CN104945615B - Fluorine-containing based compound and its manufacturing method and solidification compound, substrate - Google Patents
Fluorine-containing based compound and its manufacturing method and solidification compound, substrate Download PDFInfo
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- CN104945615B CN104945615B CN201510146322.1A CN201510146322A CN104945615B CN 104945615 B CN104945615 B CN 104945615B CN 201510146322 A CN201510146322 A CN 201510146322A CN 104945615 B CN104945615 B CN 104945615B
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Abstract
The present invention provide excellent dissolubility, the fluorine-containing based compound that can be easily synthesized and its preparation method, comprising its solidification compound, solidify with it the substrate of envelope.Following formula (1), (2) fluorine-containing based compound.[Rf1‑Z1]a‑Q1‑[CH2‑CHR1‑Z2‑CHR2‑OR3]b…(1)[R3O‑CHR2‑Z2‑CHR1‑CH2]b‑Q2‑Z1‑Rf2‑Z1‑Q2‑[CH2‑CHR1‑Z2‑CHR2‑OR3]b…(2)(Rf1For the holo-fluorine polyester of 1 valence of molecular weight 400~20,000, Rf2For the holo-fluorine polyester of the divalent of molecular weight 400~20,000, Z1For the divalent alkyl that can contain O, N, Si.Q1For the linker of (a+b) valence containing Si, Q2For the linker of (b+1) valence containing Si.Z2For the divalent alkyl that can contain O, N.R1For H or 1 valency alkyl, R2For 1 valency alkyl, Z2With R1、Z2With R2In combination with formation cyclic structure, R1With R2It include Z in combination with being formed2Cyclic structure.A, b is 1~10.R3For H or the 1 valence organic group containing acryloyl group or α substituted acryl of O, N, R can be contained3For 1 or more above-mentioned 1 valence organic group.).
Description
Technical field
The present invention relates to fluorine-containing based compound and its manufacturing method, the solidification compound comprising the compound with
And the substrate for solidifying envelope with the composition.
Background technique
So far, the means as the surface of protection resin-formed body etc., generally and widely use hard conating process.
It is to form the curing resin layer (hard conating) of hard on the surface of formed body and it is made to be difficult to damage.As composition hard conating
Material has used heat-curing resin, ultraviolet light or electronic beam solidified resin more and has had the function of the tree of the two
Rouge.
On the other hand, along with synthetic resin using the expansion in field, the trend of high additive value, for solidification
The requirement of the multifunction of resin layer (hard conating) is surging, as one of those, it is desirable that assigns soil resistance to hard conating.It is
The properties such as waterproofness, grease proofness are assigned by surface to hard conating, so that being difficult to stain or can staiing
Easily remove.
As the method for assigning soil resistance to hard conating, it has been widely used in the hard coating surface coating once formed
And/or the method for fixed fluorine-containing anti-fouling agent, for being combined by the way that fluorine-containing curability composition is added to solidified resin before curing
Object makes its coating solidification, so that the method for carrying out the formation of hard conating and the imparting of soil resistance simultaneously is also studied.Example
Such as, it shows in Japanese Laid-Open Patent Publication 6-211945 bulletin (patent document 1) by the hardening resin composition of acrylic acid series
The manufacture for adding fluoroalkyl base ester, solidifying it and imparting the hard conating of soil resistance.
The present inventor carries out as the fluorine compounds that can assign soil resistance to such hardening resin composition
Various exploitations, for example, being proposed in special open 2013-237824 bulletin (patent document 2) by matching fluorine-containing alcoholic compound
The method of soil resistance is assigned together in heat-curing resin.In addition, the present inventor, for example, proposing special open 2010-53114
Bulletin (patent document 3), special open 2010-138112 bulletin (patent document 4), special open 2010-285501 bulletin (patent text
Offer 5) shown in photo curable fluorine compounds.It is capable of the method for the fluorine compounds of photocuring as these are synthesized, makes fluorine-containing
The method that alcohol is reacted with acrylic acid halide, the acrylic compounds with isocyanate group is excellent.
In recent years, for by for the purpose of the cooperation in such curable resin by fluorine-containing alcoholic compound and fluorine-containing alcohol
The requirement of the multifunction of the fluorine-containing based compound of synthesis is surging, and strong request dissolubility is excellent, can easily close
At fluorine-containing based compound.
Existing technical literature
Patent document
[patent document 1] Japanese Laid-Open Patent Publication 6-211945 bulletin
[patent document 2] special open 2013-237824 bulletin
[patent document 3] special open 2010-53114 bulletin
[patent document 4] special open 2010-138112 bulletin
[patent document 5] special open 2010-285501 bulletin
Summary of the invention
Subject to be solved by the invention
The present invention completes in view of above-mentioned actual conditions, and it is an object of the present invention to provide dissolubility is excellent, can be easily synthesized
Fluorine-containing based compound and its manufacturing method, the solidification compound comprising the compound and consolidating with the composition
Change the substrate of envelope.
Means for solving the problems
The present inventor, as such fluorine-containing based compound, in special open 2010-53114 bulletin (patent document
3) it, in special open 2010-138112 bulletin (patent document 4), special open 2010-285501 bulletin (patent document 5) etc., proposes
Add alcoholic compound of the end with unsaturated bond with the holo-fluorine polyester with multiple Si -- Hs by hydrosilylation
At method specifically instantiate compound to have imported primary alconol below, tertiary alcohol end as intermediate.
-CH2CH2CH2OH
-CH2CH2CH2OCH2CH2OH
[changing 1]
Wherein, it has used to have imported-CH2The case where fluorine-containing alcoholic compound of the primary alconol end of OH type is as intermediate
Under, sometimes due to heating, ongoing change and be easy thickening, dissolubility reduces, on the other hand, in the case of tertiary alcohol end, with primary
The situation of alcohol is compared, it is difficult to deliquescent reduction be occurred, but because of the difference of condition, be imported reaction speed when acryloyl group sometimes
Become extremely slow.It is reacted in particular for the isocyanate compound with acryloyl group, in recent years, due to for toxicity
Worry, is become difficult using the high tin series catalysts of catalyst activity, be transferred to safer but low catalyst activity titanium system, zirconium
The catalyst of system etc., but for using the tertiary alcohol of these catalyst and reacting for isocyanates, reaction speed is tended to extremely slow.
The novel fluorine-containing based compound that therefore, it is necessary to show stable dissolubility, can be easily synthesized.
The present inventor further studies repeatedly to achieve the goals above, as a result, it has been found that, make the following general formula (3) or (4)
[Rf1-Z1]a-Q1-[H]b (3)
[H]b-Q2-Z1-Rf2-Z1-Q2-[H]b (4)
(in formula, Rf1For 1 valence of the molecular weight 400~20,000 that is made of the perfluoroalkyl of carbon number 1~6 and oxygen atom
Holo-fluorine polyester, Rf2For the divalent of the molecular weight 400~20,000 that is made of the perfluorinated alkylidene of carbon number 1~6 and oxygen atom
Holo-fluorine polyester, Z1It independently is the alkyl of the divalent for containing oxygen atom, nitrogen-atoms and silicon atom of carbon number 1~20, can be contained halfway
Cyclic structure.Q1It is the linker comprising at least (a+b) a silicon atom (a+b) valence, Q2It independently is a comprising at least (b+1)
The linker of (b+1) valence of silicon atom.The integer that a is 1~10, b independently are 1~10 integer.The a Z bracketed with []1
With b H all respectively with Q1Or Q2Silicon atom bonding in structure.)
Shown in fluorochemical and the following general formula (5)
CH2=CR1-Z2-CHR2-OH (5)
(in formula, Z2It independently is the alkyl of the divalent for containing oxygen atom and nitrogen-atoms of carbon number 1~200, ring can be contained halfway
Shape structure.R1It independently is the alkyl of 1 valence of hydrogen atom or carbon number 1~8, R2It independently is the alkyl of 1 valence of carbon number 1~8, Z2
With R1And/or Z2With R2It can respectively in connection with and with and R1、R2In conjunction with carbon atom be formed together cyclic structure, in addition, R1With R2It can
It is formed together in conjunction with and with the carbon atom of each self-bonding containing Z2Cyclic structure.)
Shown in alcohol containing terminal unsaturation group carry out obtained from hydrosilylation reactions with secondary alcohol end
For fluorine-containing alcoholic compound compared with the fluorochemical of primary alconol end, heating, thickening caused by ongoing change are few, and have used the tertiary alcohol
The situation of the fluorochemical of end is sufficiently fast compared to reaction speed, it was found that: make the fluorine-containing alcoholic compound and following formula (6)
And/or (7)
CH2=CR4COX (6)
CH2=CR4COOCH2CH2- N=C=O (7)
(in formula, R4For hydrogen atom or methyl, X is halogen atom.)
The following general formula (1) or (2) obtained from compound represented reaction
[changing 2]
[Rf1-Z1]a-Q1-[CH2-CHR1-Z2-CHR2-OR3]b (1)
[R3O-CHR2-Z2-CHR1-CH2]b-Q2-Z1-Rf2-Z1-Q2-[CH2-CHR1-Z2-CHR2-OR3]b (2)
(in formula, Rf1、Rf2、Z1、Z2、Q1、Q2、R1、R2, a, b it is as described above.R3It is each independently hydrogen atom or can
The organic group of 1 valence with acryloyl group or α substituted acryl containing oxygen atom and nitrogen-atoms, but, R3It puts down in the molecule
All have the organic group of above-mentioned 1 valence of at least one.)
Shown in fluorine-containing based compound show stable dissolubility, reaction speed when synthesis is sufficiently fast, meets
Above-mentioned requirements complete the present invention.
