CN104109369B - Photo-curable perfluoroalkyl polyether system gel combination, its curing, its gel solidification thing and the gel product for having used the solidfied material - Google Patents
Photo-curable perfluoroalkyl polyether system gel combination, its curing, its gel solidification thing and the gel product for having used the solidfied material Download PDFInfo
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Abstract
Present invention offer is a kind of to have both good keeping quality and the photo-curable perfluoroalkyl polyether system gel combination of curability.A kind of photo-curable perfluoroalkyl polyether system gel combination, it is characterised in that contain：(A) in 1 molecule with the chain multi-fluorinated compounds with perfluoropolyether structures, (B) 1 molecule in the alkenyl and main chain of more than 2 with the fluorine-containing Organhydridosiloxaneresins and (D) photoactivation type hydrosilylation reaction catalyst with more than 2 hydrogen atoms for being bonded directly to silicon atom in the polyfluoro mono-alkenyl compound with perfluoropolyether structures, (C) 1 molecule in 1 alkenyl and main chain.
Description
Technical field
It is the present invention relates to a kind of keeping quality excellent and assign good curability by light, particularly ultraviolet irradiation
Photo-curable perfluoroalkyl polyether system gel combination, its curing, its gel solidification thing and the gel system for having used the solidfied material
Product.
Background technology
At present, using the divalent holo-fluorine polyester with 2 alkenyls in 1 molecule as host, containing with being bonded to silicon atom
The fluoride gel composition of organic hydrogen diene polysiloxanes and platinum group metal series catalysts of hydrogen atom be known, its is usual
Formed at a temperature of 60~150 DEG C by the heating of 30~180 minutes or so with excellent resistance to chemical reagents, resistance to molten
Agent and the perfluoroalkyl polyether system gel solidification thing (patent document 1) of low-moisture permeability.
The addition curable perfluoroalkyl polyether system gel combination of above-mentioned being heating and curing property uses the platinum group metal system of catalytic amount
Catalyst, but from the consideration of the reasons such as good catalyst activity is shown, platinum alkenyl silica is used generally in curing catalysts
Alkane complex compound.But because the catalyst activity is high, particularly when making the composition of a liquid type, in order to obtain sufficiently
Keeping quality is, it is necessary to add reaction controlling agent.As a result, to make curability during its solidification slow in the case where room temperature etc. is than relatively low temperature
It is blunt, on the other hand, following predicament be present：When reducing the addition of reaction controlling agent to improve the curability under low temperature, nothing
Method obtains sufficient keeping quality.Therefore, actual conditions are first, sufficient amount to be added in order to obtain desired keeping quality
Reaction controlling agent, on curability, sufficient curability is obtained by implementing the heating of high temperature.
But when under above-mentioned use condition solidifying composition, it is difficult to applied to the material for having used heat resistance deficiency
The part of material or the component that can not heat because in size and performance the problem of etc., in addition, heating treatment step is necessary,
Thus, the speed that molding procedure when having to molding procedure on production line being set to intermittent mode, control production be present is asked
Topic.
Go for being unable to heater and can improve that manufacture efficiency is such, keeping quality is excellent therefore, it is desirable to develop
Perfluoroalkyl polyether system gel combination different and that good curability is shown in the case where room temperature etc. is than relatively low temperature.
On the other hand, in silicone elastomer material, existing known Photocurable composition be use by 230~
400nm UV light irradiations make the photoactivation type hydrosilylation catalysts of activation of catalyst, have filling when not carrying out light irradiation concurrently
The Photocurable composition (patent document 2 and patent document 3) of good curability when the keeping quality and light irradiation that divide.
Prior art literature
Patent document
Patent document 1：No. 3487744 publication of patent
Patent document 2：Japanese Unexamined Patent Application Publication 2011-511768 publications
Patent document 3：Japanese Unexamined Patent Publication 2010-47646 publications
The content of the invention
Invent problem to be solved
By using the photoactivation type hydrosilylation catalysts in the addition curable perfluoroalkyl polyether system gel combination,
It can be produced on and not carry out the photo-curable perfluoroalkyl polyether system Gel Compositions for showing good keeping quality during light irradiation near room temperature
Thing.But there are the following problems for said composition：Pass through the light absorbs of polymer ends structure, it is impossible to obtain sufficient curability.
Therefore, there is also following problem：Per-fluoro polyether compound as plasticizer etc. is added in the composition and suppresses end structure
Light absorbs when, although photo-curable can be improved, be difficult to freely design gel hardness.
Therefore, improved it is an object of the present invention to provide a kind of photo-curable and used photoactivation type silane
Perfluoroalkyl polyether system gel combination, its curing, its gel solidification thing and the gel for having used the solidfied material of Alkanizing catalyst
Product.
For solving the technical scheme of problem
The present inventor etc. are concentrated on studies to achieve these goals, are as a result found, containing following (A), (B),
(C) and photo-curable perfluoroalkyl polyether system's gel combination of (D) composition shows sufficient keeping quality when not carrying out light irradiation, and logical
Cross irradiation light and show good photo-curable, obtain sufficient solidfied material, complete the present invention.
Therefore, the present invention provide it is a kind of it is following shown in photo-curable perfluoroalkyl polyether system gel combinations, its curing, its
Gel solidification thing and the gel product for having used the solidfied material.
[1] a kind of photo-curable perfluoroalkyl polyether system gel combination, it is characterised in that contain：
(A) with the chain polyfluoro chemical combination with perfluoropolyether structures in the alkenyl and main chain of more than 2 in 1 molecule
The mass parts of thing 100；
(B) with the polyfluoro mono-alkenyl compound with perfluoropolyether structures in 1 alkenyl and main chain in 1 molecule
It is 1~300 mass parts relative to the mass parts of (A) composition 100；
(C) there are the fluorine-containing Organhydridosiloxaneresins of more than 2 hydrogen atoms for being bonded directly to silicon atom in 1 molecule
Make the amount of Si-H bases relative to 1 mole of amount for reaching 0.5~3.0 mole of alkenyl of (A) composition and (B) composition；
And
(D) photoactivation type hydrosilylation reaction catalyst
Relative to the mass parts of (A) composition 100,0.1~500ppm is scaled with metallic atom.
[2] the photo-curable perfluoroalkyl polyether system gel combination as described in [1], it is characterised in that as (E) composition, also contain
There is at least one kind of per-fluoro polyether compound in the compound represented selected from following formulas (1)~(3),
A-O-(CF2CF2CF2O)a-A (1)
[in formula (1), A is formula：CbF2b+1The group that-(b is 1~3 integer) represents, a is 1~500 integer.]
A-O-(CF2O)c-CF2CF2O)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 photo-curable perfluoroalkyl polyether system gel combination as described in [1] or [2], wherein, (A) composition is following formulas
(4) the chain multi-fluorinated compounds with side chain represented.
