CN104109369A - Photocuring fluorinated polyol gel composition, curing method thereof, gel curing matter thereof, and gel product using curing matter - Google Patents
Photocuring fluorinated polyol gel composition, curing method thereof, gel curing matter thereof, and gel product using curing matter Download PDFInfo
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Abstract
The invention provides a photocuring fluorinated polyol gel composition with both excellent storage performance and excellent curing performance. The photocuring fluorinated polyol gel composition comprises: (A) a chain polyfluorinated compound with one molecule containing more than two alkenyls and a main chain containing a perfluoropolyethers structure, (B) a polyfluorinated single-alkenyl compound with one molecule containing one alkenyl and a main chain containing a perfluoropolyethers structure, (C) fluorine-containing organic hydrogenated siloxane with one molecule containing more than two hydrogen atoms bonded to silicon atoms directly, and (D) a photo-activation hydrosilylation reaction catalyzer.
Description
Technical field
The present invention relates to a kind of keeping quality excellent and be gelatinous composition, its curing, its gel solidification thing and the gel product that has used this cured article by the light solidified perfluoroalkyl polyether that light, particularly ultraviolet irradiation are given good solidified nature.
Background technology
At present, taking the divalent holo-fluorine polyester in 1 molecule with 2 alkenyls as host, contain and there is organic hydrogen diene polysiloxane of the hydrogen atom that is bonded to Siliciumatom and the fluoride gel composition of platinum metals series catalysts is known, it forms the perfluoroalkyl polyether with excellent resistance to chemical reagents, solvent resistance and low-moisture permeability by the heat treated of about 30～180 minutes conventionally at the temperature of 60～150 DEG C is gel solidification thing (patent documentation 1).
The addition curable perfluoroalkyl polyether of above-mentioned being heating and curing property is the platinum metals series catalysts that gelatinous composition uses catalytic amount, but from showing the reason considerations such as good catalyst activity, conventionally in curing catalysts, uses platinum alkenyl siloxanes complex compound.But, because this catalyst activity is high, particularly, in the time making the composition of a liquid type, in order to obtain sufficient keeping quality, need to add reaction control agent.Its result, the solidified nature will make it curing at the lower temperature such as room temperature time is blunt, on the other hand, has following predicament: reduce the addition of reaction control agent during in order to improve the solidified nature under low temperature, cannot obtain sufficient keeping quality.Therefore, practical situation are, first, add the reaction control agent of q.s in order to obtain desired keeping quality, about solidified nature, obtain sufficient solidified nature by the heat treated of implementing high temperature.
But, will make composition solidify under above-mentioned working conditions time, member that is difficult to be applied to the parts of the material that has used thermotolerance deficiency or can not heat because of the problem in size and performance etc., in addition, heating treatment step is necessary, thus, there is the problem of the speed of molding procedure while having to the molding procedure on production line to be made as intermittent mode, production control.
Therefore, expect exploitation go for can not heater and can improve manufacture efficiency such, keeping quality is excellent and show that the perfluoroalkyl polyether of good solidified nature is gelatinous composition at the lower temperature such as room temperature.
On the other hand, in silicone elastomer material, existing known Photocurable composition is to use by the UV rayed of 230～400nm to make the photoactivation type hydrosilylation catalysts of catalyst activation, the Photocurable composition (patent documentation 2 and patent documentation 3) of the good solidified nature while having sufficient keeping quality while not carrying out rayed and rayed concurrently.
Prior art document
Patent documentation
Patent documentation 1: No. 3487744 communique of patent
Patent documentation 2: Japanese Unexamined Patent Application Publication 2011-511768 communique
Patent documentation 3: TOHKEMY 2010-47646 communique
Summary of the invention
Invent problem to be solved
By being to use this photoactivation type hydrosilylation catalysts in gelatinous composition at this addition curable perfluoroalkyl polyether, can not being produced on while carrying out rayed and showing that near room temperature good conservatory light solidified perfluoroalkyl polyether is gelatinous composition.But there are the following problems for said composition: by the photoabsorption of polymer ends structure, can not obtain sufficient solidified nature.Therefore, also there are the following problems: in composition, add while suppressing the photoabsorption of end structure as the per-fluoro polyether compound of softening agent etc., although can improve light solidified, be difficult to freely design the hardness of gel.
Therefore, the object of the invention is to, providing a kind of light solidified to improve and having used the perfluoroalkyl polyether of photoactivation type hydrosilylation catalysts is gelatinous composition, its curing, its gel solidification thing and the gel product that has used this cured article.
For solving the technical scheme of problem
The inventor etc. concentrate on studies to achieve these goals, found that, contain following (A), (B), (C) and (D) the light solidified perfluoroalkyl polyether of composition be that gelatinous composition shows sufficient keeping quality in the time not carrying out rayed, and pass through light irradiation and show good light solidified, obtain sufficient cured article, completed the present invention.
Therefore, the invention provides a kind of light solidified perfluoroalkyl polyether shown in following is gelatinous composition, its curing, its gel solidification thing and the gel product that has used this cured article.
[1] light solidified perfluoroalkyl polyether is a gelatinous composition, it is characterized in that, contains:
(A) in 1 molecule, there are chain multi-fluorinated compounds 100 mass parts in 2 above alkenyls and main chain with perfluoropolyether structures;
(B) in 1 molecule, having the polyfluoro mono-alkenyl Compound Phase in 1 alkenyl and main chain with perfluoropolyether structures is 1～300 mass parts for (A) composition 100 mass parts;
(C) in 1 molecule, there are 2 fluorine-containing Organhydridosiloxaneresins that are bonded directly to above the hydrogen atom of Siliciumatom
The amount that makes Si-H base with respect to (A) composition and (B) 1 mole of the alkenyl of composition reach the amount of 0.5～3.0 mole; And
(D) photoactivation type hydrosilylation reaction catalyst
With respect to (A) composition 100 mass parts, be scaled 0.1～500ppm with atoms metal.
[2] the light solidified perfluoroalkyl polyether as described in [1] is gelatinous composition, it is characterized in that, as (E) composition, also contains at least a kind of per-fluoro polyether compound in the compound that is selected from following general formula (1)～(3) expression,
A-O-(CF
2CF
2CF
2O)
a-A (1)
[in formula (1), A is formula: C
bf
2b+
1the group that-(integer that b is 1～3) represents, the integer that a is 1～500.]
A-O-(CF
2O)
c-CF
2CF
2O)
d-A (2)
(in formula (2), A is same as described above, and c and d are respectively 1～300 integer.)
(in formula (3), A is same as described above, and e and f are respectively 1～300 integer.)