Therefore, the present invention provide following fluorine-containing based compounds, its manufacturing method and solidification compound and
Substrate.
[1] the fluorine-containing based compound indicated by the following general formula (1) or (2).
[changing 3]
[Rf1-Z1]a-Q1-[CH2-CHR1-Z2-CHR2-OR3]b (1)
[R3O-CHR2-Z2-CHR1-CH2]b-Q2-Z1-Rf2-Z1-Q2-[CH2-CHR1-Z2-CHR2-OR3]b (2)
(in formula, Rf1For 1 valence of the molecular weight 400~20,000 that is made of the perfluoroalkyl of carbon number 1~6 and oxygen atom
Holo-fluorine polyester, Rf2For the divalent of the molecular weight 400~20,000 that is made of the perfluorinated alkylidene of carbon number 1~6 and oxygen atom
Holo-fluorine polyester, Z1It independently is the alkyl of the divalent for containing oxygen atom, nitrogen-atoms and silicon atom of carbon number 1~20, can be contained halfway
Cyclic structure.Q1For the linker of (a+b) valence comprising at least (a+b) a silicon atom, Q2It independently is a comprising at least (b+1)
The linker of (b+1) valence of silicon atom.Z2It independently is the alkyl of the divalent for containing oxygen atom and nitrogen-atoms of carbon number 1~200,
Midway can contain cyclic structure.R1It independently is the alkyl of 1 valence of hydrogen atom or carbon number 1~8, R2It independently is 1 valence of carbon number 1~8
Alkyl, Z2With R1And/or Z2With R2It can respectively in connection with and with and R1、R2In conjunction with carbon atom be formed together cyclic structure, in addition,
R1With R2In combination with and be formed together with the carbon atom of each self-bonding containing Z2Cyclic structure.The integer that a is 1~10, b is independently
For 1~10 integer.R3It is each independently hydrogen atom or can contain oxygen atom and nitrogen-atoms there is acryloyl group or α to take
For the organic group of 1 valence of acryloyl group, wherein R3In the molecule averagely with the organic group of above-mentioned 1 valence of at least one.)
[2] fluorine-containing based compound described in [1], wherein the following formula in general formula (1) and (2)
-Z2-CHR2-OR3
Shown in group be following formula
-Z3-OCH2CH(CH3)-OR3
(in formula, R3It is same as described above.Z3For the alkyl of the divalent for containing oxygen atom and nitrogen-atoms of carbon number 1~199, midway
Cyclic structure can be formed, in addition, adjacent R1With Z3In combination with and with and R1In conjunction with carbon atom be formed together cyclic structure.)
Shown in group.
[3] fluorine-containing based compound described in [2], wherein the following formula in general formula (1) and (2)
-Z2-CHR2-OR3
Shown in group be following formula
-CH2-[OC3H6]n-OCH2CH(CH3)-OR3
(in formula, R3It is same as described above.The integer that n is 0~64.)
Shown in group.
[4] described in any item fluorine-containing based compounds of [1]~[3] are indicated by the following general formula (8) or (9).
[changing 4]
[Rf1-Z1]a-Q1-[CH2CH2CH2[OC3H6]nOCH2CH(CH3)OCOCR4=CH2]b (8)
Rf2-{Z1-Q2-[CH2CH2CH2[OC3H6]nOCH2CH(CH3)OCONHCH2CH2OCOCR4=CH2]b}2 (9)
(in formula, Rf1、Rf2、Q1、Q2、Z1, a, b as previously mentioned, n be 0~64 integer, R4For hydrogen atom or methyl.)
[5] described in any item fluorine-containing based compounds of [1]~[4], wherein Rf1For selected from following formula (i),
(ii), the structure of (iii),
CF3O-(CF2O)p-(CF2CF2O)q-CF2- (i)
(in formula, the integer that p is 0~400, the integer that q is 0~170, the integer that p+q is 2~400.)
F[CF(CF3)CF2O]r-CF(CF3)- (ii)
(in formula, r be 1~120 integer.)
F[CF2CF2CF2O]s-CF2CF2- (iii)
(in formula, s be 1~120 integer.)
Rf2For the structure selected from following formula (iv), (v),
-CF2O-(CF2O)p-(CF2CF2O)q-CF2- (iv)
(in formula, the integer that p is 0~400, the integer that q is 0~170, the integer that p+q is 2~400.)
[changing 5]
-CF(CF3)-[OCF2CF(CF3)]t-OCF2CF2O-[CF(CF3)CF2O]u-CF(CF3)- (v)
(in formula, t+u be 2~120 integer.)
Q1Selected from following formula (vi)~(ix),
[changing 6]
(in formula, a, b are each independently 1~10 integer, the integer that c is 1~5.The arrangement of each unit be it is random,
(a+b) bonding end of a each unit etc. and a Z bracketed with []1With b CH2In any one group combine.T is (a+b)
The linker of valence is following formula (x)~(xiv)
[changing 7]
Either one or two of.)
Q2Selected from following formula (xv)~(xviii),
[changing 8]
(in formula, the integer that b is 1~10, the integer that c is 1~5.The arrangement of each unit is random, (b+1) a each unit
Deng bonding end and Z1With the b CH bracketed with []2Any one group combine.
T ' is following formula (xix)~(xxiii)
[changing 9]
Either one or two of.)
Z1Selected from following formula
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2-
[changing 10]
[6] described in any item fluorine-containing based compounds of [1]~[5], wherein fluorine-containing shown in formula (1) or (2)
Acrylic compounds are any of following formula (A1)~(A3).
[changing 11]
(in formula, Rf ' is-CF2O(CF2O)p1(CF2CF2O)q1CF2, p1, q1 are to meet q1/p1=0.8~1.5, q1+p1
=5~80 number.R1 is respectively 2~100 integer.N1 is each independently 0~30 integer.)
[7] manufacturing method of described in any item fluorine-containing based compounds of [1]~[6], which is characterized in that under making
State general formula (3) or (4)
[Rf1-Z1]a-Q1-[H]b (3)
[H]b-Q2-Z1-Rf2-Z1-Q2-[H]b (4)
(in formula, Q1、Q2、Rf1、Rf2、Z1, a, b be as previously mentioned, a Z bracketed with []1With b H all respectively with Q1
Or Q2Silicon atom in structure combines.)
Shown in fluorochemical and the following general formula (5)
CH2=CR1-Z2-CHR2-OH (5)
(in formula, R1、R2、Z2As previously described.)
Shown in alcohol containing terminal unsaturation group carry out fluorine-containing alcoholic compound that hydrosilylation reactions obtain under
State formula (6) and/or (7)
CH2=CR4COX (6)
CH2=CR4COOCH2CH2- N=C=O (7)
(in formula, R4For hydrogen atom or methyl, X is halogen atom.)
Compound represented reaction.
[8] manufacturing method described in [7], wherein formula (3) or (4) compound represented are selected from following (B-1)~(B-8),
[changing 12]
[changing 13]
(in formula, Rf ' is-CF2O(CF2O)p1(CF2CF2O)q1CF2, p1, q1 are to meet q1/p1=0.8~1.5, q1+p1
=5~80 number.R1 is respectively 2~100 integer.)
The alcohol containing terminal unsaturation group of formula (5) is selected from following formula,
CH2=CH-CH2-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)2-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)4-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)9-OCH2CH(CH3)-OH
[changing 14]
[9] solidification compound, which is characterized in that include described in any item fluorine-containing systems chemical combination of [1]~[6]
Object.
[10] by the substrate made of substrate surface is coated with and solidifies it of solidification compound described in [9].
Fluorine-containing based compound shown in 1*. the following general formula (1) or (2):
[Rf1-Z1]a-Q1-[CH2-CHR1-Z2-CHR2-OR3]b (1)
[R3O-CHR2-Z2-CHR1-CH2]b-Q2-Z1-Rf2-Z1-Q2-[CH2-CHR1-Z2-CHR2-OR3]b (2)
In formula, Rf1For with selected from following formula (i), the structure of (ii), (iii) 1 valence holo-fluorine polyester,
CF3O-(CF2O)p-(CF2CF2O)q-CF2- (i)
In formula, the integer that p is 0~400, the integer that q is 0~170, the integer that p+q is 2~400,
F[CF(CF3)CF2O]r-CF(CF3)- (ii)
In formula, the integer that r is 1~120,
F[CF2CF2CF2O]s-CF2CF2- (iii)
In formula, the integer that s is 1~120,
Rf2For with selected from following formula (iv), (v) structure divalent holo-fluorine polyester,
-CF2O-(CF2O)p-(CF2CF2O)q-CF2- (iv)
In formula, the integer that p is 0~400, the integer that q is 0~170, the integer that p+q is 2~400,
-CF(CF3)-[OCF2CF(CF3)]t-OCF2CF2O-[CF(CF3)CF2O]u-CF(CF3)- (v)
In formula, the integer that t+u is 2~120,
Z1For the divalent group selected from following formula:
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2-
Q1For the linker of (a+b) valence comprising at least (a+b) a silicon atom, Q2It independently is comprising at least (b+1) a silicon
The linker of (b+1) valence of atom；
Z2For the divalent group selected from following formula:
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2[OC2H4]d[OC3H6]e[OC4H8]f-
-CH2[OC2H4]d[OC3H6]e[OC4H8]fOCH2,
Wherein, the integer that d is 0~99, the integer that e is 0~66, the integer that f is 0~50, it is total meet carbon number 200 with
Under, it is random that the arrangement of repetitive unit is unrelated with type, in addition, each repetitive unit can not be monomer but isomers
Mixture,
R1It independently is the alkyl of 1 valence of hydrogen atom or carbon number 1~8；R2It independently is the alkyl of 1 valence of carbon number 1~8, Z2
With R1And/or Z2With R2It can respectively in connection with and with and R1、R2In conjunction with carbon atom be formed together cyclic structure, in addition, R1With R2It can
It is formed together in conjunction with and with the carbon atom of each self-bonding containing Z2Cyclic structure, for the divalent group selected from following formula:
The integer that a is 1~10, b independently are 1~10 integer, R3It is each independently hydrogen atom or can oxygen-containing original
The organic group of 1 valence with acryloyl group or α substituted acryl of son and nitrogen-atoms, but, R3Averagely have in the molecule
There is the organic group of above-mentioned 1 valence of at least one.