CH2=CH- (X)g-Rf1-(X’)g- CH=CH2 (4)
[in formula, X is-CH2-、-CH2O-、-CH2OCH2- or-Y-NR1-CO-
(here, Y is-CH2-、-Si(CH3)2CH2CH2CH2-、-Si(CH3) (CH=CH2)CH2CH2CH2- ,-Si (CH=
CH2)2CH2CH2CH2- or following structural formula (Z) represent o-, m- or p- silicyl phenylene, R1For hydrogen atom or unsubstituted
Or 1 valency alkyl of substitution),
(in formula (Z), R3、R4It is separately-CH3Or-CH=CH2。)
X ' is-CH2-、-OCH2-、-CH2OCH2- or-CO-NR2- Y '-(here, Y ' is-CH2-、-CH2CH2CH2Si
(CH3)2-、-CH2CH2CH2Si(CH3) (CH=CH2)-、-CH2CH2CH2Si (CH=CH2)2- or following structural formula (Z ') expression
O-, m- or p- silicyl phenylene, R2For with above-mentioned R1Identical group,
(in formula (Z '), R3’、R4' it is separately-CH3Or-CH=CH2。)。
G independently is 0 or 1.
Rf1The divalent holo-fluorine polyester represented for following formulas (i) or (ii),
(in formula, p and q are respectively 0 or 1~150 integer, and the average value of p and q sums is 2~200.R is 0~6
Integer, t are 2 or 3.)
(in formula, u is 1~200 integer, and v is 1~50 integer, and t is same as described above.).]
[4] the photo-curable perfluoroalkyl polyether system gel combination as any one of [1]~[3], wherein, (C) composition
Fluorine-containing Organhydridosiloxaneresins are sub- with the 1 valency perfluoroalkyl of more than 1,1 valency perfluor epoxide alkyl, divalent perfluor in 1 molecule
Alkyl or divalent perfluorooxyalkylene.
[5] the photo-curable perfluoroalkyl polyether system gel combination as any one of [1]~[4], wherein, (D) composition
Photoactivation type hydrosilylation reaction catalyst is (η5- cyclopentadienyl group) three (σ-alkyl) platinum (IV).
[6] the photo-curable perfluoroalkyl polyether system gel combination as any one of [1]~[4], wherein, (D) composition
Photoactivation type hydrosilylation reaction catalyst is beta-diketon platinum (II) complex compound.
[7] a kind of process for photocuring, it is to the photo-curable perfluoroalkyl polyether system Gel Compositions any one of [1]~[6]
Thing irradiation light and solidify said composition, it is characterised in that the light 300nm~400nm of luminescent spectrum region have most
Big spike length, and the light is in the radiancy that the radiancy of each wavelength of the wavelength region less than 300nm is the maximum peak wavelength
Less than 5%.
[8] process for photocuring as described in [7], it is characterised in that using optical filter, make to be located at less than 300nm's
The radiancy of each wavelength of wavelength region is radiometric less than the 5% of maximum peak wavelength.
[9] a kind of needle penetration (ASTM D-1403) is 1~200 gel solidification thing, and it is by any one of [1]~[6]
Obtained from described photo-curable perfluoroalkyl polyether system gel combination is solidified.
[10] a kind of gel product, it is characterised in that containing the photo-curable fluorine any one of [1]~[6] is gathered
Gel solidification thing obtained from ether system gel combination is solidified.
[11] gel product as described in [10], it is automobile using, chemical plant is used, ink-jet printer is used, semiconductor production
Line with, analysis/Physicochemical equipment with, Medical Devices with, airborne vehicle with, organic EL panel with or fuel cell material.
The effect of invention
According to the photo-curable perfluoroalkyl polyether system's gel combination and its curing of the present invention, can obtain having concurrently good
The Photocurable composition of keeping quality and curability, in addition, the solidfied material shows excellent solvent resistance, resistance to chemical reagents, heat-resisting
Property, low-temperature characteristics, low-moisture permeability, electrical characteristics.Therefore, the solidfied material is preferably as automobile using, chemical plant use, ink-jet printer
Used with, semiconductor production line, analysis/Physicochemical equipment is used, Medical Devices are used, airborne vehicle is used, organic EL panel is used or fuel electricity
Pond material.
Embodiment
Below, the present invention is illustrated in further detail.
First, the photo-curable perfluoroalkyl polyether system gel combination of the present invention is illustrated.
The photo-curable perfluoroalkyl polyether system gel combination of the present invention is characterised by, is contained：
(A) with the chain polyfluoro chemical combination with perfluoropolyether structures in the alkenyl and main chain of more than 2 in 1 molecule
Thing
(B) with the polyfluoro mono-alkenyl compound with perfluoropolyether structures in 1 alkenyl and main chain in 1 molecule
(C) have in 1 molecule more than 2 hydrogen atoms for being bonded directly to silicon atom fluorine-containing Organhydridosiloxaneresins and
(D) photoactivation type hydrosilylation reaction catalyst.
[(A) composition]
(A) composition in the photo-curable perfluoroalkyl polyether system gel combination of the present invention is with the chain of more than 2 in 1 molecule
There are the chain multi-fluorinated compounds of perfluoropolyether structures in alkenyl and main chain.Here, the number of alkenyl is preferably 2~30, it is special
Not preferably 2~6.
As (A) composition, the material of particularly preferably following formulas (4) expressions.
CH2=CH- (X)g-Rf1-(X’)g- CH=CH2 (4)
[in formula, X is-CH2-、-CH2O-、-CH2OCH2- or-Y-NR1- CO- is (here, Y is-CH2-、-Si(CH3)2CH2CH2CH2-、-Si(CH3) (CH=CH2)CH2CH2CH2- ,-Si (CH=CH2)2CH2CH2CH2- or following structural formula (Z) expression
O-, m- or p- silicyl phenylene, R1For hydrogen atom or unsubstituted or substituted 1 valency alkyl,
(in formula (Z), R3、R4It is separately-CH3Or-CH=CH2.),
X ' is-CH2-、-OCH2-、-CH2OCH2- or-CO-NR2- Y '-(here, Y ' is-CH2-、-CH2CH2CH2Si
(CH3)2-、-CH2CH2CH2Si(CH3) (CH=CH2)-、-CH2CH2CH2Si (CH=CH2)2- or following structural formula (Z ') expression
O-, m- or p- silicyl phenylene, R2For with above-mentioned R1Identical group,
(in formula (Z '), R3’、R4' it is separately-CH3Or-CH=CH2。)。
G independently is 0 or 1.
Rf1The divalent holo-fluorine polyester represented for following formulas (i) or (ii),
(in formula, p and q are respectively 0 or 1~150 integer, and the average value of p and q sums is 2~200.R is 0~6
Integer, t are 2 or 3.)
(in formula, u is 1~200 integer, and v is 1~50 integer, and t is same as described above.).]