[3] the light solidified perfluoroalkyl polyether as described in [1] or [2] is gelatinous composition, and wherein, (A) composition is the chain multi-fluorinated compounds with side chain that following general formula (4) represents.
CH
2＝CH-(X)
g-Rf
1-(X’)
g-CH＝CH
2 (4)
[in formula, X is-CH
2-,-CH
2o-,-CH
2oCH
2-or-Y-NR
1-CO-
(at this, Y is-CH
2-,-Si (CH
3)
2cH
2cH
2cH
2-,-Si (CH
3) (CH=CH
2) CH
2cH
2cH
2-,-Si (CH=CH
2)
2cH
2cH
2cH
2-or following structural formula (Z) represent neighbour, or to silyl phenylene, R
1for hydrogen atom or do not replace or replace 1 valency alkyl),
(in formula (Z), R
3, R
4be independently-CH respectively
3or-CH=CH
2.)
X ' is-CH
2-,-OCH
2-,-CH
2oCH
2-or-CO-NR
2-Y '-(at this, Y ' is-CH
2-,-CH
2cH
2cH
2si (CH
3)
2-,-CH
2cH
2cH
2si (CH
3) (CH=CH
2)-,-CH
2cH
2cH
2si (CH=CH
2)
2-or the neighbour that represents of following structural formula (Z '), or to silyl phenylene, R
2for with above-mentioned R
1identical group,
(formula (Z ') in, R
3', R
4' be independently-CH respectively
3or-CH=CH
2.)。
G is 0 or 1 independently.
Rf
1for following general formula (i) or (ii) represent divalent holo-fluorine polyester,
(in formula, p and q are respectively 0 or 1～150 integer, and the mean value of p and q sum is 2～200.R is 0～6 integer, and t is 2 or 3.)
(in formula, the integer that u is 1～200, the integer that v is 1～50, t is same as described above.)。]
[4] the light solidified perfluoroalkyl polyether as described in any one in [1]～[3] is gelatinous composition, wherein, (C) the fluorine-containing Organhydridosiloxaneresins of composition has more than 11 valency perfluoroalkyl, 1 valency perfluor oxygen base alkyl, divalent perfluorinated alkylidene or divalent perfluor oxygen base alkylidene group in 1 molecule.
[5] the light solidified perfluoroalkyl polyether as described in any one in [1]～[4] is gelatinous composition, and wherein, (D) the photoactivation type hydrosilylation reaction catalyst of composition is (η
5-cyclopentadienyl) three (σ-alkyl) platinum (IV).
[6] the light solidified perfluoroalkyl polyether as described in any one in [1]～[4] is gelatinous composition, and wherein, (D) the photoactivation type hydrosilylation reaction catalyst of composition is beta-diketon platinum (II) complex compound.
[7] a kind of process for photocuring, it is gelatinous composition light irradiation and said composition is solidified to the light solidified perfluoroalkyl polyether described in any one in [1]～[6], it is characterized in that, this light has maximum peak wavelength in the region of the 300nm～400nm of luminescent spectrum, and this light is the radiometric below 5% of described maximum peak wavelength in the radiation intensity of each wavelength of the wavelength region may that is less than 300nm.
[8] process for photocuring as described in [7], is characterized in that, uses optical filter, and the radiation intensity that makes to be positioned at each wavelength of the wavelength region may that is less than 300nm is the radiometric below 5% of maximum peak wavelength.
[9] penetration degree (ASTM D-1403) is a gel solidification thing of 1～200, and it is that gelatinous composition is cured and obtains by the light solidified perfluoroalkyl polyether described in any one in [1]～[6].
[10] gel product, is characterized in that, containing the light solidified perfluoroalkyl polyether described in any one in [1]～[6] is that gelatinous composition is cured and the gel solidification thing that obtains.
[11] gel product as described in [10], it is the material that automobile is used, chemical plant is used, ink-jet printer is used, semiconductor production line is used, analysis/Physicochemical equipment is used, medical facilities are used, flyer is used, organic EL panel is used or fuel cell is used.
The effect of invention
Light solidified perfluoroalkyl polyether according to the present invention is gelatinous composition and curing thereof, can obtain having concurrently good keeping quality and the Photocurable composition of solidified nature, in addition, this cured article shows excellent solvent resistance, resistance to chemical reagents, thermotolerance, cold property, low-moisture permeability, electrical characteristic.Therefore, this cured article is preferably used or materials in MCFC material with, chemical plant, ink-jet printer, semiconductor production line, analysiss/Physicochemical equipment, medical facilities, flyer, organic EL panel as automobile.
Embodiment
Below, the present invention is described in further detail.
First be, that gelatinous composition describes to light solidified perfluoroalkyl polyether of the present invention.
Light solidified perfluoroalkyl polyether of the present invention is that gelatinous composition is characterised in that, contains:
(A) in 1 molecule, there is the chain multi-fluorinated compounds in 2 above alkenyls and main chain with perfluoropolyether structures
(B) in 1 molecule, there is the polyfluoro mono-alkenyl compound in 1 alkenyl and main chain with perfluoropolyether structures
(C) in 1 molecule, have 2 hydrogen atoms that are bonded directly to above Siliciumatom fluorine-containing Organhydridosiloxaneresins and
(D) photoactivation type hydrosilylation reaction catalyst.
[(A) composition]
Light solidified perfluoroalkyl polyether of the present invention is that (A) composition in gelatinous composition is in 1 molecule, to have the chain multi-fluorinated compounds in 2 above alkenyls and main chain with perfluoropolyether structures.At this, the number of alkenyl is preferably 2～30, particularly preferably 2～6.
As (A) composition, the material that particularly preferably following general formula (4) represents.
CH
2＝CH-(X)
g-Rf
1-(X’)
g-CH＝CH
2 (4)
[in formula, X is-CH
2-,-CH
2o-,-CH
2oCH
2-or-Y-NR
1(at this, Y is-CH-CO-
2-,-Si (CH
3)
2cH
2cH
2cH
2-,-Si (CH
3) (CH=CH
2) CH
2cH
2cH
2-,-Si (CH=CH
2)
2cH
2cH
2cH
2-or following structural formula (Z) represent neighbour, or to silyl phenylene, R
1for hydrogen atom or do not replace or replace 1 valency alkyl,
(in formula (Z), R
3, R
4be independently-CH respectively
3or-CH=CH
2.)，
X ' is-CH
2-,-OCH
2-,-CH
2oCH
2-or-CO-NR
2-Y '-(at this, Y ' is-CH
2-,-CH
2cH
2cH
2si (CH
3)
2-,-CH
2cH
2cH
2si (CH
3) (CH=CH
2)-,-CH
2cH
2cH
2si (CH=CH
2)
2-or the neighbour that represents of following structural formula (Z '), or to silyl phenylene, R
2for with above-mentioned R
1identical group,
(formula (Z ') in, R
3', R
4' be independently-CH respectively
3or-CH=CH
2.)。
G is 0 or 1 independently.