Fluorine-containing based compound described in 2*.1*, wherein the following formula in general formula (1) and (2)
-Z2-CHR2-OR3
Shown in group be following formula shown in group:
-Z3-OCH2CH(CH3)-OR3
In formula, R3It is same as described above, Z3For the alkyl of the divalent for containing oxygen atom and nitrogen-atoms of carbon number 1~199, halfway may be used
Cyclic structure is formed, in addition, adjacent R1With Z3In combination with and with and R1In conjunction with carbon atom be formed together cyclic structure.
Fluorine-containing based compound described in 3*.2*, wherein the following formula in general formula (1) and (2)
-Z2-CHR2-OR3
Shown in group be following formula shown in group:
-CH2-[OC3H6]n-OCH2CH(CH3)-OR3
In formula, R3Integer same as described above, that n is 0~64.
Fluorine-containing based compound described in 4*.1* is indicated by the following general formula (8) or (9):
[Rf1-Z1]a-Q1-[CH2CH2CH2[OC3H6]nOCH2CH(CH3)OCOCR4=CH2]b (8)
Rf2-{Z1-Q2-[CH2CH2CH2[OC3H6]nOCH2CH(CH3)OCONHCH2CH2OCOCR4=CH2]b}2 (9)
In formula, Rf1、Rf2、Q1、Q2、Z1, a, b as described above, n be 0~64 integer, R4For hydrogen atom or methyl.
Fluorine-containing based compound described in 5*.1*, wherein
Q1Selected from following formula (vi)~(ix):
In formula, a, b are each independently 1~10 integer, and the integer that c is 1~5, the arrangement of each unit is random, (a
+ b) and (a+b-2) a each unit bonding end and a Z being bracketed with []1With b CH2In any one group combine,
T is the linker of (a+b) valence, is either one or two of following formula (x)~(xiv):
Q2Selected from following formula (xv)~(xviii):
In formula, b be 1~10 integer, c be 1~5 integer, the arrangement of each unit be it is random, (b+1) and (b-1) is a
The bonding end and Z of each unit1With the b CH bracketed with []2Any one group combine,
T ' is any of following formula (xix)~(xxiii):
Fluorine-containing based compound described in 6*.1*, wherein fluorine-containing based compound shown in formula (1) or (2)
For any of following formula (A1)~(A3):
In formula, Rf ' is-CF2O(CF2O)p1(CF2CF2O)q1CF2, p1, q1 are to meet q1/p1=0.8~1.5, q1+p1
=5~80 number, r1 are respectively 2~100 integer, and n1 is each independently 0~30 integer.
The manufacturing method of fluorine-containing based compound described in 7*.1*, which is characterized in that make the following general formula (3) or (4)
Shown in the alcohol containing terminal unsaturation group shown in fluorochemical and the following general formula (5) carry out hydrosilylation reactions and
Obtained fluorine-containing alcoholic compound is reacted with following formula (6) and/or (7) compound represented,
[Rf1-Z1]a-Q1-[H]b (3)
[H]b-Q2-Z1-Rf2-Z1-Q2-[H]b (4)
In formula, Q1、Q2、Rf1、Rf2、Z1, a, b be as previously mentioned, a Z bracketed with []1With b H all respectively with Q1Or
Q2Silicon atom in structure combines,
CH2=CR1-Z2-CHR2-OH (5)
In formula, R1、R2、Z2As previously mentioned,
CH2=CR4COX (6)
CH2=CR4COOCH2CH2- N=C=O (7)
In formula, R4For hydrogen atom or methyl, X is halogen atom.
Manufacturing method described in 8*.7*, wherein formula (3) or (4) compound represented are selected from following (B-1)~(B-8):
In formula, r1 is respectively 2~100 integer,
The alcohol containing terminal unsaturation group of formula (5) is selected from following formula:
CH2=CH-CH2-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)2-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)4-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)9-OCH2CH(CH3)-OH
9*. solidification compound, which is characterized in that described in any item fluorine-containing systems containing 1*~6*
Close object.
10*. makes the substrate made of substrate surface coating, solidification of solidification compound described in 9*.
The effect of invention
Fluorine-containing based compound of the invention, due to showing stable dissolubility, reaction speed when synthesis is enough
Fastly, it can be easily synthesized, therefore can be used as assigning the additive of soil resistance or right to thermohardening type resin combination
The antifoulant additive etc. of ultraviolet curing resin imparting soil resistance.
Specific embodiment
Fluorine-containing based compound of the invention is indicated by the following general formula (1) or (2).
[changing 15]
[Rf1-Z1]a-Q1-[CH2-CHR1-Z2-CHR2-OR3]b (1)
[R3O-CHR2-Z2-CHR1-CH2]b-Q2-Z1-Rf2-Z1-Q2-[CH2-CHR1-Z2-CHR2-OR3]b (2)
In above-mentioned formula (1), (2), Rf1It is the molecular weight 400~20 being made of the perfluoroalkyl of carbon number 1~6 and oxygen atom,
The holo-fluorine polyester of 000 1 valence, Rf2It is the molecular weight 400~20 being made of the perfluorinated alkylidene of carbon number 1~6 and oxygen atom,
The holo-fluorine polyester of 000 divalent, Rf1、Rf2Particularly preferably the structure with carbon number 1~3 below repeats list as main
Member.
-CF2O-
-CF2CF2O-
-CF(CF3)CF2O-
-CF2CF2CF2O-
These structures can be the homopolymer of any one or random, block polymer by multiple structure compositions.
As the Rf having a structure in which1Preferred example, structure for example below can be enumerated.
CF3O-(CF2O)p-(CF2CF2O)q-CF2-
(in formula, the integer that p is 0~400, preferably 0~200, the integer that q is 0~170, preferably 0~100, p+q is
2~400, preferably 3~300 integer.)
F[CF(CF3)CF2O]r-CF(CF3)-
(in formula, r be 1~120, preferably 1~80 integer.)
F[CF2CF2CF2O]s-CF2CF2-
(in formula, s be 1~120, preferably 1~80 integer.)
In addition, as Rf2Preferred example, structure for example below can be enumerated.
-CF2O-(CF2O)p-(CF2CF2O)q-CF2-
(in formula, the integer that p is 0~400, preferably 0~200, the integer that q is 0~170, preferably 0~100, p+q is
2~400, preferably 3~300 integer.)
-CF(CF3)-[OCF2CF(CF3)]t-OCF2CF20-[CF(CF3)CF20]u-CF(CF3)-
(in formula, t+u be 2~120, preferably 4~100 integer.)
For these Rf1、Rf2The number-average molecular weight of the molecular weight of group, the structure division is separately contained in 400~20,
000, in the range of preferably 800~10,000, its molecular weight distribution is not particularly limited.It should be noted that of the invention
In, molecular weight is by being based on1H-NMR and19The number-average molecular weight that the end structure of F-NMR and the ratio of backbone structure calculate.
Above-mentioned Rf1And Rf2Bonding end whole and Z1In conjunction with.Z1For carbon number 1~20, preferably 2~16, can oxygen-containing original
The alkyl of the divalent of son, nitrogen-atoms and silicon atom, can contain cyclic structure halfway.As Z1Particularly preferred structure, can enumerate with
Under structure.
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2-
[changing 17]
In above-mentioned formula (1), (2), a and b are each independently 1~10 integer, preferably 1~8 integer, more preferably
1~4 integer.
In above-mentioned formula (1), Q1For the linker of (a+b) valence comprising at least (a+b) a silicon atom, cyclic annular knot can be formed
Structure.As such Q1Preferred example, can enumerate respectively with (a+b) a Si atom siloxane structure, it is unsubstituted or
The connection of (a+b) valence that silicon alkylen structures, silicon arlydene structure or these the combination of more than two kinds that halogen replaces are constituted
Base.As particularly preferred structure, specifically, following structures is shown.
Wherein, a and b is identical as a, b of above-mentioned formula (1), is each independently 1~10 integer, preferably 1~8 it is whole
Number, more preferably 1~4 integer.The integer that c is 1~5, preferably 3~5 integer.The arrangement of each unit is random, (a+
B) bonding end of a each unit etc. and a Z bracketed with []1With b CH2In any one group bonding.
[changing 18]
Wherein, T is the linker of (a+b) valence, can illustrate group for example below.
[changing 19]
In above-mentioned formula (2), Q2For the linker of (b+1) valence comprising at least (b+1) a silicon atom, cyclic annular knot can be formed
Structure.As such Q2Preferred example, can enumerate respectively with (b+1) a Si atom siloxane structure, it is unsubstituted or
The connection of (b+1) valence that silicon alkylen structures, silicon arlydene structure or these the combination of more than two kinds that halogen replaces are constituted
Base.As particularly preferred structure, specifically, following structures is shown.
Wherein, b is identical as the b of above-mentioned formula (2), independently is 1~10 integer, preferably 1~8 integer, more preferably
For 1~4 integer.The integer that c is 1~5, preferably 1~3 integer.The arrangement of each unit is random, (b+1) a each
The bonding end and Z of unit etc.1With the b CH bracketed with []2Any one group bonding.