Here, as R1、R2, preferably hydrogen atom, carbon number 1~12, particularly preferred 1~10 alkyl, as alkyl,
Specifically, can enumerate：The alkyl such as methyl, ethyl, propyl group, butyl, hexyl, cyclohexyl, octyl group；The aryl such as phenyl, tolyl；
The substitution 1 that aralkyl such as benzyl, phenylethyl etc. and the halogen atom such as part or all of hydrogen atom fluorine by these groups substitute
Valency alkyl etc..
Here, the Rf in above-mentioned formula (4)1For divalent holo-fluorine polyester, the change of preferably following formulas (i) or (ii) expression
Compound.
(in formula, p and q are respectively 1~150 integer, preferably 10~150 integer, and the average value of p and q sums is
2~200, preferably 20~160.In addition, r is 0~6 integer, preferably 0~4 integer, t is 2 or 3.)
(in formula, u be 1~200 integer, preferably 20~160 integer, v be 1~50 integer, preferably 5~40
Integer, t is same as described above.)
As Rf1The preferable example of base, example 3 groups described as follows can be enumerated.Wherein, the knot of particularly preferred first formula
The divalent group of structure.
(in formula, p1 and q1 are respectively 1~150 integer, p1+q1 (average)=2~200.L is 2~6 integer.)
(in formula, p2 and q2 are respectively 1~150 integer, p2+q2 (average)=2~200.L is 2~6 integer.)
(in formula, u1 is 1~200 integer, and v1 is 1~50 integer.)
As the preferable example of (A) composition, the compound that following formulas (5) represent can be enumerated.
[in formula, X1Expression-CH2-、-CH2O-、-CH2OCH2- or-Y-NR11- CO- (Y represents group same as described above,
R11For hydrogen atom, methyl, phenyl or pi-allyl), X1' it is-CH2-、-OCH2-、-CH2OCH2- or-CO-NR12-Y’-(R12Represent
With above-mentioned R11Identical group, Y ' represent group same as described above) group that represents, g independently be 0 or 1, L be 2~6
Integer, p3 and q3 are respectively 1~150 integer, p3+q3 (average)=2~200.]
The concrete example of the chain multi-fluorinated compounds represented as formula (4), the material of following formula expression can be enumerated.
(in formula, p ' and q ' are respectively 1~150 integer, represent the number for meeting p '+q '=6~200.)
(in formula, p ' ' and q ' ' are respectively 1~150 integer, represent the number for meeting p ' '+q ' '=2~200.)
Contained alkene base unit weight is preferably 0.005~0.050 to rub in the chain multi-fluorinated compounds that above-mentioned formula (4) represents
That/100g, more preferably 0.007~0.040 mole/100g.Contained alkene base unit weight mistake in chain perfluoroalkyl polyether compound
When few, the physical strength of solidfied material reduces sometimes, it is impossible to obtains solidfied material, when alkene base unit weight is excessive, oil leak occurs sometimes.
It should be noted that the viscosity (23 DEG C) of the chain multi-fluorinated compounds of above-mentioned formula (4) is 100~100,
000mm2/ s, more preferably 500~50,000mm2/ s, further preferred 1,000~20,000mm2In the range of/s, sealing, pouring
When this composition is used in filling, coating, impregnation etc., even solidfied material also has appropriate physical characteristic, therefore preferably.Formula
(4) chain multi-fluorinated compounds select the material of most suitable viscosity according to purposes.Alternatively, it is also possible to by the polymerization of low viscosity
Thing and highly viscous polymer are mixed, and are adjusted to desired viscosity and are used.In addition, in the present invention it is possible to utilize
Ostwald's relative viscometer determines viscosity.
Moreover, in the present invention, it is desired in order to be adjusted to the chain multi-fluorinated compounds of above-mentioned formula (4) according to purpose
Weight average molecular weight, chain per-fluoro polyether compound as described above and intramolecular can also be made to contain 2 silyl hydrides in advance
The organo-silicon compound of base (Si-H yls) usual way and under the conditions of carry out hydrosilylation reactions, chain length is extended
Product uses as (A) composition.
These chain multi-fluorinated compounds can be used alone, or two or more is applied in combination.
[(B) composition]
(B) composition is with the polyfluoro mono-alkenyl with perfluoropolyether structures in 1 alkenyl and main chain in 1 molecule
Compound.
As (B) composition, the polyfluoro mono-alkenyl compound of particularly preferred following formula (6) expression.
Rf3-(X’)g- CH=CH2 (6)
[in formula (6), X ' is-CH2-、-OCH2-、-CH2OCH2- or-CO-NR2- Y '-(wherein, Y ' is-CH2-、-
CH2CH2CH2Si(CH3)2-、-CH2CH2CH2Si(CH3) (CH=CH2)-or following structural formula (Z ')
（O-, m- or p- dimetylsilyl phenylene）The group of expression, R2For hydrogen atom or unsubstituted or substituted
1 valency alkyl, the R with above-mentioned formula (4) can be illustrated2The same group of the group of middle illustration.).G is 0 or 1.Rf3It is that containing for 1 valency is complete
The group of perfluoroalkyl polyether structure, the structure of following formula expression is preferably comprised,
Cs’F2S’+1(ChF2hO)iCt’F2t’-
(in formula, s ' be 0~8 integer, h be 1~6 integer, i be 0~200 integer, preferably 10~100 integer,
More preferably 20~50 integer, t ' are 1 or 2.).]
In above-mentioned formula (6), as Rf3, following group can be illustrated.
(in formula, s is 1~8 integer, and i1 is 0~200 integer, and i2+i3 is 0~200 integer.)
The concrete example of the polyfluoro mono-alkenyl compound represented as above-mentioned formula (6), can enumerate example chemical combination described as follows
Thing.
(in above-mentioned formula, i ' is 0~200 integer.)
Contained alkene base unit weight is preferably 0.005~0.050 mole/100g in above-mentioned polyfluoro mono-alkenyl compound, is entered
One step is preferably 0.010~0.040 mole/100g.When contained alkene base unit weight is very few in polyfluoro mono-alkenyl compound, sometimes
The increase of concomitant polymerization thing viscosity, its result causes the reduction of operability, when alkene base unit weight is excessive, sometimes to the dissolving of composition
Property reduce, the physical characteristic of bad order and solidfied material it is uneven.
It should be noted that from the aspect of in order to obtain the physical characteristic of uniform solidfied material, ensure operability, preferably
(B) viscosity (23 DEG C) of the polyfluoro mono-alkenyl compound of composition is in 50~5000mm2/ s, more preferably 100~2000mm2/ s, enter
One step preferably 200~1000mm2In the range of/s.Most suitable viscosity can be selected according to purposes in the range of viscosities.