Rf
1for following general formula (i) or (ii) represent divalent holo-fluorine polyester,
(in formula, p and q are respectively 0 or 1～150 integer, and the mean value of p and q sum is 2～200.R is 0～6 integer, and t is 2 or 3.)
(in formula, the integer that u is 1～200, the integer that v is 1～50, t is same as described above.)。]
At this, as R
1, R
2, preferably hydrogen atom, carbonatoms 1～12, particularly preferably 1～10 alkyl, as alkyl, particularly, can enumerate: the alkyl such as methyl, ethyl, propyl group, butyl, hexyl, cyclohexyl, octyl group; The aryl such as phenyl, tolyl; The aralkyl such as benzyl, phenylethyl etc. and replacement 1 valency alkyl that the part or all of hydrogen atom of these groups is replaced with the halogen atom such as fluorine etc.
At this, the Rf in above-mentioned general formula (4)
1for divalent holo-fluorine polyester, preferred following general formula (i) or (ii) compound of expression.
(in formula, p and q are respectively 1～150 integer, are preferably 10～150 integer, and the mean value of p and q sum is 2～200, are preferably 20～160.In addition, the integer that r is 0～6, preferably 0～4 integer, t is 2 or 3.)
(in formula, the integer that u is 1～200, is preferably 20～160 integer, and the integer that v is 1～50 is preferably 5～40 integer, and t is same as described above.)
As Rf
1the preferred example of base, can enumerate example 3 groups described as follows.Wherein, the divalent group of the structure of the first formula particularly preferably.
(in formula, p1 and q1 are respectively 1～150 integer, p1+q1 (on average)=2～200.L is 2～6 integer.)
(in formula, p2 and q2 are respectively 1～150 integer, p2+q2 (on average)=2～200.L is 2～6 integer.)
(in formula, the integer that u1 is 1～200, the integer that v1 is 1～50.)
As the preferred example of (A) composition, can enumerate the compound that following general formula (5) represents.
[in formula, X
1expression-CH
2-,-CH
2o-,-CH
2oCH
2-or-Y-NR
11(Y represents group same as described above, R to-CO-
11for hydrogen atom, methyl, phenyl or allyl group), X
1' be-CH
2-,-OCH
2-,-CH
2oCH
2-or-CO-NR
12-Y '-(R
12represent and above-mentioned R
11identical group, Y ' represents group same as described above) group that represents, g is 0 or 1, the L integer that is 2～6 independently, p3 and q3 are respectively 1～150 integer, p3+q3 (on average)=2～200.]
The concrete example of the chain multi-fluorinated compounds representing as general formula (4), can enumerate the material that following formula represents.
(in formula, p ' and q ' are respectively 1～150 integer, represent to meet the number of p '+q '=6～200.)
(in formula, p ' ' and q ' ' are respectively 1～150 integer, represent to meet the number of p ' '+q ' '=2～200.)
In the chain multi-fluorinated compounds that above-mentioned general formula (4) represents, contained alkene base unit weight is preferably 0.005～0.050 mole/100g, more preferably 0.007～0.040 mole/100g.When in chain perfluoroalkyl polyether compound, contained alkene base unit weight is very few, the physical strength of cured article reduces sometimes, can not obtain cured article, when alkene base unit weight is too much, leakage of oil occurs sometimes.
It should be noted that, the viscosity (23 DEG C) of the chain multi-fluorinated compounds of above-mentioned general formula (4) is at 100～100,000mm
2/ s, more preferably 500～50,000mm
2/ s, further preferably 1,000～20,000mm
2in the scope of/s, use this composition in sealing, pouring, coating, impregnation etc. time, even cured article also has suitable physical property, therefore preferred.The chain multi-fluorinated compounds of general formula (4) is selected the material of optimal viscosity according to purposes.In addition, also low viscous polymkeric substance and full-bodied polymkeric substance can be mixed, be adjusted into desired viscosity and use.In addition, in the present invention, can utilize Ostwald's relative viscosity instrumentation to determine viscosity.
And, in the present invention, for the chain multi-fluorinated compounds of above-mentioned formula (4) being adjusted to desired weight-average molecular weight according to object, the silicoorganic compound that also can make in advance chain per-fluoro polyether compound as above and molecule contain 2 hydrogenation silyls (Si-H yl) carry out hydrosilylation reactions under usual method and condition, and the resultant that chain length has been extended uses as (A) composition.
These chain multi-fluorinated compounds can use separately a kind, or are used in combination two or more.
[(B) composition]
(B) composition is in 1 molecule, to have the polyfluoro mono-alkenyl compound in 1 alkenyl and main chain with perfluoropolyether structures.
As (B) composition, the polyfluoro mono-alkenyl compound that particularly preferably following formula (6) represents.
Rf
3-(X’)
g-CH＝CH
2 (6)
[in formula (6), X ' is-CH
2-,-OCH
2-,-CH
2oCH
2-or-CO-NR
2-Y '-(wherein, Y ' is-CH
2-,-CH
2cH
2cH
2si (CH
3)
2-,-CH
2cH
2cH
2si (CH
3) (CH=CH
2)-or following structural formula (Z ')
The group that (adjacent, or to dimetylsilyl phenylene) represents, R
2for hydrogen atom or do not replace or replace 1 valency alkyl, can illustrate the R with above-mentioned formula (4)
2in the same group of illustrative group.)。G is 0 or 1.Rf
3be the group of the perfluoro-polyether structure of 1 valency, preferably contain the structure that following formula represents,
C
s’F
2S’＋
1(C
hF
2hO)iC
t’F
2t’-
(in formula, the integer that s ' is 0～8, the integer that h is 1～6, the integer that i is 0～200, preferably 10～100 integer, more preferably 20～50 integer, t ' is 1 or 2.)。]
In above-mentioned formula (6), as Rf
3, can illustrate following group.
(in formula, the integer that s is 1～8, the integer that i1 is 0～200, the integer that i2+i3 is 0～200.)
The concrete example of the polyfluoro mono-alkenyl compound representing as above-mentioned general formula (6), can enumerate routine compound described as follows.
(in above-mentioned formula, the integer that i ' is 0～200.)