[changing 20]
Wherein, T ' is the linker of (b+1) valence, can illustrate group for example below.
[changing 21]
In above-mentioned formula (1), (2), Z2For carbon number 1~200, preferably 2~80, divalent that oxygen atom and nitrogen-atoms can be contained
Alkyl, cyclic structure can be contained halfway.As Z2Preferred structure, structure below can be enumerated.
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2[OC2H4]d[OC3H6]e[OC4H8]f-
-CH2[OC2H4]d[OC3H6]e[OC4H8]fOCH2-
Wherein, the integer that d is 0~99, the integer that e is 0~66, the integer that f is 0~50 are total to meet 200 or less carbon number
?.The arrangement of repetitive unit, it is unrelated with type, it is random.In addition, each repetitive unit can not be monomer but isomers
Mixture.
As Z2, as particularly preferred structure, structure below can be enumerated, wherein the structure that preferred e is 1~30.
-CH2[OC3H6]eOCH2-
In above-mentioned formula (1), (2), R1For hydrogen atom or the alkyl of 1 valence of carbon number 1~8, preferably 1~6, R2For carbon number 1~
8, the alkyl of preferably 1~6 1 valence specifically, can enumerate methyl, ethyl, propyl, isopropyl, fourth as the alkyl of 1 valence
The naphthenic base such as the alkyl such as base, isobutyl group, tert-butyl, amyl, neopentyl, hexyl, octyl, cyclohexyl, vinyl, allyl, third
Aralkyl such as the aryl such as the alkenyls such as alkenyl, phenyl, tolyl, xylyl, benzyl, phenylethyl etc..As R1, preferably hydrogen
Atom and methyl, as R2, preferred methyl.
In addition, Z2With R1And/or Z2With R2Can respectively be self-bonded and with and R1、R2In conjunction with carbon atom be formed together cyclic annular knot
Structure, in addition, R1With R2In combination with and be formed together with the carbon atom of each self-bonding containing Z2Cyclic structure.
As Z2With R1Or Z2With R2In conjunction with the example for foring cyclic structure, structure below can be enumerated.Further more, key
Close end and OH and CHR1Or CHR2And CH2Bonding.
[changing 22]
In addition, as R1With R2It is formed together in conjunction with and with the carbon atom of each self-bonding containing Z2Cyclic structure example, can
Enumerate structure below.It should be noted that the bonding end being represented by dashed line and OH and CHR1Or CHR2And CH2In conjunction with.
[changing 23]
In above-mentioned formula (1), (2), R3It is each independently hydrogen atom or can contain oxygen atom and nitrogen-atoms has propylene
1 valence organic group of acyl group or α substituted acryl.As 1 valence organic group, preferably there is at least one, preferably in end
The group of 1~5 acryloyl group or α substituted acryl can enumerate methyl, ethyl, F, CF as the substituent3、Cl、Br
Deng.In addition, way can have amido bond, ehter bond, ester bond etc. in the structure.
As such structure, structure for example below can be enumerated.
CH2=CHCO-
CH2=C (CH3)CO-
CH2=C (C2H5)CO-
CH2=CFCO-
CH2=CClCO-
CH2=CBrCO-
CH2=C (CF3)CO-
CH2=CHCOOCH2CH2-NHCO-
CH2=C (CH3)COOCH2CH2-NHCO-
CH2=C (CH3)COOCH2CH2OCH2CH2-NHCO-
(CH2=CHCOOCH2CH2)2C(CH3)-NHCO-
Wherein, particularly preferably
CH2=CHCOOCH2CH2-NHCO-
CH2=C (CH3)COOCH2CH2-NHCO-。
Wherein, R3A part can be hydrogen atom, but not all hydrogen atoms, in a molecule averagely comprising 1 with
On above-mentioned acryloyl group and/or α substituted acryl.
- Z in above-mentioned formula (1), (2)2-CHR2-OR3Shown in group, preferably following formula
-Z3-OCH2CH(CH3)-OR3
Shown in group.
Wherein, Z3For carbon number 1~199, preferably 1~60, the alkyl of divalent that oxygen atom and nitrogen-atoms can be contained, midway
Cyclic structure can be formed, in addition, adjacent R1With Z3In combination with and with and R1In conjunction with carbon atom be formed together cyclic structure.Make
For Z3Preferred structure, structure below can be enumerated.
-CH2[OC2H4]d[OC3H6]e[OC4H8]f-
(in formula, d, e, f are same as described above.The arrangement of repetitive unit, it is unrelated with type, it is random.In addition, each repeat
Unit can not be monomer, but the mixture of isomers.)
As Z3, as particularly preferred structure, structure below can be enumerated, wherein the structure that preferred e is 1~30.
-CH2[OC3H6]e-
In addition,-the Z in general formula (1), (2)2-CHR2-OR3Shown in group be more preferably following formula
-CH2-[OC3H6]n-OCH2CH(CH3)-OR3
(wherein, the integer that n is 0~64, preferably 0~40, more preferably 1~30.) shown in group.
As fluorine-containing based compound shown in above-mentioned formula (1), (2), preferably the following general formula (8), change shown in (9)
Close object.
[changing 24]
[Rf1-Z1]a-Q1-[CH2CH2CH2[OC3H6]nOCH2CH(CH3)OCOCR4=CH2]b (8)
Rf2-{Z1-Q2-[CH2CH2CH2[OC3H6]nOCH2CH(CH3)OCONHCH2CH2OCOCR4=CH2]b}2 (9)
(in formula, Rf1、Rf2、Q1、Q2、Z1, a, b, n be as described above, R4For hydrogen atom or methyl.)
As fluorine-containing based compound shown in above-mentioned formula (1), (2), more specifically, can illustrate it is following shown in
Compound.
[changing 25]
[changing 26]
[changing 27]
(in formula, Rf ' is-CF2O(CF2O)p1(CF2CF2O)q1CF2, p1, q1 are to meet q1/p1=0.8~1.5, q1+p1
=5~80 number.R1 is respectively the integer of 2~100, preferably 2~50.N1 is each independently 0~30, preferably 1~15
Integer.)
Fluorine-containing based compound shown in such general formula (1) or (2), to its synthetic method, there is no particular restriction, example
Such as, firstly, by making the following general formula (3) or (4)
[Rf1-Z1]a-Q1-[H]b (3)
[H]b-Q2-Z1-Rf2-Z1-Q2-[H]b (4)
(in formula, Rf1、Rf2、Z1、Q1、Q2, a, b it is same as described above, a Z bracketed with []1With b H all respectively with
Q1Or Q2Silicon atom bonding in structure.)
Shown in multifunctional Si -- H perfluoroalkyl polyether compound and the following general formula (5)
CH2=CR1-Z2-CHR2-OH (5)
(in formula, R1、R2、Z2It is same as described above.)
Shown in the alcohol compound of alkenyl and secondary alcohol (in molecule with) containing terminal unsaturation group carry out silane
Alkylation reaction, so as to obtain the fluorine-containing alcoholic compound as intermediate.
Wherein, it as the perfluoroalkyl polyether compound shown in above-mentioned formula (3), (4) with multifunctional Si -- H, can illustrate
Following compounds represented.
[changing 28]
[changing 29]
[changing 30]
[changing 31]
(in formula, Rf ', r1 are same as described above.)
In addition, the following general formula (a) institute can be illustrated as the alcohol containing terminal unsaturation group shown in above-mentioned formula (5)
The alcohol shown.
CH2=CR1-Z3-OCH2CH(CH3)-OH (a)
(in formula, R1、Z3It is same as described above.)
As the alcohol containing terminal unsaturation group shown in above-mentioned formula (a), preferably alcohol shown in the following general formula (b).
CH2=CH-CH2-[OC3H6]n-OCH2CH(CH3)-OH (b)
(in formula, n is same as described above.)
As the alcohol containing terminal unsaturation group shown in above-mentioned formula (5), specifically, can illustrate it is following shown in
Alcohol.
CH2=CH-CH2-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)2-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)4-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)9-OCH2CH(CH3)-OH
[changing 32]
The hydrosilylation (addition) reaction, it is preferable that with multifunctional Si -- H shown in formula (3) or (4)
Alcohol mixing shown in perfluoroalkyl polyether compound and formula (5) containing terminal unsaturation group, in platinum group metal, the addition reaction of system is urged
In the presence of agent, 50~150 DEG C of reaction temperature, reaction 1 minute~48 hours, particularly 10 are carried out at preferably 60~120 DEG C
Minute~12 hours.If reaction temperature is too low, in the case where reaction is not sufficiently carried out, reaction stops sometimes, if mistake
Height not can control reaction sometimes due to temperature caused by the reaction heat of hydrosilylation rises, and the decomposition of bumping, raw material occurs
Deng.
In this case, there is the perfluoroalkyl polyether compound of multifunctional Si -- H as shown in formula (3) or (4) and by formula
(5) reaction ratio of the alcohol containing terminal unsaturation group shown in, it is multifunctional relative to having as shown in formula (3) or (4)
The total mole number of the H of the perfluoroalkyl polyether compound of Si -- H bracketed with [], it is preferable to use 0.5~5.0 times mole, especially
The terminal unsaturation group of the alcohol containing terminal unsaturation group as shown in formula (5) on 0.9~2.0 times mole of ground and keep it anti-
It answers.As formula (5) if shown in the alcohol containing terminal unsaturation group it is very few in contrast, be difficult to obtain with highly dissoluble
Fluorine-containing alcoholic compound, if excessive more than it, the homogeneity of reaction solution is reduced, and reaction speed becomes unstable, and
And only increasing remaining unreacted alcohol when the removing of the alcohol containing terminal unsaturation group shown in the laggard line (5) of reaction
Degree on strictly control heating, decompression, extract etc. conditions.