In the curability perfluoroalkyl polyether system gel combination of the present invention, the polyfluoro mono-alkenyl compound of (B) composition is matched somebody with somebody
Resultant is 1~300 mass parts relative to the mass parts of fluoropolymer 100 of the straight-chain of above-mentioned (A) composition, preferably 1~150
Mass parts.When it is less than 1 mass parts, the crosslink density rise after solidifying sometimes, it is difficult to as gel solidification thing, turn into rubber
Shape solidfied material, when it is more than 300 mass parts, the crosslink density step-down after solidifying sometimes, turn into liquid object, it is difficult to as gel
Solidfied material.It should be noted that (B) composition can be used singly or in combination of two or more.
[(C) composition]
(C) composition be 1 molecule in more than 1, preferably 1~10 fluorine-containing organic group and with more than 2, it is excellent
Select the fluorine-containing organic hydride silica of 3~50 hydrogen atoms for being bonded directly to silicon atom (i.e. the hydrosilyl that Si-H is represented)
Alkane.(C) composition of the present invention extends agent as the crosslinking agent and/or chain length of above-mentioned (A) composition and (B) composition and worked, in addition,
From with the viewpoint such as the uniformity after the intermiscibility of (A) composition and (B) composition, dispersiveness, solidification, as fluorine-containing organic group
, with 1 valency perfluoroalkyl, 1 valency perfluor epoxide alkyl, divalent perfluorinated alkylidene or the divalent perfluor of more than 1 in preferably 1 molecule
The group of the fluoro-containing groups such as epoxide alkylidene.
As 1 valency or the fluorine-containing organic group of divalent, can enumerate such as the group that following formulas represent.
CjF2j+1-
-CjF2j-
(in formula, j be 1~20 integer, preferably 2~10 integer.)
(in formula, k is 1~200 integer, and preferably 1~100 integer, l is 1~3 integer.)
(in formula, w and x are respectively more than 1 integer, and preferably 1~100 integer, w+x average value is 2~200, excellent
Elect 2~100 as.)
-(CF2O)y-(CF2CF2O)z-CF2-
(wherein, y and z is respectively 1~50 integer, preferably 1~40 integer.)
In addition, these perfluoroalkyls, perfluor epoxide alkyl, perfluorinated alkylidene or perfluorooxyalkylene and silicon atom are preferred
Connected using divalent concatenating group, as the divalent concatenating group, can be alkylidene, arlydene and combinations thereof or make ehter bond, oxygen
The group that atom, amido link, carbonyl bond, ester bond, two organic silicylenes etc. are present in these groups, can be enumerated for example：
-CH2CH2-、
-CH2CH2CH2-、
-CH2CH2CH2OCH2-、
-CH2CH2CH2-NH-CO-、
-CH2CH2CH2-N(Ph)-CO-、
-CH2CH2CH2-N(CH3)-CO-、
-CH2CH2CH2-N(CH2CH3)-CO-、
-CH2CH2-Si(CH3)2-Ph’-N(CH3)-CO-、
-CH2CH2CH2-Si(CH3)2-Ph’-N(CH3)-CO-、
-CH2CH2CH2-O-CO-
(wherein, Ph be phenyl, Ph ' be phenylene.)
Divalent concatenating group Deng carbon number 2~12 etc..
In addition, as should (C) composition fluorine-containing Organhydridosiloxaneresins in the fluorine-containing organic group of above-mentioned 1 valency or divalent and
The 1 valency substituent for being bonded to silicon atom in addition to the hydrogen atom for being bonded to silicon atom, can be enumerated for example：Methyl, ethyl, third
The alkyl such as base, butyl, hexyl, cyclohexyl, octyl group, decyl；The alkenyls such as vinyl, pi-allyl；Phenyl, tolyl, naphthyl etc.
Aryl；The part or all of hydrogen atom of the aralkyl such as benzyl, phenylethyl and these groups is by the substituted base such as chlorine atom, cyano group
Group, the carbon number 1~20 such as chloromethyl, chloropropyl, cyano ethyl, preferably 1~12 unsubstituted or substituted 1 valency hydrocarbon
Base.
Can be ring-type, chain, three-dimensional netted and combinations thereof as the fluorine-containing Organhydridosiloxaneresins of (C) composition
It is any.The silicon atom number of the fluorine-containing Organhydridosiloxaneresins is not particularly limited, and usually 2~60, preferably 3~30 is left
It is right.
As this (C) composition with 1 valency or the fluorine-containing organic group of divalent and silicon atom bonding hydrogen atom, example can be enumerated
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.
Contained Si-H base unit weights are preferably 0.0005~0.0100 to rub in the fluorine-containing Organhydridosiloxaneresins of above-mentioned (C) composition
That/g, more preferably 0.0010~0.0050 mole/g.Contained Si-H base unit weights are very few in fluorine-containing Organhydridosiloxaneresins
When, occasionally resulting in the physical characteristic of solidfied material reduces, and when Si-H base unit weights are excessive, is bubbled sometimes in solidification, or obtained solidification
Rheological parameters' change with time occurs for the physical characteristic of thing.
These fluorine-containing Organhydridosiloxaneresins can be used alone or two or more is applied in combination.
The use level of above-mentioned (C) composition is to carry out hydrosilylation reactions with the alkenyl in (A) composition and (B) composition
Effective dose, it is to make to be commonly angled relative to 1 mole of the alkenyls such as vinyl contained in (A) composition and (B) composition, pi-allyl, cycloalkenyl group
(C) hydrosilyl of composition, i.e. Si-H bases turn into preferably 0.5~3.0 mole, more preferably 0.8~2.0 mole of amount.Hydrogen
When change silicyl (≡ Si-H) is very few, crosslinking degree is insufficient sometimes, as a result can not obtain solidfied material, or even if consolidated
Change, the rheological parameters' change with time of the physical characteristic of solidfied material also becomes big, in addition, when its is excessive, is bubbled sometimes in solidification, or solidfied material
The rheological parameters' change with time of physical characteristic become big.
[(D) composition]
(D) composition of the present invention is photoactivation type hydrosilylation reaction catalyst.Photoactivation type hydrosilylation reactions
Catalyst is to be irradiated by light, particularly 300~400nm ultraviolet to be activated, promote in (A) composition and (B) composition
The catalyst of the addition reaction of hydrosilyl in alkenyl and (C) composition.The photoactivation type hydrosilylation reactions are urged
Agent is mainly equivalent to platinum group metal catalystses or nickel system metallic catalyst, as platinum group metal catalystses, have platinum group, palladium system,
The metal complex compounds of rhodium system, as nickel system metallic catalyst, there is the golden group complex compound of nickel system, iron system, cobalt system.
Wherein, platinum series metal complex compound becomes more readily available and shows good catalyst activity, therefore preferably fully makes
With.
