CN1944538B - Silicone composition for release film - Google Patents
Silicone composition for release film Download PDFInfo
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- CN1944538B CN1944538B CN2006101016464A CN200610101646A CN1944538B CN 1944538 B CN1944538 B CN 1944538B CN 2006101016464 A CN2006101016464 A CN 2006101016464A CN 200610101646 A CN200610101646 A CN 200610101646A CN 1944538 B CN1944538 B CN 1944538B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
- Silicon Polymers (AREA)
Abstract
The present invention provided a silicone composition giving releasable layer having improved adhesion to plastic film. The silicone composition for release film making an organopolysiloxane as a main component comprises, based on (A) 100 pts.mass of the organopolysiloxane, (B) 0.3-3 pts.mass of an adduct of a diphenylalkane derivative and an organopolysiloxane derivative having at least one organoxy group and (C) 0.1-2 pts.mass of an isocyanurate, wherein at least one substituent bound to a nitrogen atom has an epoxy or trialkoxysilyl group.
Description
Technical field
The present invention relates to silicone composition for release film, in particular to the silicone composition for release film that can form with the good cured film of the adaptation of various film substrates.
Background technology
Layer generally is set on various substrate surfaces such as laminated paper, plastics film, this base material can be stripped from.As the material that forms this separability layer, use silicone composition, the for example known silicone composition that contains following substances: contain the thiazolinyl organopolysiloxane, gather organohydrogensiloxanes and platinum compound (patent documentation 1,2).
This silicone composition is because solidified nature is good, and working life is also long and be widely used.But also have following problems: according to the difference of base material, the cured film of said composition and the adaptation of base material are also insufficient, can substrates coated be restricted, and perhaps must carry out the pre-treatment of base material etc.
In recent years, as base material, quality is uniform and stable, smoothness is high, and the utilization that can carry out the plastics film of filmization increase, strong day by day for the requirement that improves the adaptation between these plastics and the siloxanes curing tunicle.
Various trials have been carried out in order to improve adaptation.The method that in silicone composition, cooperates organic resinoid or silane coupling agent etc. and the adaptation of the plastics material better than silicone resin is at first arranged.But the separability of the tunicle that this method of usefulness obtains has the tendency of reduction.In addition, also known to having the RSiO of containing in the basic polymerized unit structure that makes silicone resin
3/2Unitary branched structure improves the method for adaptation, but adaptation and insufficient (patent documentation 3～6).In order to reduce the speed dependence of stripping performance, known have and with the method for solvent-borne type silicone composition and no-solvent type silicone composition, but aspect adaptation, do not surmount solvent-borne type silicone composition (with reference to patent documentation 7,8).In addition, also known siloxanes chemistry additive thing, that have good raising adaptation effect (patent documentation 9,10) of ad hoc structure alkyl that contained bonding.Though this adaptation rising agent can obtain good effect for specific end use, but still can not obtain to be used for the promising result of stripping film.The inventor finds in addition; Through in silicone composition for release paper, cooperate have in 1 molecule 2 or more than contain the siloxane compound of the multi-ring alkyl of carbon-to-carbon double bond, can obtain the curing tunicle good (patent documentation 11) with the adaptation of base material.
[patent documentation 1] special public clear 49-26798 communique
[patent documentation 2] spy opens clear 62-86061 communique
[patent documentation 3] spy opens clear 63-251465 communique
[patent documentation 4] special fair 3-19267 communique
[patent documentation 5] spy opens flat 9-78032 communique
[patent documentation 6] spy opens flat 11-193366 communique
[patent documentation 7] spy opens the 2000-169794 communique
[patent documentation 8] spy opens the 2000-177058 communique
[patent documentation 9] spy opens the 2000-265062 communique
[patent documentation 10] spy opens the 2005-2142 communique
[patent documentation 11] spy opens the 2005-015666 communique
Summary of the invention
As stated, up to now, the method that has improved adaptation though proposed not influence the separability of siloxanes tunicle has necessity of further improvement.Therefore the object of the present invention is to provide the silicone composition of the separability layer that a kind of adaptation that forms with plastics film further improved.
The inventor furthers investigate, and the result finds, through silicone composition for release paper is cooperated compound and the isocyanurate derivative with ad hoc structure, can achieve the above object.
That is, the present invention is a kind of silicone composition, and it is characterized in that for being the silicone composition for release film of principal constituent with the organopolysiloxane,
With respect to above-mentioned (A) organopolysiloxane 100 mass parts, contain:
(B) the diphenyl alkane verivate with have affixture 0.3～3 mass parts of the poly organo alkane derivatives of at least one organic oxygen base (オ Le ガ ノ オ キ シ); With
(C) 0.1～2 mass parts isocyanuric acid ester, said isocyanuric acid ester with nitrogen atom bonding substituent at least one have epoxy group(ing) or trialkoxysilyl.
When the curing tunicle that is obtained by the compsn of the invention described above has the peel property of organopolysiloxane tunicle, significantly more excellent than organopolysiloxane tunicle with the adaptation of base material.