Addition reaction catalyst is able to use such as the compound comprising platinum group metal platinum, rhodium or palladium.Wherein preferred packet
The compound of platiniferous is able to use chlordene platinum (IV) sour hexahydrate, platinum carbonyl ethenyl methyl complex, platinum-divinyl
Tetramethyl disiloxane complex compound, platinum-cyclovinylmethylsiloxane complex compound, platinum-octanal/octanol complex or load
In the platinum of active carbon.
The use level of addition reaction catalyst, relative to the fluorine as shown in formula (3) or (4) with multifunctional Si -- H
Polyether compound, preferably contained amount of metal are 0.1~5,000 mass ppm, more preferably 1~1,000 mass ppm.
Above-mentioned addition reaction can also be implemented even if there be no solvent, but available solvent dilution as needed.At this point, dilute
Releasing solvent can be using the general widely used organic solvent such as toluene, dimethylbenzene, isooctane, preferably reaction of the boiling point in target
It more than temperature, and does not hinder to react, the compound of the formula (1) or (2) that generate after reaction is solvable under above-mentioned reaction temperature.Make
For such solvent, preferably the fluorine richness aromatic hydrocarbon series solvent such as hexafluoro meta-xylene, trifluoromethylbenzene, methyl perfluoro fourth
The solvent of the parts fluorine richness such as the fluorine richness ether series solvent such as base ether, particularly preferred hexafluoro meta-xylene.
In the case where using solvent, usage amount, relative to as shown in formula (3) or (4) have multifunctional Si -- H
100 mass parts of perfluoroalkyl polyether compound, preferably 5~2,000 mass parts, more preferably 50~500 mass parts.If than it
Few, the diluted effect that solvent generates is weak, if more, dilution is excessively increased, and incurs the reduction of reaction speed sometimes.
After reaction, it is preferred to use method well known to decompression distillation, extraction, absorption etc. will be shown in unreacted formula (5)
The alcohol containing terminal unsaturation group, retarder thinner remove, but also can be directly following containing these reaction mixture
Reaction in use.
As the fluorine-containing alcoholic compound obtained in this way, following compounds represented can be illustrated.
[changing 33]
[changing 34]
[changing 35]
(in formula, r1, n1, Rf ' it is same as described above.)
Next, fluorine-containing can be obtained by importing acryloyl group in fluorine-containing alcoholic compound obtained above
Based compound.As the method that acryloyl group is imported fluorine-containing alcoholic compound, one can be enumerated and propylene shown in following formula (6)
Carboxylic acid halides reacts and the method that forms ester, another can be enumerated and the isocyanation esterification containing acryloyl group shown in following formula (7)
The method for closing object reaction can obtain the fluorine-containing based compound of target of the invention using these methods.
CH2=CR4COX (6)
CH2=CR4COOCH2CH2- N=C=O (7)
(in formula, R4For hydrogen atom or methyl, X is the halogen atoms such as fluorine atom, chlorine atom, bromine atom.)
Wherein, as acryloyl halide shown in formula (6), following compounds represented can be enumerated.
CH2=CHCOX
CH2=CCH3COX
(in formula, X is same as described above.)
Particularly preferred acryloyl chloride, methacrylic chloride.
In addition, as the isocyanate compound containing acryloyl group shown in formula (7), can enumerate it is following shown in chemical combination
Object.
CH2=CHCOOCH2CH2- N=C=O
CH2=CCH3COOCH2CH2- N=C=O
These acryloyl halides or isocyanate compound containing acryloyl group, can be relative to the hydroxyl of fluorine-containing alcoholic compound
Amount it is total, be packed into equimolar or more and make its reaction, react whole hydroxyls, can also relative to 1 mole of fluorine-containing alcoholic compound,
1 mole or more of acryloyl group is averagely imported, can not make unreacted acryloyl halide by keeping hydroxyl excessive or contain acryloyl
The isocyanate compound of base remains.Specifically, the fluorine-containing alcoholic compound amount in reaction system is denoted as x moles, by fluorine-containing alcoholization
When amount of hydroxyl groups total for closing object is denoted as y moles, preferably acryloyl halide or the isocyanate compound containing acryloyl group rubs for x
Above 2y moles of that hereinafter, particularly preferably 0.6y moles or more 1.3y moles or less.In the case of fewer than 0.6y moles, do not have
A possibility that all fluorine-containing alcoholic compound of importing acryloyl group is remaining increases, it is possible to which the dissolubility of product reduces.If
More than 1.3y moles, the residue removal of unreacted acryloyl halide or the isocyanate compound containing acryloyl group becomes tired
It is difficult.
These reactions can be diluted with solvent appropriate as needed and be reacted.As such solvent, as long as not
With the hydroxyl of fluorine-containing alcoholic compound, the halogen atom of acryloyl halide, isocyanate compound containing acryloyl group isocyanic acid
The solvent of ester group reaction, then can be used without special restrictions, specifically, it is molten can to enumerate the hydrocarbon systems such as toluene, dimethylbenzene, isooctane
The ether series solvents such as agent, tetrahydrofuran, Di Iso Propyl Ether, dibutyl ethers, acetone, methyl ethyl ketone, methyl butyl ketone, methyl tert-butyl
The fluorine richness aromatic hydrocarbon series solvents, methyl perfluoro such as the ketone series solvents such as base ketone, cyclohexanone, hexafluoro meta-xylene, trifluoromethylbenzene
Fluorine richness ether series solvent such as butyl ether etc..The solvent can be removed using method well known to decompression distillation etc. after the reaction, can also be former
Used in intended applications as dilute solution to sample.
In addition, polymerization inhibitor can be added as needed when reaction.As polymerization inhibitor, there is no particular restriction, is able to use usually
The polymerization inhibitor of polymerization inhibitor as acrylic compounds.Specifically, quinhydrones, Hydroquinone monomethylether, 4- tert-butyl can be enumerated
Tea phenol, dibutyl hydroxy toluene etc..
In the case of reacting fluorine-containing alcoholic compound with acryloyl halide, particularly preferably make acryloyl chloride, methacrylic chloride
Reaction generates ester.The ester generate reaction, while by above-mentioned reaction intermediate (fluorine-containing alcoholic compound), antacid mixing while incite somebody to action
Acryloyl halide is instilled and is carried out.Antacid is able to use triethylamine, pyridine, urea etc..
For instilling, the temperature of reaction mixture is maintained 0~35 DEG C, 20~60 minutes is lasted and carries out.Then, into
One step persistently stirs 30 minutes~10 hours.After reaction, by by unreacted acryloyl halide, by reaction generate salt and
Reaction dissolvent etc. uses distillation, absorption, filters the methods of clean removing, can obtain fluorine-containing system chemical combination of the invention
Object.
In addition, when reaction stops the alcoholic compounds such as methanol, ethyl alcohol can be added into system, by unreacted acryloyl halide
Esterification.The esters of acrylic acid of generation can be removed using same method is removed with unreacted acryloyl halide, also can be residual
It is used in the case where depositing.
In the case where the reacting of fluorine-containing alcoholic compound and the isocyanate compound containing acryloyl group, by fluorine-containing alcohol compound
Object and isocyanate compound containing acryloyl group stir together with solvent as needed, are reacted.
In the reaction, in order to increase the speed of reaction, catalyst appropriate can be added.As catalyst, can illustrate for example
Dibutyltin diacetate, dibutyl tin dilaurate, two sad dibutyl tins, two acetic acid dioctyl tins, tin dilaurate dioctyl
Tin alkyls ester compounds, tetraisopropoxy titanium, four titanium n-butoxides, the four (2- such as tin, two sad dioctyl tins, two stannous octoates
Ethyl hexyl oxy) titanate esters or the titanium chelate chemical combination such as titanium, bis- (acetylacetone,2,4-pentanedione) titaniums of dipropoxy, isopropoxy ethohexadiol titanium
Object, four acetylacetone,2,4-pentanedione zirconiums, three butoxy single acetyl acetone zirconiums, bis- (ethyl acetoacetate) zirconiums of only son's oxygroup acetylacetone,2,4-pentanedione, two fourths
Bis- (ethyl acetoacetate) zirconiums of oxygroup, four acetylacetone,2,4-pentanedione zirconiums, zirconium chelate compound etc..These are not limited to its a kind, can
Mixture as 2 kinds or more than it uses, particularly preferably the use of the low titanium compound, zirconium compounds of the influence to environment.
By the way that relative to reactant gross mass, these of addition 0.01~2 mass %, preferably 0.05~1 mass % are urged
Agent can be such that reaction speed increases.React small in 0~120 DEG C, preferably 10~70 DEG C of at a temperature of progress 1 minute~500
When, preferably 10 minutes~48 hours.If reaction temperature is too low, reaction speed is excessively slack-off sometimes, if reaction temperature mistake
It is high, it is possible to the polymerization of acryloyl group occur as side reaction.
After reaction, by the way that unreacted isocyanate compound and reaction dissolvent etc. are used distillation, absorption, filtering
It is the methods of clean to remove, fluorine-containing based compound of the invention can be obtained.
In addition, when reaction stops the alcoholic compounds such as methanol, ethyl alcohol can be added into system, with unreacted isocyanates
Compound forms urethane bond.The urethane acrylate esters of generation can be using similarly square with unreacted isocyanate compound
Method removes, and can also use in the case where remaining.