As the platinum series metal complex compound of photoactivation type, such as there is (η5- cyclopentadienyl group) three (σ-alkyl) platinum
Complex compounds and beta-diketon platinum complex compound etc., specifically, it can enumerate：(methyl cyclopentadienyl) trimethyl platinum
(IV), (cyclopentadienyl group) trimethyl platinum (IV), (1,2,3,4,5- pentamethylcyclopentadienes base) trimethyl platinum (IV), (ring penta
Dialkylene) dimethyl ethyl platinum (IV), (cyclopentadienyl group) dimethylacetamide base platinum (IV), (trimethyl silyl ring penta 2
Alkenyl) trimethyl platinum (IV), (methoxycarbonyl cyclopentadienyl group) trimethyl platinum (IV), (dimethylphenylsilyl ring penta
Dialkylene) front three cyclopentadienyl group platinum (IV), trimethyl (acetylacetone,2,4-pentanedione) close platinum (IV), trimethyl (3,5- heptanedionatos)
Platinum (IV), trimethyl (methyl-acetoacetic ester) platinum (IV), double (ketone acid of 2,4- pentanes two) platinum (II), double (2,4- hexanediones
Acid) platinum (II), double (ketone acid of 2,4- heptane two) platinum (II), double (ketone acid of 3,5- heptane two) platinum (II), double (1- phenyl -1,3- fourths
The ketone acid of alkane two) platinum (II), double (1,3- diphenyl -1,3- pentanediones acid) platinum (II), double (hexafluoroacetylacetones) close platinum (II)
Deng.
When using these catalyst, when it is solid catalyst, it can also be used with solid-like, it is more equal in order to obtain
Even solidfied material, the multi-fluorinated compounds of the material and (A) composition and/or (B) composition that preferably make to be dissolved in suitable solvent mix
And use.
(D) usage amount of composition is scaled 0.1~500ppm, preferably relative to the mass parts of (A) composition 100 with metallic atom
For 1~100ppm.When usage amount is very few, it is impossible to sufficient photo-curable is obtained, on the other hand, when its is excessive, it is possible to right
The heat resistance of solidfied material produces harmful effect.It should be noted that (D) composition can be used alone, can also be applied in combination
Two or more.
[(E) composition]
It can further coordinate being selected from as (E) composition in the photo-curable perfluoroalkyl polyether system gel combination of the present invention
At least one kind of no functionality per-fluoro polyether compound in the compound that following formula (1)~(3) represent.
A-O-(CF2CF2CF2O)a-A (1)
[in formula (1), A is formula：CbF2b+1The group that-(b is 1~3 integer) represents, a is 1~500 integer, especially
It is 10~300 integer.]
A-O-(CF2O)c-(CF2CF2O)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.)
Optionally coordinate the per-fluoro polyether compound as (E) composition, by coordinating the composition, other physical property can not be damaged
Deng and assign resistance to chemical reagents, solvent resistance, low-temperature characteristics excellent gel solidification thing.Particularly it is being matched with curability perfluoroalkyl polyether
In the case of being gel combination, glass transition temperature etc. can be reduced, obtains excellent low-temperature characteristics.
(E) use level of composition is preferably 0~150 matter relative to the mass parts of total amount 100 of (A) composition and (B) composition
Measure part, more preferably 0.1~100 mass parts, particularly preferred 0.5~50 mass parts.When it is more than 150 mass parts, sometimes from solid
In the gelling material of change through when spill.It should be noted that (E) composition can be used alone, 2 can also be applied in combination
More than kind.
[other compositions]
In the present compositions, in order to improve its practicality, in addition to above-mentioned (A)~(E) compositions, can also add
Its own known various compounding ingredient.As such composition, the reaction controlling agent of such as hydrosilylation reactions can be enumerated.Make
For the example of reaction controlling agent, can enumerate for example：1- acetenyl -1- hydroxycyclohexans, 3- methyl isophthalic acids-butine -3- alcohol, 3,5- bis-
The acetylene alcohols such as methyl isophthalic acid-hexin -3- alcohol, 3- Methyl-1-pentene -3- alcohol, phenylbutynol and 3- methyl-pirylene,
Fluorine-containing acetylene alcoholic compound that the acetylides such as 3,5- dimethyl -3- hexene -1- alkynes or following structural formula represent,
Or Polymethyl methacrylate ring type compound, organic phosphorus compound etc., it is possible thereby to suitably keep solidification
Reactivity and storage stability.The control ability of these reaction controlling agent is different because of its chemical constitution, accordingly, with respect to addition
Amount, should be adjusted to most suitable amount respectively, it is however generally that, when the addition of controlling agent is very few, it is impossible to obtain long-term guarantor at room temperature
Sustainability, when its is excessive, curability is blunt sometimes, it is impossible to obtains sufficient curability.
Furthermore it is possible to the various compounding ingredients such as inanimate matter filler are added as needed on as other any conditions.Do not damaging
Do harm to the scope of the purpose of the present invention and do not damage in the limit of the characteristic of composition and the physical property of solidfied material, these additives are matched somebody with somebody
Resultant is arbitrary.
As inanimate matter filler, can enumerate for example：Aerosil, wet silicon dioxide etc. utilize the ratio of BET method
Surface area is 50~1,000m2/ g or so SiO 2 powder and quartz powder, vitreous silica powder, diatomite, calcium carbonate
Deng inorganic pigment, titanium oxide, iron oxide, the charcoal such as the property strengthened or the accurate property strengthened filler, titanium oxide, iron oxide, carbon black, cobalt aluminate
The heat-resisting enhancer such as black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, manganese carbonate, aluminum oxide, boron nitride, carborundum, metal
Conductivity-imparting agents such as the heat conductivity such as powder imparting agent, carbon black, silver powder, electroconductive zinc oxide etc..
[photo-curable perfluoroalkyl polyether system gel combination]
The manufacture method of curability perfluoroalkyl polyether system gel combination of the present invention is not particularly limited, can be by will be above-mentioned
Composition is kneaded and manufactured, for example, can by by above-mentioned (A)~(D) composition and other any conditions using planetary-type mixer,
The mixing arrangements such as ROSS mixers, HOBART mixers, equably mixed using kneading devices such as three rollers to manufacture as needed.
Alternatively, it is also possible to as such as (A), (B), (C), (E) composition with (A), (B), (D), (E) composition, two liquid compositions are made,
Mixed when in use.
In terms of operability and discharge, molding processibility is ensured, photo-curable perfluoroalkyl polyether system gel preferably of the invention
The viscosity (23 DEG C) of composition 50~100,000mPas, more preferably 100~70,000mPas, it is further preferred 300~
In the range of 50,000mPas.In order to be adjusted to such viscosity, preferably the molecular weight of the polymer used is chosen to be most
Suitable molecular weight, or the polymer of low viscosity and the blending of highly viscous polymer are used, or the PFPE of adjustment (E) composition
The use level of compound.