In above-mentioned polyfluoro mono-alkenyl compound, contained alkene base unit weight is preferably 0.005～0.050 mole/100g, more preferably 0.010～0.040 mole/100g.When in polyfluoro mono-alkenyl compound, contained alkene base unit weight is very few, sometimes follow the increase of polymer viscosity, its result causes the reduction of operability, and when alkene base unit weight is too much, the physical property of solvability reduction, bad order and the cured article to composition is inhomogeneous sometimes.
It should be noted that, from the viewpoint of the physical property in order to obtain uniform cured article, guarantee operability, preferably the viscosity (23 DEG C) of the polyfluoro mono-alkenyl compound of (B) composition is at 50～5000mm
2/ s, more preferably 100～2000mm
2/ s, further preferred 200～1000mm
2in the scope of/s.Can in this range of viscosities, select optimal viscosity according to purposes.
Be in gelatinous composition at solidified nature perfluoroalkyl polyether of the present invention, (B) use level of the polyfluoro mono-alkenyl compound of composition is 1～300 mass parts with respect to fluoropolymer 100 mass parts of the straight chain shape of above-mentioned (A) composition, is preferably 1～150 mass parts.When it is during lower than 1 mass parts, the cross-linking density after sometimes solidifying raises, and is difficult to become gel solidification thing, becomes rubber-like cured article, and in the time that it exceedes 300 mass parts, the cross-linking density step-down after sometimes solidifying, becomes liquid object, is difficult to become gel solidification thing.It should be noted that, (B) composition can be used singly or in combination of two or more.
[(C) composition]
(C) composition be in 1 molecule, have 1 above, preferably 1～10 fluorine-containing organic group and have 2 above, preferably 3～50 be bonded directly to the fluorine-containing Organhydridosiloxaneresins of the hydrogen atom (being the hydrogenation silyl that Si-H represents) of Siliciumatom.(C) of the present invention composition as above-mentioned (A) composition and (B), work by linking agent and/or the chain length prolongation agent of composition, in addition, from with (A) composition and (B) viewpoint such as intermiscibility, dispersiveness, the homogeneity solidifying of composition, as fluorine-containing organic group, preferably in 1 molecule, there is the group of the fluoro-containing groups such as 1 above 1 valency perfluoroalkyl, 1 valency perfluor oxygen base alkyl, divalent perfluorinated alkylidene or divalent perfluor oxygen base alkylidene group.
As this 1 valency or the fluorine-containing organic group of divalent, can enumerate group that such as following general formula represents etc.
C
jF
2j＋1-
-C
jF
2j-
(in formula, the integer that j is 1～20, is preferably 2～10 integer.)
(in formula, the integer that k is 1～200, is preferably 1～100 integer, the integer that l is 1～3.)
(in formula, w and x are respectively more than 1 integer, preferably 1～100 integer, and the mean value of w+x is 2～200, is preferably 2～100.)
-(CF
2O)
y-(CF
2CF
2O)
z-CF
2-
(wherein, y and z are respectively 1～50 integer, are preferably 1～40 integer.)
In addition, these perfluoroalkyls, perfluor oxygen base alkyl, perfluorinated alkylidene or perfluor oxygen base alkylidene group preferably utilize divalent concatenating group to be connected with Siliciumatom, as this divalent concatenating group, can or make ehter bond, Sauerstoffatom, amido linkage, ketonic linkage, ester bond, two organic silicylene etc. be present in the group in these groups for alkylidene group, arylidene and their combination, for example can enumerate:
-CH
2CH
2-、
-CH
2CH
2CH
2-、
-CH
2CH
2CH
2OCH
2-、
-CH
2CH
2CH
2-NH-CO-、
-CH
2CH
2CH
2-N(Ph)-CO-、
-CH
2CH
2CH
2-N(CH
3)-CO-、
-CH
2CH
2CH
2-N(CH
2CH
3)-CO-、
-CH
2CH
2-Si(CH3)
2-Ph’-N(CH
3)-CO-、
-CH
2CH
2CH
2-Si(CH
3)
2-Ph’-N(CH
3)-CO-、
-CH
2CH
2CH
2-O-CO-
(wherein, Ph is that phenyl, Ph ' are phenylene.)
Deng divalent concatenating group of carbonatoms 2～12 etc.
In addition, as above-mentioned 1 valency in the fluorine-containing Organhydridosiloxaneresins of this (C) composition or the fluorine-containing organic group of divalent and the 1 valency substituting group that is bonded to Siliciumatom except being bonded to the hydrogen atom of Siliciumatom, for example can enumerate: the alkyl such as methyl, ethyl, propyl group, butyl, hexyl, cyclohexyl, octyl group, decyl; The alkenyl such as vinyl, allyl group; The aryl such as phenyl, tolyl, naphthyl; The carbonatoms 1～20 such as group, such as chloromethyl, chloropropyl, cyano ethyl that the part or all of hydrogen atom of the aralkyl such as benzyl, phenylethyl and these groups is replaced by chlorine atom, cyano group etc., preferred 1～12 the 1 valency alkyl that does not replace or replace.
As the fluorine-containing Organhydridosiloxaneresins of (C) composition, can be ring-type, chain, three-dimensional netted and their any of combination.The Siliciumatom number of this fluorine-containing Organhydridosiloxaneresins is not particularly limited, and is generally 2～60, preferably 3～30 left and right.
As this (C) composition with 1 valency or the fluorine-containing organic group of divalent and silicon atom bonding hydrogen atom, can enumerate routine compound described as follows.These compounds can be used singly or in combination of two or more.It should be noted that, in following formula, Me represents methyl, and Ph represents phenyl.
In the fluorine-containing Organhydridosiloxaneresins of above-mentioned (C) composition, contained Si-H base unit weight is preferably 0.0005～0.0100 mole/g, more preferably 0.0010～0.0050 mole/g.When contained Si-H base unit weight is very few in fluorine-containing Organhydridosiloxaneresins, sometimes cause the physical property of cured article to reduce, when Si-H base unit weight is too much, foaming when curing sometimes, or the physical property generation rheological parameters' change with time of the cured article obtaining.
These fluorine-containing Organhydridosiloxaneresins can use separately a kind or be used in combination two or more.
The use level of above-mentioned (C) composition for (A) composition and (B) alkenyl in composition carry out the significant quantity of hydrosilylation reactions, conventionally with respect to (A) composition and (B) in composition 1 mole of the thiazolinyl such as contained vinyl, allyl group, cycloalkenyl group for making the hydrogenation silyl of (C) composition, Si-H base becomes preferably 0.5～3.0 mole, the more preferably amount of 0.8～2.0 mole.When hydrogenation silyl (≡ Si-H) is very few, sometimes crosslinking degree is insufficient, result can not obtain cured article, even if or be cured, the rheological parameters' change with time of the physical property of cured article also becomes greatly, in addition, and in the time that it is too much, sometimes when curing, bubble, or the rheological parameters' change with time of the physical property of cured article becomes large.