The embodiment of another way of the invention is comprising obtained fluorine-containing based compound as described above
(A) solidification compound, as the solidification compound, in particular it is preferred to be solidified using active energy ray.(A) ingredient
Its solidification can also individually be made, for example, by cooperating with the active energy ray-curable ingredient (B) other than (A) ingredient, Neng Gou
In the case where maintaining the characteristic as the solidfied material of (B) ingredient such as hardness, the excellent of (A) ingredient generation is given on the surface and is prevented
Dirty characteristic.
It is suitable for the active energy ray-curable ingredient of (B) ingredient used in the present invention, as long as can be mixed with (A) ingredient
It closes, solidification, is able to use any ingredient, particularly preferably esters of acrylic acid, it can be mentioned, for example include 1,6- hexylene glycol, two (first
Base) acrylate, neopentyl glycol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, isocyanuric acid ethylene oxide
Modified two (methyl) acrylate, isocyanuric acid EO modified three (methyl) acrylate, trimethylolpropane tris (methyl) propylene
Acid esters, pentaerythrite three (methyl) acrylate, glycerol three (methyl) acrylate, tricresyl phosphate (methyl) acryloxy second
Ester, hydrogen phthalate-(2,2,2- tri--(methyl) acryloyloxymethyl) ethyl ester, glycerol three (methyl) acrylate, season penta
Tetrol four (methyl) acrylate, two (trimethylolpropane) four (methyl) acrylate, dipentaerythritol five (methyl) propylene
(methyl) propylene of 2~6 functions such as acid esters, dipentaerythritol six (methyl) acrylate, sorbierite six (methyl) acrylate
It is sour based compound, the ethylene oxide of these (methyl) acrylic compounds, propylene oxide, epichlorohydrin, fatty acid, alkyl-modified
Product make epoxy resin and Epoxy Acrylates that acrylic acid addition obtains and import in the side chain of acrylate copolymer
The ingredient of the copolymer of (methyl) acryloyl group etc..
It is further possible to using urethane acrylate esters, make (methyl) acrylate with hydroxyl and polyisocyanates
Product obtained from reaction, make the polyester of polyisocyanates and terminal diol with hydroxyl (methyl) acrylate reactions and
Obtained product, make polyisocyanates obtained from excessive diisocyanate and polyol reaction with (methyl) of hydroxyl
Product obtained from acrylate reactions.Wherein, preferably make from (methyl) acrylic acid 2- hydroxy methacrylate, methacrylic acid 2- hydroxyl
(methyl) acrylate with hydroxyl selected in base -3- acryloxy propyl ester and pentaerythritol triacrylate with from six
In methylene diisocyanate, isophorone diisocyanate, xylene diisocyanate and methyl diphenylene diisocyanate
Urethane acrylate esters made of the polyisocyanates reaction of selection.Above compound can be used alone, can also be by two or more simultaneously
With.In addition, the esters of acrylic acid of 1 function can be cooperated for the physical property of regulation composition.
In addition, solidification compound of the invention, is used as (C) ingredient by containing Photoepolymerizationinitiater initiater, can become benefit
With the solidification compound of ultraviolet curing.
(C) Photoepolymerizationinitiater initiater of ingredient, as long as can be irradiated by ultraviolet light solidifies acrylic compounds, then
It is not particularly limited, it is preferable that it can be mentioned, for example acetophenone, 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-1-(4- methyl mercapto phenyl)-2- morpholino propane-1- ketone, 2-
Benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butanone -1,2- (dimethylamino) -2- [(4- aminomethyl phenyl) first
Base] -1- [4- (4- morpholinyl) phenyl] -1- butanone, 2,4,6- trimethylbenzoy-diphenies-phosphine oxide, bis- (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- acetyl group oxime), 2- hydroxyl -1- { 4- [4- (2-
Hydroxy-2-methyl-propiono)-benzyl] phenyl } -2- methyl-propan -1- ketone etc., it can be used alone, it can also be by two or more simultaneously
With.
In solidification compound of the invention, the use level of each ingredient can be according to required waterproofness, grease proofness, combination
Dissolubility, condition of cure of object etc. suitably determine, have no special limit to the compounding ratio of (A) ingredient, (B) ingredient, (C) ingredient
System, for example, the use level of (B) ingredient, relative to 100 mass parts of (A) ingredient, preferably 1~10,000 mass parts, more preferably 5
~1,000 mass parts, particularly preferably 10~200 mass parts.In addition, in the case of using (C) ingredient, the cooperation of (C) ingredient
Amount, when the total amount of (A) ingredient, (B) ingredient is calculated as 100 mass parts, preferably 0.1~10 mass parts, particularly preferably 0.5~
5 mass parts.
Further more, the hard paint of above-mentioned (B) ingredient and (C) ingredient has been cooperated to sell various products by each company.The present invention
Solidification compound can be the product that (A) ingredient is added in the hard paint of such commercially available product.As commercially available product
Hard paint, it can be mentioned, for example Arakawa Chemical Industries (strain) " ビ ー system セ ッ ト ", bridge chemical industry (strain) " ユ ー ビ ッ Network ", オ リ
ジ Application electrical (strain) " UV コ ー ト ", カ シ ュ ー (strain) " カ シ ュ ー UV ", JSR (strain) " デ ソ ラ イ ト ", work of refining big day
Industry (strain) " セ イ カ ビ ー system ", Japan synthesize chemical (strain) " purple light ", Teng Cang is melted 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 invention, in addition, according to purpose, it can also cooperate organic solvent, polymerization inhibitor, antistatic
Agent, defoaming agent, viscosity modifier, resistance to light stabilizer, heat-resisting stabilizing agent, antioxidant, surfactant, colorant and filler
Deng.Even in addition, as described above using commercially available product hard paint in the case where, also can according to purpose cooperate organic solvent,
Polymerization inhibitor, antistatic agent, defoaming agent, viscosity modifier, resistance to light stabilizer, heat-resisting stabilizing agent, antioxidant, surfactant,
Colorant and filler etc..
As organic solvent, 1- propyl alcohol, 2- propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, diacetone alcohol can be enumerated
Equal alcohols；The ketones such as methyl propyl ketone, metacetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone；Dipropyl ether, two fourths
Base ether, anisole, dioxanes, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl
The ethers such as ether acetic acid ester；Esters such as propyl acetate, butyl acetate, cyclohexyl acetate etc..Above-mentioned solvent can be used alone a kind,
Two or more can be used in mixed way.
To the usage amount of solvent, there is no particular restriction, relative to total 100 mass parts of (A)~(C) ingredient, preferably 50~
10,000 mass parts, particularly preferred 100~1,000 mass parts.
In addition, as polymerization inhibitor, antistatic agent, defoaming agent, viscosity modifier, resistance to light stabilizer, heat-resisting stabilizing agent, antioxygen
Agent, surfactant, colorant and filler can use in the range of not damaging the purpose of the present invention with no particular limitation
Well known substance.
The curing method of solidification compound of the invention is not particularly limited, for example, the case where containing (B) ingredient
Under, its solidification can be made using active energy ray, it, can be using purple also in the case where the Photoepolymerizationinitiater initiater containing (C) ingredient
Outside line makes its solidification.
As previously discussed, if it is solidification compound of the invention, then become the curability composition of hard coating composition
With the compatibility of fluorine-containing based compound it is good, can using ultraviolet light isoreactivity energy line curing, be capable of forming it is antifouling
The solidification compound of the curing resin layer of property, excellent scratch resistance.
In addition, providing in the present invention and being coated with above-mentioned solidification compound of the invention on surface and keep its cured
Substrate.As described above, if can be formed on the surface of substrate has excellent surface using solidification compound of the invention
The solidification envelope (curing resin layer) of characteristic.Particularly, it can be used for assigning the surface of acrylic acid series hard conating waterproofness, grease proofing
Property, soil resistance.Thereby, it is possible to the contaminations for giving the generations such as fingerprint, sebum, sweat et al. rouge, cosmetics to substrate to be difficult to adhere to, and
And erasing property also excellent hard coating surface.Therefore, solidification compound of the invention is capable of providing connects for being possible to human body
It touches, by the coated film or protective film on the surface of the substrate (article) of the contaminations such as people's rouge, cosmetics.
Using the solidification envelope (curing resin layer) that solidification compound of the invention is formed can be used as Tablet PC,
The employments such as portable (communication) information terminal such as notebook PC, mobile phone smart phone, digital media player, e-book
Shell, the Wristwatch-type glasses type wearable computer of the various equipment of hand-held band；Liquid crystal display, plasma scope,
Organic EL (electroluminescent) display, back side projection type display, fluorescent display tube (VFD), the field emission projection display,
CRT, the display operation equipment surface to the picture of the various flat-panel monitors such as system display and TV etc., the exterior of automobile, steel
The stone surface for building such as qin, the glossy surface of furniture, marble, lavatory, bathtub, vanity top etc. around water decorative building material,
Artistic products are shown with protection glass, show window, showcase, photo frame cover, wrist-watch, automotive glazings, train, aircraft etc.
The transparent glass system such as glass pane, car headlamp, taillight or transparent plastics system (acrylic acid series, polycarbonate etc.) component,
The coated film and surface protection film of various reflection mirror components etc..
Particularly, it can be used as the display that the finger or palm with employment such as contact panel display carry out the operation on picture
The various equipment of input unit, such as Tablet PC, notebook PC, mobile phone, portable (communication) information terminal, number
Navigation device, the cash of media player, e-book, digital frame, game machine, digital camera, DV, automobile etc.
Automatic access device, cash dispenser, automatic vending machine, number mark (electronic bill-board), security system terminal, POS
The surface protection film of the display input devices such as the various controllers such as terminal, remote controler, car-mounted device panel-switch etc..