[process for photocuring of photo-curable perfluoroalkyl polyether system gel combination]
Manufactured photo-curable perfluoroalkyl polyether system gel combination can be cured by light irradiation.During solidification, preferably
Maximum peak wavelength in the luminescent spectrum of the light of irradiation is located at 300~400nm region, and positioned at the wavelength zone less than 300nm
The radiancy of each wavelength in domain is radiometric less than the 5% of above-mentioned maximum peak wavelength, preferably less than 1%, more preferably less than 0.1%,
In other words, it is more preferred closer to 0%.Irradiation, which is located at, to be less than 300nm wavelength region, there is radiancy to be more than above-mentioned maximum
During the light of radiometric 5% big wavelength of spike length, it is possible to cause the decomposition of polymer ends base, or the one of catalyst
Decomposed etc., it is impossible to obtain sufficient solidfied material.
The active ray species of photo-curable perfluoroalkyl polyether system gel combination solidification for making the present invention does not limit especially
Determine, preferably ultraviolet.In terms of good curability is obtained, preferably ultraviolet irradiation amount (illumination) is calculated as with accumulative light quantity
100mJ/cm2~100,000mJ/cm2, preferably 1,000mJ/cm2~10,000mJ/cm2, more preferably 5,000~10,
000mJ/cm2.In the case that ultraviolet irradiation amount (illumination) is less than above range, by the photoactivation type hydrosilanes in composition
When changing catalysts activation, it is possible to sufficient energy can not be obtained, it is impossible to sufficient solidfied material is obtained, it is on the other hand, purple
Outside line exposure (illumination) be it is more than above range in the case of, the energy of the above is needed to composition irradiation, it is possible to cause
Polymer ends base decomposes or partial catalyst inactivates etc., it is impossible to obtains sufficient solidfied material.
Ultraviolet irradiation can be the light with multiple luminescent spectrums, or have the light of single luminescent spectrum.
In addition, single luminescent spectrum can have the spectrum of wealthy width in 300nm~400nm region.With single luminescent spectrum
Light be that there is the light of peak (i.e. maximum peak wavelength) in 300nm~400nm, preferably 350nm~380nm scope.As irradiation
The light source of such light, it is ultraviolet that ultraviolet LED (ultraviolet LED) and luminescence-utraviolet semiconductor laser etc. can be enumerated
Line luminescent diode component light source.
As the light source of light of the irradiation with multiple luminescent spectrums, can enumerate：Metal halide lamp, xenon lamp, carbon arc lamp, change
Learn gas laser, the organic pigment solution such as the nitrogen such as the lamps such as lamp, sodium vapor lamp, Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp
Liquid laser, Solid State Laser containing rare earth ion etc. in inorganic single crystals.
Above-mentioned light has a case that peak or in the ripple less than 300nm in luminescent spectrum in the wavelength region less than 300nm
Radiometric 5% radiometric wavelength with the maximum peak wavelength being more than in above-mentioned luminescent spectrum be present in long region
In (such as the situation of luminescent spectrum by wide area wavelength region for wealthy width), it is located at using optical filter removing and is less than 300nm
Wavelength region wavelength light.Thus, the radiancy for making to be located at each wavelength of the wavelength region less than 300nm is maximum spike
Long radiometric less than 5%, preferably less than 1%, more preferably less than 0.1%, further preferred 0%.In addition, in luminescent spectrum
In the case that 300nm~400nm wavelength region has multiple peaks, the spike length for the absorbance for wherein showing maximum is set to most
Big spike length.As long as optical filter stops the wavelength less than 300nm, just without particular limitation using known optically filtering
Device.It can use such as 365nm bandpass filters.It should be noted that the illumination of ultraviolet, spatial distribution can be used
Spectroradiometer, such as USR-45D (USHIO motors) are measured.
As light irradiation device, it is not particularly limited, such as point type irradiation unit, face formula irradiation unit, line can be used
The irradiation units such as formula irradiation unit, conveyor type irradiation unit.
When making the photo-curable perfluoroalkyl polyether system gel combination solidification of the present invention, the light irradiation time is, for example, 1~300
Second, preferably 10~200 seconds, more preferably 30~150 seconds, after irradiation 1~60 minute, particularly coagulated after 5~30 minutes
Gel.Gelation refers to that photo-curable perfluoroalkyl polyether system's gel combination part carries out curing reaction in the present invention, and composition loses
The state of mobility.
[photo-curable perfluoroalkyl polyether system gel solidification thing]
Composition of the invention using above-mentioned (A)~(D) composition as main component can be formed resistance to by above-mentioned photocuring
Medicine and excellent solvent resistance and the low gel solidification thing of penetrability.It should be noted that in this manual, gel is solid
Compound refers to the state for partly having three-dimensional structure, deformation and mobility being shown according to stress, specifically, refers to ASTM
The gel solidification thing that needle penetration in D-1403 (1/4 cone) is 1~200 or the gel that hardness is less than 0 in JIS hardometers
Solidfied material.Being formed for gel solidification thing can be by injecting the present composition or in appropriate matrix in appropriate container
After upper carry out coating, carry out light irradiation and the existing known method such as its solidification is easily carried out.
The photo-curable perfluoroalkyl polyether system gel solidification thing of the present invention can be used as automobile using, chemical plant to use, ink-jet printer
Used with, semiconductor production line, analysis/Physicochemical equipment is used, Medical Devices are used, airborne vehicle is used, organic EL panel is used, fuel cell
Preferably used with component etc. is waited.
When being described in further detail, solidfied material of the invention and gel product containing solidfied material can be used as automotive part,
Chemical plant sets spare unit, medical treatment with part, semiconductor with part, ink-jet printer with production line with part, analysis/Physicochemical
If spare unit, electric and electronic dampproof coating material, sensor embedding agent, organic EL panel encapsulant, fuel are electric
Pond is preferably used with encapsulant etc..
Especially as electric and electronic dampproof coating material, sensor with embedding agent use in the case of, can be to gas
Pressure sensor, hydrostatic sensor, temperature sensor, humidity sensor, turn-sensitive device, G sensor, Time Pick-off Units, air
Flowmeter, electronic circuit, semiconductor subassembly, various control units etc. preferably use.
In addition, in the case of using the solidfied material of the composition of the present invention as uses such as embedding agent, coating materials, in order to
The adaptation or cementability with matrix material are improved, and the priming paint known to is useful.Priming paint can be utilized to prevent from matrix
Material interface immerses medicine and solvent, can improve part overall acid resistance, resistance to chemical reagents and solvent resistance.
As priming paint it is preferable to use the silane system priming paint based on silane coupler, with organic poly- silicon of hydrogen diene
Oxygen alkane is the priming paint of main body, using polyurethane resin as the priming paint of main component, using epoxy resin as priming paint of main component etc..
Embodiment
Hereinafter, embodiment and comparative example are shown, to the present invention specifically illustrate, but the present invention be not restricted to it is following
Embodiment.It should be noted that in following embodiments, part represents mass parts.
