 valency of hydrogen atom or carbon number 1 ~ 8 independently; R
2be the alkyl of 1 valency of carbon number 1 ~ 8 independently, Z
2with R
1and/or Z
2with R
2can combine respectively and with and R
1, R
2in conjunction with carbon atom form ring texture together, in addition, R
1with R
2can in conjunction with and formed containing Z together with the carbon atom separately to combine
2ring texture; A is the integer of 1 ~ 10, and b is the integer of 1 ~ 10 independently, R
3be hydrogen atom or the organic group with 1 valency of acryl or α substituted acryl that can contain Sauerstoffatom and nitrogen-atoms independently of one another, but, R
3on average there is the organic group of at least 1 above-mentioned 1 valency in the molecule.
2. fluorine-containing based compound according to claim 1, wherein, the following formula in general formula (1) and (2)
-Z
2-CHR
2-OR
3
Shown group is the group shown in following formula:
-Z
3-OCH
2CH(CH
3)-OR
3
In formula, R
3same as described above, Z
3for the alkyl of Han the Sauerstoffatom of carbon number 1 ~ 199 and the divalent of nitrogen-atoms, midway can form ring texture, in addition, and adjacent R
1with Z
3can in conjunction with and with and R
1in conjunction with carbon atom form ring texture together.
3. fluorine-containing based compound according to claim 2, wherein, the following formula in general formula (1) and (2)
-Z
2-CHR
2-OR
3
Shown group is the group shown in following formula:
-CH
2-[OC
3H
6]
n-OCH
2CH(CH
3)-OR
3
In formula, R
3same as described above, n is the integer of 0 ~ 64.
4. fluorine-containing based compound according to claim 1, it is represented by following general formula (8) or (9):
[Rf
1-Z
1]
a-Q
1-[CH
2CH
2CH
2[OC
3H
6]
nOCH
2CH(CH
3)OCOCR
4＝CH
2]
b(8)
Rf
2-{Z
1-Q
2-[CH
2CH
2CH
2[OC
3H
6]
nOCH
2CH(CH
3)OCONHCH
2CH
2OCOCR
4＝CH
2]
b}
2
(9)
In formula, Rf
1, Rf
2, Q
1, Q
2, Z
1, a, b be described above, n is the integer of 0 ~ 64, R
4for hydrogen atom or methyl.
5. fluorine-containing based compound according to claim 1, wherein, Rf
1for being selected from the structure of following formula (i), (ii), (iii):
CF
3O-(CF
2O)
p-(CF
2CF
2O)
q-CF
2- (i)
In formula, p is the integer of 0 ~ 400, and q is the integer of 0 ~ 170, and p+q is the integer of 2 ~ 400,
F[CF(CF
3)CF
2O]
r-CF(CF
3)- (ii)
In formula, r is the integer of 1 ~ 120,
F[CF
2CF
2CF
2O]
s-CF
2CF
2- (iii)
In formula, s is the integer of 1 ~ 120,
Rf
2for being selected from the structure of following formula (iv), (v):
-CF
2O-(CF
2O)
p-(CF
2CF
2O)
q-CF
2- (iv)
In formula, p is the integer of 0 ~ 400, and q is the integer of 0 ~ 170, and p+q is the integer of 2 ~ 400,
-CF(CF
3)-[OCF
2CF(CF
3)]
t-OCF
2CF
2O-[CF(CF
3)CF
2O]
u-CF(CF
3)- (v)
In formula, t+u is the integer of 2 ~ 120,
Q
1be selected from following formula (vi) ~ (ix):
In formula, a, b are the integer of 1 ~ 10 independently of one another, and c is the integer of 1 ~ 5, and the arrangement of each unit is random, bonding end and a the Z bracketed with [] of (a+b) individual each unit etc.
1with b CH
2in any one group combine,
T is the connection base of (a+b) valency, is any one of following formula (x) ~ (xiv):
Q
2be selected from following formula (xv) ~ (xviii):
In formula, b is the integer of 1 ~ 10, and c is the integer of 1 ~ 5, and the arrangement of each unit is random, the bonding end of (b+1) individual each unit etc. and Z
1with b the CH bracketed with []
2any one group combine,
T ' is any one in following formula (xix) ~ (xxiii):
Z
1be selected from following formula:
-CH
2CH
2-
-CH
2CH
2CH
2-
-CH
2CH
2CH
2CH
2-
-CH
2OCH
2CH
2-
-CH
2OCH
2CH
2CH
2-
6. fluorine-containing based compound according to claim 1, wherein, formula (1) or the fluorine-containing based compound shown in (2) they are any one in following formula (A1) ~ (A3):
In formula, Rf ' is-CF
2o (CF
2o)
p1(CF
2cF
2o)
q1cF
2-, p1, q1 are the numbers meeting q1/p1=0.8 ~ 1.5, q1+p1=5 ~ 80, and r1 is respectively the integer of 2 ~ 100, and n1 is the integer of 0 ~ 30 independently of one another.
7. the manufacture method of fluorine-containing based compound according to claim 1, it is characterized in that, make shown in following general formula (3) or the fluorochemicals shown in (4) and following general formula (5) carry out hydrosilylation reactions containing the alcohol of terminal unsaturation group and the fluorine-containing alcohol compound that obtains and following formula (6) and/or the compound shown in (7) react
[Rf
1-Z
1]
a-Q
1-[H]
b(3)
[H]
b-Q
2-Z
1-Rf
2-Z
1-Q
2-[H]
b(4)
In formula, Q
1, Q
2, Rf
1, Rf
2, Z
1, a, b as previously mentioned, a the Z bracketed with []
1with b H all respectively with Q
1or Q
2siliciumatom in structure combines,
CH
2＝CR
1-Z
2-CHR
2-OH (5)
In formula, R
1, R
2, Z
2as previously mentioned,
CH
2＝CR
4COX (6)
CH
2＝CR
4COOCH
2CH
2-N＝C＝O (7)
In formula, R
4for hydrogen atom or methyl, X is halogen atom.
8. manufacture method according to claim 7, wherein, formula (3) or the compound shown in (4) are selected from following (B-1) ~ (B-8):
In formula, Rf ' is-CF
2o (CF
2o)
p1(CF
2cF
2o)
q1cF
2-, p1, q1 are the numbers meeting q1/p1=0.8 ~ 1.5, q1+p1=5 ~ 80, and r1 is respectively the integer of 2 ~ 100,
The alcohol containing terminal unsaturation group of formula (5) is selected from following formula:
CH
2＝CH-CH
2-OCH
2CH(CH
3)-OH
CH
2＝CH-CH
2-(OC
3H
6)
2-OCH
2CH(CH
3)-OH
CH
2＝CH-CH
2-(OC
3H
6)
4-OCH
2CH(CH
3)-OH
CH
2＝CH-CH
2-(OC
3H
6)
9-OCH
2CH(CH
3)-OH
9. solidification compound, is characterized in that, the fluorine-containing based compound described in any one containing claim 1 ~ 6.
10. make solidification compound according to claim 9 at the base material of substrate surface coating, solidification.
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| JP2015022895A JP6402643B2 (en) | 2014-03-31 | 2015-02-09 | Fluorine-containing acrylic compound, method for producing the same, curable composition, and substrate |
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| CN107298751B (en) * | 2016-04-15 | 2021-10-26 | 信越化学工业株式会社 | Fluorine-containing acrylic composition, method for producing same, fluorine-containing active energy ray-curable composition, and article |
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