In addition, the solidification envelope formed by solidification compound of the invention also is used as the optical recordings such as photomagneto disk, CD
Medium；Eyeglass lens, prism, lens, pellicle, polarizing film, optical filter, biconvex lens, Fresnel lens, antireflective
The surface protection envelope of the optical components optical device such as film, optical fiber, photo-coupler.
Embodiment
Synthesis example, embodiment and comparative example described below, specifically describe the present invention, but the present invention is not by following
Embodiment limitation.
[synthesis example 1]
Following formula is packed into the 1L four-hole boiling flask with reflux unit and agitating device
[changing 36]
Single terminal allylic ether (Japan of compound represented (I) 200g (Si-H value 0.00061mol/g), polypropylene glycol
Grease (strain) ユ ニ Le ー Block MA-35 processed, molecular weight 639, secondary alcohol containing ratio 100%) 89g (allyl base unit weight 0.0016mol/
G), hexafluoro meta-xylene 300g, heating stirring is until 90 DEG C under nitrogen atmosphere.Platinum/1,3- divinyl-tetramethyl is put into thereto
The toluene solution 0.442g of base disiloxane complex compound (in terms of Pt simple substance, contains 1.1 × 10-6Mol), interior temperature is being maintained 90
DEG C or more in the state of continue stirring 4 hours, use1The peak disappearance of allyl, Si -- H of the H-NMR confirmation from raw material
?.Next, being packed into hexane 3L in the flask of the 5L with agitating device, instills be cooled to the above-mentioned anti-of room temperature while stirring
Solution is answered, and then is stirred 1 hour.After stirring stops, standing 2 hours, the hexane layer on upper layer decantation removed, with evaporator from
Obtained sediment removes the solvent of remaining, has obtained the chemical combination as shown in following formula of translucent faint yellow highly viscous liquid
Object (II) 272g.
[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-has been used in addition to replacing ユ ニ ル ー Block MA-35
2,2,6- trimethyl -6- vinyl oxinanes) other than 22g, similarly to Example 1, obtain translucent faint yellow high viscous
Thick liquid by following formula compound represented (III) 201g.
By compound (III)1H-NMR chemical shift is shown in table 2.
[table 2]
[synthesis example 3]
Under dry nitrogen atmosphere, following formula is put into 2, the 000mL three-necked flask with reflux unit and agitating device
CH2=CH-CH2-O-CH2-Rf’-CH2-O-CH2- CH=CH2
Rf ' :-CF2(OCF2CF2)q(OCF2)pOCF2-
(q/p=0.9, p+q ≒ 45)
Shown in perfluoropolyether 500g [0.125mol] and hexafluoro meta-xylene 700g and tetramethyl-ring tetrasiloxane 361g
[1.50mol] is heated to 90 DEG C while stirring.Platinum/1,3- divinyl-tetramethyl disiloxane complex compound is put into thereto
Toluene solution 0.442g (in terms of Pt simple substance, contains 1.1 × 10-6Mol), continue in the state that interior temperature is maintained 90 DEG C or more
Stirring 4 hours.With1After H-NMR confirms that the allyl of raw material disappears, solvent and the decompression of excessive tetramethyl-ring tetrasiloxane are evaporated
It removes.Then, active carbon processing is carried out, colorless and transparent liquid compound (IV) 498g as shown in following formula has been obtained.
[changing 39]
Rf ' :-CF2(OCF2CF2)q(OCF2)pOCF2-
(q/p=0.9, p+q ≒ 45)
Under dry air atmosphere, relative to compound obtained above (IV) 50.0g [Si -- H amount
0.0669mol], by five propylene glycol mono allyl ether 27.5g [0.0789mol], hexafluoro meta-xylene with secondary alcohol end
50.0g and chloroplatinic acid/vinylsiloxane complex compound toluene solution 0.0442g (in terms of Pt monomer, contain 1.1 × 10- 7Mol it) mixes, is stirred 4 hours at 100 DEG C.With1After H-NMR and IR confirmation Si -- H disappears, reaction solution is cooled to room
Temperature.Next, being packed into hexane 500mL in the flask of the 2L with agitating device, instills be cooled to the upper of room temperature while stirring
Reaction solution is stated, is stirred for 1 hour.Stirring stands 2 hours after stopping, and the hexane layer on upper layer decantation is removed, evaporator is used
It is removed from obtained sediment by the solvent of remaining, has obtained the change as shown in following formula of translucent faint yellow highly viscous liquid
Close object (V) 45.1g.
[changing 40]
Rf ' :-CF2(OCF2CF2)q(OCF2)pOCF2-
(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 compound (IV) 50.0g [Si -- H amount 0.0669mol], the 2- alkene of synthesis example 3
Allyloxyethanol 7.05g [allyl base unit weight 0.0690mol], hexafluoro meta-xylene 50.0g and chloroplatinic acid/vinylsiloxane network
The toluene solution 0.0442g for closing object (in terms of Pt simple substance, contains 1.1 × 10-7Mol it) mixes, is stirred 4 hours at 100 DEG C.With1After H-NMR and IR confirmation Si -- H disappears, solvent and superfluous 2- allyloxyethanol are depressurized into distillation, carry out active carbon
Processing, the liquid for having obtained the pale yellow transparent as shown in following formula contain the compound of perfluoropolyether (VI) 55.2g.
[changing 41]
Rf ' :-CF2(OCF2CF2)q(OCF2)pOCF2-
(q/p=0.9, p+q ≒ 45)
By compound (VI)1H-NMR chemical shift is shown in table 4.
[table 4]
[synthesis example 5]
リ ナ ロ ー Le オ キ シ De (Off ラ ノ イ De) (2- (2- hydroxyl has been used in addition to replacing ユ ニ ル ー Block MA-35
Base -2- propyl) -5- methyl -5- vinyl tetrahydrofuran) other than 22g, similarly to Example 1, obtain translucent faint yellow
Highly viscous liquid by following formula compound represented (VII) 198g.
[changing 42]
By compound (VII)1H-NMR chemical shift is shown in table 5.
[table 5]
[embodiment 1,2 and comparative example 1]
It will be for each compound 10.0g and first of fluorine-containing alcoholic compound (II), (III) and (VII) obtained in synthesis example
Base ethyl ketone 10.0g, 4- methoxyhydroquinon 0.01g is respectively charged into the burning of 2 mouthfuls of the 100mL eggplant type with reflux unit and blender
In bottle, and then the acrylic acid 2- isocyanatoethyl of amount shown in table 6 below is added, is heated to 40 under dry atmosphere
℃.Next, 10 mass % methyl ethyl ketone solution 0.2g of four monooctyl ester of metatitanic acid are added thereto, continue to heat at 40 DEG C.
It for reaction solution, is sampled within every 12 hours, carries out the measurement of IR spectrum, confirm 2,280cm from isocyanate group-1's
The time that peak disappears.Result is shown in table 6 together.
[table 6]
For the reaction solution of embodiment 1 and embodiment 2, it is cooled to room temperature respectively after the peak of isocyanate groups disappears
Afterwards, hexane 100g is put into, is stirred 1 hour.It after stirring, is filtered, is made with hexafluoro meta-xylene residual on filter paper with filter paper
The ingredient dissolution stayed, decompression distillation in 2 hours is carried out at 80 DEG C/0.13kPa, has obtained the fluorine-containing system chemical combination of target
Object.
The compound of embodiment 1 described below.
[changing 43]
Yield 9.2g
By the compound of embodiment 11H-NMR chemical shift is shown in table 7.
[table 7]
The compound of embodiment 2 described below.
[changing 44]
Yield 8.5g
By the compound of embodiment 21H-NMR chemical shift is shown in table 8.
[table 8]
[embodiment 3,4 and comparative example 2,3]
Fluorine-containing alcoholic compound (V) and (VI) obtained in synthesis example are fitted into glass dish, it will be under nitrogen atmosphere 100
DEG C/the 12 small samples heated at present are denoted as (V '), (VI ') respectively.
For fluorine-containing alcoholic compound (V) and (VI) obtained in synthesis example and heat treatment will be carried out to them
Each compound 10.0g and methyl ethyl ketone 10.0g, 4- methoxyhydroquinon 0.01g of (V ') and (VI '), which are respectively charged into, has reflux
In 2 mouthfuls of 100mL eggplant type flask of device and blender, and then the acrylic acid 2- isocyanide of amount shown in table 9 below is added
Perester radical ethyl ester is heated to 40 DEG C under dry atmosphere.Next, 10 mass % methyl second of four monooctyl ester of metatitanic acid are added thereto
Base ketone solution 0.2g, continues to heat at 40 DEG C.Each reaction solution is sampled after 12 hours, carries out the measurement of IR spectrum,
It all confirmed the 2,280cm from isocyanate groups in all situations-1Peak disappearance.
Reaction solution is put into hexane 100g, stirred after being cooled to room temperature respectively after the peak of isocyanate groups disappears
It mixes 1 hour.It after stirring, is filtered, is dissolved ingredient remaining on filter paper with hexafluoro meta-xylene, 50 with filter paper
DEG C/0.13kPa under carry out decompression distillation in 2 hours, obtained the fluorine-containing based compound of target.
By obtained fluorine-containing based compound and 5 mass parts of solution for being diluted to 20 mass % with methyl iso-butyl ketone (MIBK)
With diacrylate 1, the mixing of 100 mass parts of 6- hexylene glycol ester after standing 1 hour at room temperature, carries out visual confirmation, if do not had
Muddiness is generated, then is dissolution.These result is shown in table 9 together.