[embodiment 1]
Polymer (the viscosity 5,800mm that following formula (7) represents is added in planetary-type mixer2/ s, ethene base unit weight
0.013 mole/100g) 55 parts, polymer (the viscosity 600mm that represents of following formula (8)2/ s, 0.023 mole of ethene base unit weight/
100g) 20 parts, 25 parts of Demnum S-65 (perfluoro polyether oil, Daikin Industries (strain) trade name processed), are mixed to uniform.Wherein according to
Double (trifluoromethyl) benzole solns (the mass % of platinum concentration 6.0) of 1,3- of secondary addition (methyl cyclopentadienyl) trimethyl platinum (IV)
0.04 part, following formula (9) represent 0.002 part of fluorine-containing acetylene alcohol, following formula (10) represent fluorine-containing Organhydridosiloxaneresins
18.09 parts (0.00062 mole/g of Si-H base unit weights), as mixing in a manner of uniform, to prepare solidification compound.
(m+n average value (weight average degree of polymerization) ≒ 90)
[embodiment 2]
In above-described embodiment 1, substitute 55 parts of the polymer of above-mentioned formula (7) expression, use following formula (11) to represent poly-
Compound (viscosity 5,800mm20.012 mole/s, ethene base unit weight/100g) 55 parts, in addition, similarly operate, prepare solidification
Property composition.
(m+n average value (weight average degree of polymerization) ≒ 90)
[embodiment 3]
In above-described embodiment 1, substitute 0.002 part of the fluorine-containing acetylene alcohol of above-mentioned formula (9) expression, be changed to acetenyl hexamethylene
0.006 part of the toluene solution (5 mass %) of alcohol, in addition, similarly operates, prepares solidification compound.
[embodiment 4]
It is in above-described embodiment 1, double (trifluoromethyl) benzene of the 1 of (methyl cyclopentadienyl) trimethyl platinum (IV), 3- are molten
0.04 part of liquid (the mass % of platinum concentration 6.0) is changed to the acetic acid 2- (2- Butoxyethoxies) of double (2,4- heptadione acid) platinum (II)
0.48 part of ethyl ester solution (the mass % of platinum concentration 0.5), in addition, similarly operates, prepares solidification compound.
[embodiment 5]
In above-described embodiment 1, by 18.09 parts of (Si-H base unit weights of fluorine-containing Organhydridosiloxaneresins of above-mentioned formula (10) expression
0.00062 mole/g) be changed to following formula (12) expression 2.24 parts of fluorine-containing Organhydridosiloxaneresins (Si-H base unit weights 0.0050 are rubbed
That/g), in addition, similarly operate, prepare solidification compound.
[reference example]
In above-described embodiment 1, substitute photoactivation type hydrosilylation reaction catalyst：Methyl cyclopentadienyl) front three
Double 0.04 part of (trifluoromethyl) benzole solns (the mass % of platinum concentration 6.0) of 1,3- of base platinum (IV), are changed to non-photoactivation type silane
Alkylation reaction catalyst：The ethanol solution (the mass % of platinum concentration 3.0) 0.08 of platinum-divinyl tetramethyl disiloxane complex compound
Part, in addition, similarly operate, prepare solidification compound.
[keeping quality evaluation]
The solidification compound obtained in above-described embodiment, reference example is placed 2 weeks at shading, 23 DEG C, glued with initial stage
Degree is compared.The results are shown in table 1.In addition, the measure of viscosity uses TV-10U type rotary viscosities according to JIS K7117-1
(Rod No.H6,23 DEG C, 50rpm) is counted to carry out.
【Table 1】
(it should be noted that " ← " in table is represented with recording the numerical value phase described in the left adjacent column on the column for being somebody's turn to do " ← "
Together.)
Learnt by the result of table 1：, can at shading, 23 DEG C by using photoactivation type hydrosilylation reaction catalyst
Obtain good keeping quality.
[photo-curable evaluation]
Embodiment 1~5
The Photocurable composition obtained by above-described embodiment 1~5 is respectively put into 30 × 14mm of φ glass plate, made
Light irradiation is carried out with the SP-V types ultraviolet radiation device (USHIO systems) for being provided with uniform irradiation optical unit.Now, utilize
365nm bandpass filters (USHIO motors society system) remove the light for being located at the wavelength region less than 300nm, with the 365nm of dominant wavelength
The accumulative light quantity of light be 9,000mJ/cm2Mode carry out 90 seconds irradiate.Shading immediately after light irradiation, stands at 23 DEG C,
After determining to the gelation time for the mobility for losing composition, and measure light irradiation after 2 hours, after 4 hours, after 24 hours
Needle penetration.Table 2 shows its result.In addition, the needle penetration of solidfied material is measured according to ASTM D-1403, with 1/4 cone.
Comparative example 1~5
In above-described embodiment 1~5,365nm bandpass filters (USHIO motors society is not used when ultraviolet irradiates
System), in addition, carry out same operation.The results are shown in table 2.
【Table 2】
Learnt by the result of table 2：Filtered by photo-curable perfluoroalkyl polyether system's gel combination to the present invention with 365nm band logicals
Ripple device blocks the light positioned at the wavelength domain less than 300nm and carries out light irradiation, shows good curability.In addition, do not make
In comparative example with 365nm bandpass filters, the most surface whole xanthochromia of photoirradiated surface, uncured portion be present, it is impossible to filled
The solidfied material divided.
Claims (9)
1. a kind of manufacture method of gel solidification thing, this method include：To photo-curable perfluoroalkyl polyether system gel combination irradiation light
Solidify said composition,
Wherein, the light has maximum peak wavelength in 300nm~400nm of luminescent spectrum region, and the light is less than 300nm's
The radiancy of each wavelength of wavelength region is radiometric less than the 5% of the maximum peak wavelength,
The photo-curable perfluoroalkyl polyether system gel combination, it contains：
(A) with the mass parts of chain multi-fluorinated compounds 100 with perfluoropolyether structures in 2 alkenyls and main chain in 1 molecule；
(B) with the polyfluoro mono-alkenyl compound phase pair with perfluoropolyether structures in 1 alkenyl and main chain in 1 molecule
In the mass parts of (A) composition 100 be 1~300 mass parts；
(C) there are the fluorine-containing Organhydridosiloxaneresins of more than 2 hydrogen atoms for being bonded directly to silicon atom in 1 molecule
Make the amount of Si-H bases relative to 1 mole of amount for reaching 0.5~3.0 mole of alkenyl of (A) composition and (B) composition；And
(D) photoactivation type hydrosilylation reaction catalyst
Relative to the mass parts of (A) composition 100,0.1~500ppm is scaled with metallic atom.