[(D) composition]
(D) of the present invention composition is photoactivation type hydrosilylation reaction catalyst.Photoactivation type hydrosilylation reaction catalyst is to be activated, to promote (A) composition and (B) alkenyl in composition and (C) catalyzer of the addition reaction of the hydrogenation silyl in composition by the uviolizing of light, particularly 300～400nm.This photoactivation type hydrosilylation reaction catalyst is mainly equivalent to platinum group metal catalysts or nickel is metal catalyst, as platinum group metal catalysts, there is the metal complex compounds of platinum group, palladium system, rhodium system, be metal catalyst as nickel, have the golden group complex compound of nickel system, iron system, cobalt system.Wherein, platinum series metal complex compound becomes more readily available and shows and therefore preferably uses good catalyst activity fully.
As the platinum series metal complex compound of photoactivation type, for example, there is (η
5-cyclopentadienyl) three (σ-alkyl) platinum complex compound and beta-diketon platinum complex compound etc., particularly, can enumerate: (methyl cyclopentadienyl) trimethylammonium platinum (IV), (cyclopentadienyl) trimethylammonium platinum (IV), (1,2,3,4,5-pentamethyl-cyclopentadienyl) trimethylammonium platinum (IV), (cyclopentadienyl) dimethyl ethyl platinum (IV), (cyclopentadienyl) dimethyl ethanoyl platinum (IV), (trimethyl silyl cyclopentadienyl) trimethylammonium platinum (IV), (methoxycarbonyl cyclopentadienyl) trimethylammonium platinum (IV), (3,5-dimethylphenyl silyl cyclopentadienyl) trimethylammonium cyclopentadienyl platinum (IV), trimethylammonium (methyl ethyl diketone) closes platinum (IV), trimethylammonium (3,5-heptane diketo) platinum (IV), trimethylammonium (methyl-acetoacetic ester) platinum (IV), two (2,4-pentane, two ketone acids) platinum (II), two (2,4-hexane, two ketone acids) platinum (II), two (2,4-heptane, two ketone acids) platinum (II), two (3,5-heptane, two ketone acids) platinum (II), two (1-phenyl-1,3-butane two ketone acids) platinum (II), two (1,3-phenylbenzene-1,3-propane two ketone acids) platinum (II), two (hexafluoroacetylacetones) close platinum (II) etc.
In the time using these catalyzer, in the time that it is solid catalyst, also can use with solid state, in order to obtain more uniform cured article, preferably make to be dissolved in the material of applicable solvent and (A) composition and/or (B) multi-fluorinated compounds of composition mix and use.
(D) usage quantity of composition is scaled 0.1～500ppm, is preferably 1～100ppm with atoms metal with respect to (A) composition 100 mass parts.When usage quantity is very few, can not obtain sufficient light solidified, on the other hand, in the time that it is too much, likely the thermotolerance of cured article be produced to detrimentally affect.It should be noted that, (D) composition can be used singly or in combination of two or more.
[(E) composition]
Be in gelatinous composition, can further coordinate as at least a kind in the compound that is selected from following general formula (1)～(3) expression of (E) composition without functionality per-fluoro polyether compound at light solidified perfluoroalkyl polyether of the present invention.
A-O-(CF
2CF
2CF
2O)
a-A (1)
[in formula (1), A is formula: C
bf
2b+
1the group that-(integer that b is 1～3) represents, the integer that a is 1～500, particularly 10～300 integer.]
A-O-(CF
2O)
c-(CF
2CF
2O)
d-A (2)
(in formula (2), A is same as described above, and c and d are respectively 1～300 integer, particularly 2～100 integer.)
(in formula (3), A is same as described above, and e and f are respectively 1～300 integer, particularly 2～100 integer.)
The optional per-fluoro polyether compound coordinating as (E) composition, by coordinating this composition, can not damage other physical property etc. and give the gel solidification thing of resistance to chemical reagents, solvent resistance, cold property excellence.Particularly, in the situation that being matched with solidified nature perfluoroalkyl polyether and being gelatinous composition, can reduce second-order transition temperature etc., obtain excellent cold property.
(E) use level of composition with respect to (A) composition and (B) total amount 100 mass parts of composition be preferably 0～150 mass parts, more preferably 0.1～100 mass parts, particularly preferably 0.5～50 mass parts.In the time that it exceedes 150 mass parts, sometimes from curing gelling material through time spill.It should be noted that, (E) composition can be used singly or in combination of two or more.
[other composition]
In composition of the present invention, in order to improve its practicality, except above-mentioned (A)～(E) composition, also can add himself known various Synergist S-421 95.As such composition, can enumerate the reaction control agent of for example hydrosilylation reactions.As the example of reaction control agent, for example can enumerate: 1-ethynyl-1-hydroxyl hexanaphthene, 3-methyl isophthalic acid-butine-3-alcohol, 3, acetylene alcohol and the 3-methyl-pirylenes, 3 such as 5-dimethyl-1-hexin-3-alcohol, 3-Methyl-1-pentene-3-alcohol, phenyl butynol, fluorine-containing acetylene alcohol compound that the acetylides such as 5-dimethyl-3-hexene-1-alkynes or following structural formula represent,
Or poly-ethylene methacrylic radical siloxane ring type compound, organo phosphorous compounds etc., can suitably keep thus solidification reactivity and storage stability.The controllability of these reaction control agents is because of its chemical structure difference, therefore, about addition, should be adjusted into respectively the suitableeest amount, generally speaking, when the addition of control agent is very few, can not obtain the long-term keeping quality under room temperature, in the time that it is too much, solidified nature is blunt sometimes, can not obtain sufficient solidified nature.
In addition, can add as required the various Synergist S-421 95s such as inanimate matter weighting agent as other any composition.Do not damage the scope of object of the present invention and do not damage the characteristic of composition and the limit of the physical property of cured article in, the use level of these additives is for arbitrarily.