[table 9]
The compound of embodiment 3 and 4 described below.
[changing 45]
Rf ' :-CF2(OCF2CF2)q(OCF2)pOCF2-
(q/p=0.9, p+q ≒ 45)
By the compound of embodiment 3 and 41H-NMR chemical shift shown in table 10.
[table 10]
[evaluation of the soil resistance of the production and solidfied material surface of solidfied material]
Will as (A) ingredient Examples 1 to 3 and comparative example 21 mass parts of compound, as 4 functions of (B) ingredient
Acrylate (EBECRYL 40 (ダ イ セ Le オ Le ネ Network ス society system) 100 mass parts, the 1- hydroxyl ring as (C) ingredient
3 mass parts of hexyl phenyl ketone and as solvent 142 mass parts of 2- propyl alcohol mix, modulate solidification compound.
By each composition of modulation with wire rod No.7 coating (16.0 μm of wet coating thickness) on polycarbonate substrate.After coating
Carry out 100 DEG C, after drying in 1 minute, using conveying type metal halide UV irradiation unit (パ Na ソ ニ ッ Network electrician system),
By cumulative exposure 1,600mJ/cm in nitrogen atmosphere2Ultraviolet light be irradiated to coated face, solidify composition.Solidification to obtaining
The water contact angle of film, oleic acid contact angle, magic ink erasing property are measured, evaluate.In order to compare, for being free of (A) ingredient
Sample has also carried out same evaluation as comparative example 4.By their result shown in table 11.
(measuring and evaluating method)
1) water contact angle measurement
Using contact angle meter (republicanism interface science society DropMaster), the drop of 2 μ L is dripped in cured film, is measured
Contact angle after 1 second.Using the average value of N=5 as measured value.
2) oleic acid contact angle determination
Using contact angle meter (republicanism interface science society DropMaster), the drop of 7 μ L is dripped in cured film, is measured
Contact angle after 1 second.Using the average value of N=5 as measured value.
3) evaluation of magic ink erasing property
Describe straight line with magic ink (ゼ Block ラ society Ha イ マ ッ キ ー (registered trademark) boldface letter) in solidification film surface, leads to
Crossing visually observation evaluation, it repels situation.
[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 | It does not wipe |
Claims (10)
1. fluorine-containing based compound shown in the following general formula (1) or (2):
[Rf1-Z1]a-Q1-[CH2-CHR1-Z2-CHR2-OR3]b (1)
[R3O-CHR2-Z2-CHR1-CH2]b-Q2-Z1-Rf2-Z1-Q2-[CH2-CHR1-Z2-CHR2-OR3]b (2)
In formula, Rf1For with selected from following formula (i), the structure of (ii), (iii) 1 valence holo-fluorine polyester,
CF3O-(CF2O)p-(CF2CF2O)q-CF2- (i)
In formula, the integer that p is 0~400, the integer that q is 0~170, the integer that p+q is 2~400,
F[CF(CF3)CF2O]r-CF(CF3)- (ii)
In formula, the integer that r is 1~120,
F[CF2CF2CF2O]s-CF2CF2- (iii)
In formula, the integer that s is 1~120,
Rf2For with selected from following formula (iv), (v) structure divalent holo-fluorine polyester,
-CF2O-(CF2O)p-(CF2CF2O)q-CF2- (iv)
In formula, the integer that p is 0~400, the integer that q is 0~170, the integer that p+q is 2~400,
-CF(CF3)-[OCF2CF(CF3)]t-OCF2CF2O-[CF(CF3)CF2O]u-CF(CF3)- (v)
In formula, the integer that t+u is 2~120,
Z1For the divalent group selected from following formula:
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2-
Q1For the linker of (a+b) valence comprising at least (a+b) a silicon atom, Q2It independently is comprising at least (b+1) a silicon atom
(b+1) valence linker；
Z2For the divalent group selected from following formula:
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2[OC2H4]d[OC3H6]e[OC4H8]f-
-CH2[OC2H4]d[OC3H6]e[OC4H8]fOCH2-,
Wherein, the integer that d is 0~99, the integer that e is 0~66, the integer that f is 0~50 are total to meet carbon number 200 hereinafter, weight
The arrangement of multiple unit is unrelated with type, is random, in addition, each repetitive unit can not be monomer but the mixing of isomers
Object,
R1It independently is the alkyl of 1 valence of hydrogen atom or carbon number 1~8；R2It independently is the alkyl of 1 valence of carbon number 1~8, Z2With R1
And/or Z2With R2It can respectively in connection with and with and R1、R2In conjunction with carbon atom be formed together cyclic structure, in addition, R1With R2It is combinable
And it is formed together with the carbon atom of each self-bonding containing Z2Cyclic structure, for the divalent group selected from following formula:
The integer that a is 1~10, b independently are 1~10 integer, R3Be each independently hydrogen atom or can contain oxygen atom and
The organic group of 1 valence with acryloyl group or α substituted acryl of nitrogen-atoms, but, R3It is average in the molecule to have extremely
The organic group of few 1 above-mentioned 1 valence.
2. fluorine-containing based compound described in claim 1, wherein the following formula in general formula (1) and (2)
-Z2-CHR2-OR3
Shown in group be following formula shown in group:
-Z3-OCH2CH(CH3)-OR3
In formula, R3It is same as described above, Z3For the alkyl of the divalent for containing oxygen atom and nitrogen-atoms of carbon number 1~199, can be formed halfway
Cyclic structure, in addition, adjacent R1With Z3In combination with and with and R1In conjunction with carbon atom be formed together cyclic structure.
3. fluorine-containing based compound as claimed in claim 2, wherein the following formula in general formula (1) and (2)
-Z2-CHR2-OR3
Shown in group be following formula shown in group:
-CH2-[OC3H6]n-OCH2CH(CH3)-OR3
In formula, R3Integer same as described above, that n is 0~64.
4. fluorine-containing based compound described in claim 1 is indicated by the following general formula (8) or (9):
[Rf1-Z1]a-Q1-[CH2CH2CH2[OC3H6]nOCH2CH(CH3)OCOCR4=CH2]b (8)
Rf2-{Z1-Q2-[CH2CH2CH2[OC3H6]nOCH2CH(CH3)OCONHCH2CH2OCOCR4=CH2]b}2 (9)
In formula, Rf1、Rf2、Q1、Q2、Z1, a, b as described above, n be 0~64 integer, R4For hydrogen atom or methyl.
5. fluorine-containing based compound described in claim 1, wherein
Q1Selected from following formula (vi)~(ix):
In formula, a, b are each independently 1~10 integer, and the integer that c is 1~5, the arrangement of each unit is random, (a+b)
The bonding end of (a+b-2) a each unit and a Z bracketed with []1With b CH2In any one group combine,
T is the linker of (a+b) valence, is either one or two of following formula (x)~(xiv):
Q2Selected from following formula (xv)~(xviii):
In formula, the integer that b is 1~10, the integer that c is 1~5, the arrangement of each unit is random, (b+1) and (b-1) a each list
The bonding end and Z of member1With the b CH bracketed with []2Any one group combine,
T ' is any of following formula (xix)~(xxiii):
6. fluorine-containing based compound described in claim 1, wherein fluorine-containing system chemical combination shown in formula (1) or (2)
Object is any of following formula (A1)~(A3):
In formula, Rf ' is-CF2O(CF2O)p1(CF2CF2O)q1CF2, p1, q1 be meet q1/p1=0.8~1.5, q1+p1=5~
80 number, r1 are respectively 2~100 integer, and n1 is each independently 0~30 integer.
7. the manufacturing method of fluorine-containing based compound described in claim 1, which is characterized in that make the following general formula (3) or
(4) fluorochemical shown in and the alcohol progress hydrosilylation shown in the following general formula (5) containing terminal unsaturation group are anti-
Fluorine-containing alcoholic compound obtained from answering is reacted with following formula (6) and/or (7) compound represented,
[Rf1-Z1]a-Q1-[H]b (3)
[H]b-Q2-Z1-Rf2-Z1-Q2-[H]b (4)
In formula, Q1、Q2、Rf1、Rf2、Z1, a, b be as previously mentioned, a Z bracketed with []1With b H all respectively with Q1Or Q2Knot
Silicon atom in structure combines,
CH2=CR1-Z2-CHR2-OH (5)
In formula, R1、R2、Z2As previously mentioned,
CH2=CR4COX (6)
CH2=CR4COOCH2CH2- N=C=O (7)
In formula, R4For hydrogen atom or methyl, X is halogen atom.
8. manufacturing method as claimed in claim 7, wherein formula (3) or (4) compound represented are selected from following (B-1)~(B-
8):
In formula, r1 is respectively 2~100 integer,
The alcohol containing terminal unsaturation group of formula (5) is selected from following formula:
CH2=CH-CH2-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)2-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)4-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)9-OCH2CH(CH3)-OH
9. solidification compound, which is characterized in that described in any item fluorine-containing systems chemical combination containing claim 1~6
Object.
10. making solidification compound as claimed in claim 9 substrate made of substrate surface coating, solidification.
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| JP6497350B2 (en) * | 2016-04-15 | 2019-04-10 | 信越化学工業株式会社 | Fluorine-containing acrylic composition and method for producing the same, fluorine-containing active energy ray-curable composition and article |
| JP6658449B2 (en) * | 2016-10-25 | 2020-03-04 | 信越化学工業株式会社 | Fluorine-containing acrylic compound, method for producing the same, and curable composition and article |
| KR102624940B1 (en) * | 2018-01-19 | 2024-01-15 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Fluorine-containing activated energy ray curable compositions and articles |
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| CN104945615A (en) | 2015-09-30 |
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