2. the manufacture method of gel solidification thing as claimed in claim 1, wherein, as (E) composition, the photo-curable fluorine gathers
Also contain at least one kind of PFPE chemical combination in the compound represented selected from following formulas (1)~(3) in ether system gel combination
Thing,
A-O-(CF2CF2CF2O)a-A (1)
In formula (1), A is formula：CbF2b+1- the group represented, wherein, b is 1~3 integer, and a is 1~500 integer；
A-O-(CF2O)c-(CF2CF2O)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 manufacture method of gel solidification thing as claimed in claim 1 or 2, wherein, (A) composition represents for following formulas (4)
The chain multi-fluorinated compounds with side chain,
CH2=CH- (X)g-Rf1-(X’)g- CH=CH2 (4)
In formula, X is-CH2-、-CH2O-、-CH2OCH2- or-Y-NR1- CO-,
Wherein, Y is-CH2-、-Si(CH3)2CH2CH2CH2-、-Si(CH3) (CH=CH2)CH2CH2CH2- ,-Si (CH=CH2)2CH2CH2CH2- or following structural formula (Z) represent o-, m- or p- silicyl phenylene, R1For hydrogen atom or unsubstituted or take
The 1 valency alkyl in generation,
In formula (Z), R3、R4It is separately-CH3Or-CH=CH2,
X ' is-CH2-、-OCH2-、-CH2OCH2- or-CO-NR2- Y '-,
Wherein, Y ' is-CH2-、-CH2CH2CH2Si(CH3)2-、-CH2CH2CH2Si(CH3) (CH=CH2)-、-CH2CH2CH2Si(CH
=CH2)2- or following structural formula (Z ') represent o-, m- or p- silicyl phenylene, R2For with above-mentioned R1Identical group,
In formula (Z '), R3’、R4’It is separately-CH3Or-CH=CH2,
G independently is 0 or 1,
Rf1The divalent holo-fluorine polyester represented for following formulas (i) or (ii),
In formula, p and q are respectively 0 or 1~150 integer, and the average value of p and q sums is the integer that 2~200, r is 0~6, t
For 2 or 3,
In formula, u is 1~200 integer, and v is 1~50 integer, and t is same as described above.
4. the manufacture method of gel solidification thing as claimed in claim 1 or 2, wherein, the fluorine-containing organic hydride silica of (C) composition
Alkane has 1 valency perfluoroalkyl, 1 valency perfluor epoxide alkyl, divalent perfluorinated alkylidene or the divalent perfluor oxygen of more than 1 in 1 molecule
Base alkylidene.
5. the manufacture method of gel solidification thing as claimed in claim 3, wherein, the fluorine-containing Organhydridosiloxaneresins of (C) composition
There is 1 valency perfluoroalkyl, 1 valency perfluor epoxide alkyl, divalent perfluorinated alkylidene or the divalent perfluor epoxide of more than 1 in 1 molecule
Alkylidene.
6. the manufacture method of gel solidification thing as claimed in claim 1 or 2, wherein, the photoactivation type hydrosilanes of (D) composition
Change catalysts are (η5- cyclopentadienyl group) three (σ-alkyl) platinum (IV).
7. the manufacture method of gel solidification thing as claimed in claim 3, wherein, the photoactivation type hydrosilylation of (D) composition
Catalysts are (η5- cyclopentadienyl group) three (σ-alkyl) platinum (IV).
8. the manufacture method of gel solidification thing as claimed in claim 1 or 2, wherein, the photoactivation type hydrosilanes of (D) composition
Change catalysts are beta-diketon platinum (II) complex compound.
9. the manufacture method of gel solidification thing as claimed in claim 3, wherein, the photoactivation type hydrosilylation of (D) composition
Catalysts are beta-diketon platinum (II) complex compound.
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| JP2013086423A JP6020327B2 (en) | 2013-04-17 | 2013-04-17 | Photo-curable fluoropolyether gel composition, curing method thereof, gel cured product, and gel product using the cured product |
| JP2013-086423 | 2013-04-17 |
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| JP6130288B2 (en) * | 2013-11-22 | 2017-05-17 | 信越化学工業株式会社 | Allyl group-modified fluorooxyalkylene group-containing polymer and production method thereof |
| JP6565723B2 (en) * | 2015-02-04 | 2019-08-28 | 信越化学工業株式会社 | Photocurable fluoropolyether rubber composition, cured product thereof, and curing method thereof |
| JP6344256B2 (en) * | 2015-02-18 | 2018-06-20 | 信越化学工業株式会社 | Method for bonding photocurable fluoropolyether elastomer composition |
| JP6459845B2 (en) * | 2015-08-18 | 2019-01-30 | 信越化学工業株式会社 | Method for bonding photocurable fluoropolyether elastomer composition |
| JP6390591B2 (en) * | 2015-11-05 | 2018-09-19 | 信越化学工業株式会社 | Organosilicon compound |
| JP6512120B2 (en) * | 2016-01-26 | 2019-05-15 | 信越化学工業株式会社 | Method of bonding fluorine-containing elastomer to substrate |
| JP6614039B2 (en) * | 2016-06-08 | 2019-12-04 | 信越化学工業株式会社 | Fluoropolyether rubber, method for suppressing foaming of hermetic cured fluoropolyether rubber, and rubber adhesive |
| CN108239193B (en) * | 2016-12-26 | 2023-07-04 | 重庆鑫景特种玻璃有限公司 | Perfluoro polyether silane dendritic compound, preparation method thereof and film containing perfluoro polyether silane dendritic compound |
| CN110869418B (en) * | 2017-06-30 | 2022-10-28 | 昭和电工株式会社 | Organic fluorine compound, lubricant, and method for treating magnetic recording medium |
| WO2019035297A1 (en) * | 2017-08-18 | 2019-02-21 | Ａｇｃ株式会社 | Composition and article |
| JP6866810B2 (en) * | 2017-09-14 | 2021-04-28 | 信越化学工業株式会社 | A thixotropic photocurable fluoropolyether-based rubber composition, a cured product thereof, and a curing method thereof. |
| JP7255610B2 (en) * | 2018-12-04 | 2023-04-11 | 信越化学工業株式会社 | METHOD FOR FORMING COATING FILM OF PHOTOCURABLE FLUOROPOLYETHER ELASTOMER COMPOSITION |
| KR20220116444A (en) * | 2019-12-17 | 2022-08-23 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Curable perfluoropolyether adhesive composition, adhesive using cured product thereof, and adhesive tape |
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| JP5246212B2 (en) * | 2010-07-14 | 2013-07-24 | 信越化学工業株式会社 | Curable perfluoropolyether gel composition and gel product using the cured product |
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2013
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2014
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- 2014-04-16 TW TW103113863A patent/TWI609049B/en active
- 2014-04-17 CN CN201410154768.4A patent/CN104109369B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101157758A (en) * | 2006-09-29 | 2008-04-09 | 三星电子株式会社 | Copolymer, composition for forming banks, and method for forming banks using the composition |
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| Publication number | Publication date |
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| KR20140124724A (en) | 2014-10-27 |
| TW201506080A (en) | 2015-02-16 |
| CN104109369A (en) | 2014-10-22 |
| JP2014210831A (en) | 2014-11-13 |
| JP6020327B2 (en) | 2016-11-02 |
| TWI609049B (en) | 2017-12-21 |
| KR102167471B1 (en) | 2020-10-19 |
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