As inanimate matter weighting agent, for example can enumerate: it is 50～1,000m that aerosil, wet silicon dioxide etc. utilizes the specific surface area of BET method
2the SiO 2 powder of/g left and right and quartz powder, fused quartz powder, diatomite, calcium carbonate etc. add epistasis or standard adds the electroconductibility imparting agents such as heat conductivity imparting agent, carbon black, silver powder, the electroconductive zinc oxides such as the heat-resisting rising agent such as the mineral dyes such as epistasis weighting agent, titanium oxide, ferric oxide, carbon black, Leyden blue, titanium oxide, ferric oxide, carbon black, cerium oxide, cerous hydroxide, zinc carbonate, magnesiumcarbonate, manganous carbonate, aluminum oxide, boron nitride, silicon carbide, metal-powder etc.
[light solidified perfluoroalkyl polyether is gelatinous composition]
The manufacture method that solidified nature perfluoroalkyl polyether of the present invention is gelatinous composition is not particularly limited, can be by manufacturing mixing mentioned component, for example, can be by by above-mentioned (A)～(D) composition and other any mixing device such as planetary-type mixer, ROSS mixing machine, HOBART mixing machine for composition, mix equably to manufacture with kneading devices such as three rollers as required.In addition, also can be as for example (A), (B), (C), (E) composition and (A), (B), (D), (E) composition, make two fluid compositions, mix in use.
Guaranteeing aspect operability and spuing property, forming process, the viscosity (23 DEG C) that preferred light solidified perfluoroalkyl polyether of the present invention is gelatinous composition is 50～100,000mPas, more preferably 100～70,000mPas, further preferably 300～50, in the scope of 000mPas.In order to be adjusted into such viscosity, preferably the molecular weight of the polymkeric substance of use is chosen to be to the suitableeest molecular weight, or low viscous polymkeric substance and the blending of full-bodied polymkeric substance are used, or adjust the use level of the per-fluoro polyether compound of (E) composition.
[light solidified perfluoroalkyl polyether is the process for photocuring of gelatinous composition]
The light solidified perfluoroalkyl polyether of manufacturing is that gelatinous composition can be cured by rayed.While solidifying, maximum peak wavelength in the luminescent spectrum of the light preferably irradiating is positioned at the region of 300～400nm, and the radiation intensity that is positioned at each wavelength of the wavelength region may that is less than 300nm is the radiometric below 5% of above-mentioned maximum peak wavelength, preferably below 1%, more preferably below 0.1%, in other words, more more preferred close to 0%.Irradiation be positioned at be less than 300nm wavelength region may, there is the light time that radiation intensity is greater than radiometric 5% large wavelength of above-mentioned maximum peak wavelength, likely cause the decomposition of polymer ends base, or the part decomposition of catalyzer etc., can not obtain sufficient cured article.
Be that the curing active ray kind of gelatinous composition is not particularly limited for making light solidified perfluoroalkyl polyether of the present invention, be preferably ultraviolet ray.Obtaining aspect good solidified nature, preferably ultraviolet irradiation amount (illumination) is counted 100mJ/cm with accumulative total light quantity
2～100,000mJ/cm
2, preferably 1,000mJ/cm
2～10,000mJ/cm
2, more preferably 5,000～10,000mJ/cm
2.In the situation of ultraviolet irradiation amount (illumination) lower than above-mentioned scope, when photoactivation type hydrosilylation reaction catalyst in composition is activated, likely can not obtain sufficient energy, can not obtain sufficient cured article, on the other hand, ultraviolet irradiation amount (illumination) is in situation more than above-mentioned scope, and composition is irradiated and needs above energy, likely cause the decomposition of polymer ends base or partially catalyzed agent inactivation etc., can not obtain sufficient cured article.
Uviolizing can be for having the light of multiple luminescent spectrums, can be also the light with single luminescent spectrum.In addition, single luminescent spectrum can have in the region of 300nm～400nm the spectrum of wealthy width.The light with single luminescent spectrum is to have the light of peak (being maximum peak wavelength) in the scope of 300nm～400nm, preferred 350nm～380nm.As the light source that irradiates such light, can enumerate the luminescence-utraviolet semiconductor element light sources such as ultraviolet LED (ultraviolet LED) and luminescence-utraviolet semiconductor laser.
There is the light source of the light of multiple luminescent spectrums as irradiation, can enumerate: the liquid laser of the gas lasers such as the nitrogen such as the lamps such as metal halide lamp, xenon lamp, carbon arc lamp, chemical lamp, sodium vapor lamp, Cooper-Hewitt lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, organic pigment solution, the Solid State Laser that contains rare earth ion in inorganic single crystal etc.
The wavelength region may that above-mentioned light has the situation at peak or is being less than 300nm in the wavelength region may that is less than 300nm in luminescent spectrum for example exists, in the situation (situation that luminescent spectrum is wealthy width through wide area wavelength region may) of radiometric wavelength of radiometric 5% with the maximum peak wavelength that is greater than in above-mentioned luminescent spectrum, utilizes optical filter to remove to be positioned at the light of the wavelength of the wavelength region may that is less than 300nm.Thus, the radiation intensity that makes to be positioned at each wavelength of the wavelength region may that is less than 300nm be maximum peak wavelength radiometric below 5%, preferably below 1%, more preferably below 0.1%, further preferably 0%.In addition, in luminescent spectrum, exist multiple peaks in the wavelength region may of 300nm～400nm, the spike length that wherein shows maximum absorbancy is made as to maximum peak wavelength.As long as optical filter stops the wavelength that is less than 300nm, just use without particular limitation known optical filter.Can use such as 365nm bandpass filter etc.It should be noted that, ultraviolet illumination, spectral distribution can be measured with spectroradiometer, for example USR-45D (USHIO motor).
As light irradiation device, be not particularly limited, can use the irradiating units such as such as point type irradiating unit, face formula irradiating unit, line formula irradiating unit, conveyor type irradiating unit.
Be gelatinous composition while solidifying making light solidified perfluoroalkyl polyether of the present invention, the rayed time is for example 1～300 second, preferably 10～200 seconds, more preferably 30～150 seconds, irradiating after 1～60 minute, particularly carry out gelation after 5～30 minutes.In the present invention, gelation refers to that light solidified perfluoroalkyl polyether is that gelatinous composition part is cured reaction, and composition has lost the state of mobility.
[light solidified perfluoroalkyl polyether is gel solidification thing]
Composition of the present invention taking above-mentioned (A)～(D) composition as main component can form resistance to chemical reagents and solvent resistance excellence and the low gel solidification thing of water vapour permeability by above-mentioned photocuring.It should be noted that, in this manual, gel solidification thing refers to the state that partly has three-dimensional structure, shows distortion and mobility according to stress, particularly, refer to gel solidification thing that the penetration degree in ASTM D-1403 (1/4 cone) is 1～200 or in JIS sclerometer hardness be the gel solidification thing below 0.The formation of gel solidification thing can by after injecting the present composition or carry out coating in suitable container on suitable matrix, carry out rayed and make its solidify etc. existing known method easily carry out.
Light solidified perfluoroalkyl polyether of the present invention is that gel solidification thing can be used as automobile, chemical plant, ink-jet printer, semiconductor production line, analysis/Physicochemical equipment, medical facilities, flyer, organic EL panel, fuel cell and the member etc. such as uses preferably to use.
While being described in further detail, cured article of the present invention and the gel product that contains cured article can be used as automotive part, parts for chemical plant, for ink-jet printer parts, semi-conductor parts, analysis/Physicochemical for production line establish spare unit, parts, electric and electronic dampproof coating material, embedding agent, the preferred use such as sealing material, fuel cell sealing material organic EL panel for sensor for for medical facilities.
Particularly, as in the situation that for electric and electronic, dampproof coating material, sensor embedding agent use, can preferably use baroceptor, hydrauliccapsule, temperature sensor, humidity sensor, turn-sensitive device, G sensor, Time Pick-off Units, air flowmeter, electronic circuit, semiconductor subassembly, various control units etc.
In addition, in the case of using the cured article of composition of the present invention as embedding agent, coated material etc., in order to improve and adaptation or the cementability of body material, and with known priming paint be useful.Can utilize priming paint to prevent from immersing medicine and solvent from body material interface, can improve acid resistance, resistance to chemical reagents and the solvent resistance of parts entirety.
As priming paint, can preferably to use silane taking silane coupling agent as main body be priming paint, taking organic hydrogen diene polysiloxane as the priming paint of main body, the priming paint taking urethane resin as main component, the priming paint taking epoxy resin as main component etc.
Embodiment
Below, embodiment and comparative example are shown, the present invention is described particularly, but the present invention is not restricted to following embodiment.It should be noted that, in following embodiment, part expression mass parts.
[embodiment 1]
The polymkeric substance (viscosity 5, the 800mm that in planetary-type mixer, add following formula (7) to represent
2/ s, 0.013 mole/100g of ethene base unit weight) polymkeric substance (the viscosity 600mm that represents of 55 parts, following formula (8)
2/ s, 0.023 mole/100g of ethene base unit weight) 25 parts of 20 parts, Demnum S-65 (perfluoro polyether oil, Daikin Industries (strain) trade(brand)name processed), be mixed to evenly.Wherein add successively 1 of (methyl cyclopentadienyl) trimethylammonium platinum (IV), 18.09 parts of 0.002 part of the fluorine-containing acetylene alcohols that 0.04 part of two (trifluoromethyl) benzole soln (platinum concentration 6.0 quality %) of 3-, following formula (9) represent, the fluorine-containing Organhydridosiloxaneresins that following formula (10) represents (0.00062 mole of Si-H base unit weight/g), mix to become uniform mode, prepare solidification compound.
(the mean value (weight average degree of polymerization) ≒ 90) of m+n
[embodiment 2]
In above-described embodiment 1, replace 55 parts, the polymkeric substance that above-mentioned formula (7) represents, the polymkeric substance (viscosity 5, the 800mm that use following formula (11) to represent
2/ s, 0.012 mole/100g of ethene base unit weight) 55 parts, in addition, similarly operation, prepares solidification compound.
(the mean value (weight average degree of polymerization) ≒ 90) of m+n
[embodiment 3]
In above-described embodiment 1, replace 0.002 part of the fluorine-containing acetylene alcohol that above-mentioned formula (9) represents, change to 0.006 part of the toluene solution (5 quality %) of ethynylcyclohexanol, in addition, similarly operation, prepares solidification compound.
[embodiment 4]
In above-described embodiment 1, by 1 of (methyl cyclopentadienyl) trimethylammonium platinum (IV), 0.04 part of two (trifluoromethyl) benzole soln (platinum concentration 6.0 quality %) of 3-change to two (2, the acid of 4-heptadione) 0.48 part of acetic acid 2-(2-butoxy oxyethyl group) the ethyl ester solution (platinum concentration 0.5 quality %) of platinum (II), in addition, similarly operation, prepares solidification compound.
[embodiment 5]
In above-described embodiment 1, (0.00062 mole of Si-H base unit weight/g) changes to 2.24 parts of the fluorine-containing Organhydridosiloxaneresins that following formula (12) represents (0.0050 mole of Si-H base unit weight/g) for 18.09 parts of fluorine-containing Organhydridosiloxaneresins that above-mentioned formula (10) is represented, in addition, similarly operation, prepares solidification compound.
[reference example]
In above-described embodiment 1, replace photoactivation type hydrosilylation reaction catalyst: methyl cyclopentadienyl) trimethylammonium platinum (IV) 1,0.04 part of two (trifluoromethyl) benzole soln (platinum concentration 6.0 quality %) of 3-, change to non-photoactivation type hydrosilylation reaction catalyst: 0.08 part of the ethanolic soln (platinum concentration 3.0 quality %) of platinum-divinyl tetramethyl disiloxane complex compound, in addition, similarly operation, prepares solidification compound.
[keeping quality evaluation]
The solidification compound obtaining in above-described embodiment, reference example is placed 2 weeks at shading, 23 DEG C, compared with initial stage viscosity.The results are shown in table 1.In addition, the mensuration of viscosity, according to JIS K7117-1, is used TV-10U type rotational viscosimeter (Rod No.H6,23 DEG C, 50rpm) to carry out.
[table 1]
(it should be noted that, " ← " expression in table is identical with the numerical value of recording in the left neighbour's on the hurdle of record this " ← " hurdle.)
Result by table 1 is learnt: by using photoactivation type hydrosilylation reaction catalyst, at shading, 23 DEG C, can obtain good keeping quality.
[light solidified evaluation]
Embodiment 1～5
The Photocurable composition being obtained by above-described embodiment 1～5 is put into respectively to the glass disc of φ 30 × 14mm, used the SP-V type ultraviolet radiation device (USHIO system) that uniform irradiation optical unit is installed to carry out rayed.Now, utilize 365nm bandpass filter (USHIO motor society system) to remove the light that is positioned at the wavelength region may that is less than 300nm, taking the accumulative total light quantity of the light of the 365nm of predominant wavelength as 9,000mJ/cm
2mode carry out 90 seconds irradiate.Shading immediately after rayed leaves standstill at 23 DEG C, measures to the gelation time of mobility that loses composition, and measures the penetration degree after 2 hours, after 4 hours, after 24 hours after rayed.Table 2 illustrates its result.In addition, the penetration degree of cured article is according to ASTM D-1403, measure with 1/4 cone.
Comparative example 1～5
In above-described embodiment 1～5, in the time of uviolizing, do not use 365nm bandpass filter (USHIO motor society system), in addition, carry out same operation.The results are shown in table 2.
[table 2]
Result by table 2 is learnt: by being that gelatinous composition 365nm bandpass filter is blocked and is positioned at the light of the wavelength domain that is less than 300nm and carries out rayed to light solidified perfluoroalkyl polyether of the present invention, show good solidified nature.In addition, not using in the comparative example of 365nm bandpass filter,, there is uncured portion in the whole xanthochromias of the most surface of photoirradiated surface, can not obtain sufficient cured article.
Claims (11)
1. light solidified perfluoroalkyl polyether is a gelatinous composition, and it contains:
(A) in 1 molecule, there are chain multi-fluorinated compounds 100 mass parts in 2 above alkenyls and main chain with perfluoropolyether structures;
(B) in 1 molecule, having the polyfluoro mono-alkenyl Compound Phase in 1 alkenyl and main chain with perfluoropolyether structures is 1～300 mass parts for (A) composition 100 mass parts;
(C) in 1 molecule, there are 2 fluorine-containing Organhydridosiloxaneresins that are bonded directly to above the hydrogen atom of Siliciumatom
The amount that makes Si-H base with respect to (A) composition and (B) 1 mole of the alkenyl of composition reach the amount of 0.5～3.0 mole; And
(D) photoactivation type hydrosilylation reaction catalyst
With respect to (A) composition 100 mass parts, be scaled 0.1～500ppm with atoms metal.
2. light solidified perfluoroalkyl polyether as claimed in claim 1 is gelatinous composition, wherein, as (E) composition, also contains at least a kind of per-fluoro polyether compound in the compound that is selected from following general formula (1)～(3) expression,
A-O-(CF
2CF
2CF
2O)
a-A (1)
In formula (1), A is formula: C
bf
2b+1the group of-expression, wherein, the integer that b is 1～3, the integer that a is 1～500;
A-O-(CF
2O)
c-(CF
2CF
2O)
d-A (2)
In formula (2), A is same as described above, and c and d are respectively 1～300 integer;
In formula (3), A is same as described above, and e and f are respectively 1～300 integer.
3. light solidified perfluoroalkyl polyether as claimed in claim 1 or 2 is gelatinous composition, and wherein, (A) composition is the chain multi-fluorinated compounds with side chain that following general formula (4) represents,
CH
2＝CH-(X)
g-Rf
1-(X’)
g-CH＝CH
2 (4)
In formula, X is-CH
2-,-CH
2o-,-CH
2oCH
2-or-Y-NR
1-CO-,
Wherein, Y is-CH
2-,-Si (CH
3)
2cH
2cH
2cH
2-,-Si (CH
3) (CH=CH
2) CH
2cH
2cH
2-,-Si (CH=CH
2)
2cH
2cH
2cH
2-or following structural formula (Z) represent neighbour, or to silyl phenylene, R
1for hydrogen atom or do not replace or replace 1 valency alkyl,
In formula (Z), R
3, R
4be independently-CH respectively
3or-CH=CH
2,
X ' is-CH
2-,-OCH
2-,-CH
2oCH
2-or-CO-NR
2-Y '-,
Wherein, Y ' is-CH
2-,-CH
2cH
2cH
2si (CH
3)
2-,-CH
2cH
2cH
2si (CH
3) (CH=CH
2)-,-CH
2cH
2cH
2si (CH=CH
2)
2-or the neighbour that represents of following structural formula (Z '), or to silyl phenylene, R
2for with above-mentioned R
1identical group,
Formula (Z ') in, R
3', R
4' be independently-CH respectively
3or-CH=CH
2,
G is 0 or 1 independently,
Rf
1for following general formula (i) or (ii) represent divalent holo-fluorine polyester,
In formula, p and q are respectively 0 or 1～150 integer, and the mean value of p and q sum is that 2～200, r is 0～6 integer, and t is 2 or 3,
In formula, the integer that u is 1～200, the integer that v is 1～50, t is same as described above.
4. the light solidified perfluoroalkyl polyether as described in any one in claim 1～3 is gelatinous composition, wherein, (C) the fluorine-containing Organhydridosiloxaneresins of composition has more than 11 valency perfluoroalkyl, 1 valency perfluor oxygen base alkyl, divalent perfluorinated alkylidene or divalent perfluor oxygen base alkylidene group in 1 molecule.
5. the light solidified perfluoroalkyl polyether as described in any one in claim 1～4 is gelatinous composition, and wherein, (D) the photoactivation type hydrosilylation reaction catalyst of composition is (η
5-cyclopentadienyl) three (σ-alkyl) platinum (IV).
6. the light solidified perfluoroalkyl polyether as described in any one in claim 1～4 is gelatinous composition, and wherein, (D) the photoactivation type hydrosilylation reaction catalyst of composition is beta-diketon platinum (II) complex compound.
7. a process for photocuring, the method comprises: to the light solidified perfluoroalkyl polyether described in any one in claim 1～6 be gelatinous composition light irradiation and make said composition solidify, wherein, this light has maximum peak wavelength in the region of the 300nm～400nm of luminescent spectrum, and this light is the radiometric below 5% of described maximum peak wavelength in the radiation intensity of each wavelength of the wavelength region may that is less than 300nm.
8. process for photocuring as claimed in claim 7, wherein, uses optical filter, and the radiation intensity that makes to be positioned at each wavelength of the wavelength region may that is less than 300nm is the radiometric below 5% of maximum peak wavelength.
9. penetration degree (ASTM D-1403) is a gel solidification thing of 1～200, and it is that gelatinous composition is cured and obtains by the light solidified perfluoroalkyl polyether described in any one in claim 1～6.
10. a gel product, wherein, containing the light solidified perfluoroalkyl polyether described in any one in claim 1～6 is that gelatinous composition is cured and the gel solidification thing that obtains.
11. gel products as claimed in claim 10, it is the material that automobile is used, chemical plant is used, ink-jet printer is used, semiconductor production line is used, analysis/Physicochemical equipment is used, medical facilities are used, flyer is used, organic EL panel is used or fuel cell is used.
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Also Published As
| Publication number | Publication date |
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| TW201506080A (en) | 2015-02-16 |
| CN104109369B (en) | 2017-12-29 |
| KR20140124724A (en) | 2014-10-27 |
| TWI609049B (en) | 2017-12-21 |
| JP2014210831A (en) | 2014-11-13 |
| JP6020327B2 (en) | 2016-11-02 |
| KR102167471B1 (en) | 2020-10-19 |
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