Embodiment
In the present invention; (B) diphenyl alkane verivate and affixture (below be called " affixture ") with poly organo alkane derivatives of at least one organic oxygen base; Owing to have polarity different organo-siloxane part and aromatic series part, therefore improved the closing force of silicone composition and film.The preparation method of this affixture does not have special qualification, for example can make through following method: make the silicon compound that on 1 phenyl, has unsaturated substituent diphenyl alkane verivate at least and have reactive hydrogens such as SiH base or sulfydryl carry out addition reaction.As this hydrocarbon substituent that contains two keys, can enumerate for example vinyl (CH
2=CH-).Vinyl and SiH base or SH radical reaction, formation-CH
2-CH
2-Si or-CH
2-CH
2The bond structure that-S representes.
Preferably (B) affixture contain formula (I) or (II) expression compound, also can be their mixture.In the formula A be formula (i) or (ii) the expression group.
At this, R
4Independent mutually, be Wasserstoffatoms or methyl.R
5For being selected from the group in hydroxyl and the methyl, a is 0～2, when a is 2, and R
5Can be hydroxyl and methyl.R
6For carbonatoms 1～10 can substituted monovalence alkyl, R
7For carbonatoms 1～8 can substituted monovalence alkyl.R
6, R
7Can be identical, for example be alkyl such as methyl, ethyl, propyl group, butyl, hexyl, octyl group; Naphthenic base such as cyclohexyl; Thiazolinyls such as vinyl, allyl group, propenyl, crotonyl, hexenyl; Aryl such as phenyl, tolyl; Aralkyl such as benzyl, styroyl; The perhaps group that obtained by replacements such as halogen atom such as chlorine, fluorine, bromines of the part of these group Wasserstoffatomss, for example trifluoro propyl etc.R
6Be preferably methyl.R
7Be preferably alkyl and alkoxyalkyl, most preferable in the industry.B is 1～3 integer, and c is 0 or 1, but b+c is 2 or 3, and x is 1～8 integer.
Formula (ii) in, c is 1 o'clock, this sulfydryl also comprise reacting, for example be bonded in sulfydryl on the diphenyl alkane molecule different with the diphenyl alkane molecule of the sulfhydryl residue bonding that has reacted.
As following formula (I) or compound (II), can enumerate following compound.
(B) affixture also can be 2 kinds or above mixture.With respect to 100 weight parts (A) organopolysiloxane, use level is 0.3～3 weight part, is preferably 0.5～2 weight part.Use level then can not get enough adaptations less than above-mentioned lower value, even and surpass above-mentioned higher limit and cooperate, also can not get and the proportional adaptation of use level improves.
(C) of the present invention isocyanuric acid ester is the material that together is matched with compsn with (B) affixture, is used to improve the adaptation of formed curing tunicle.To improve effect different because of the difference of base material kind or working conditions for its adaptation when only using (B) affixture, but through and with (C) isocyanuric acid ester, can more stably obtain high adaptation.That is, do not limit main points of the present invention, but the mechanism that can obtain high adaptation is inferred as follows.(B) diphenyl alkane of affixture part interacts alkoxysilyl and siloxanes tunicle generation chemically bonded with film substrate.In view of the above, film substrate and siloxane layer are combined closely.(C) in the isocyanuric acid ester, the main and film substrate generation chemically bonded of isocyanuric acid ester group, the main and siloxane layer bonding of epoxy group(ing) or alkoxysilyl, thus make two-layer driving fit.The adaptation that only also can get to a certain degree through epoxy group(ing) and/or alkoxyl group improves effect, but does not have the such effect of isocyanuric acid ester.On the other hand, low only with the isocyanuric acid ester group with the intermiscibility of siloxane layer, and can play catalyzer poison.Like this, through and with having respectively with (B) of film substrate and the interactional different sites of siloxanes tunicle and (C), can improving the adaptation effect greatly, simultaneously, no matter how the kind or the surface treatment state of film all can obtain stable effect.
(C) isocyanurate derivative is the substituted isocyanuric acid ester of hydrogen on the isocyanuric acid nitrogen-atoms, and at least 1 this substituting group contains epoxy group(ing) or trialkoxysilyl.The preferred compound that uses following formula (7) expression.
In the formula, at least one T is the organic group that following formula is (iii) represented,
(R
1O)
3Si-R
2- (iii)
[formula (iii) in, R
1Be the alkyl of carbonatoms 1～8, R
2Alkylidene group for carbonatoms 2～5]
Or the organic group (iv) represented of following formula,
Q-R
3- (iv)
[formula (iv) in, Q is an epoxy group(ing), R
3Alkylidene group for carbonatoms 1～3]
Other T independently is mutually 1～8 alkyl, aryl, aralkyl or simple function property thiazolinyl for carbonatoms.
Carbonatoms is that 1～8 alkyl can be straight chain shape or branched, can enumerate for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, hexyl, octyl group etc.Can enumerate for example phenyl, tolyl, xylyl, benzyl etc. as aryl, aralkyl.Can enumerate the group of the carbonatoms 2～5 of straight chain shape or branched, have the thiazolinyl of 1 carbon-to-carbon double bond, for example vinyl, allyl group, pseudoallyl, crotonyl, a pentenyl etc. simultaneously as simple function property thiazolinyl.Wherein preferred allyl group.
The R of formula in (iii)
1For carbonatoms is 1～8 alkyl, can be the group of as above enumerating.Be preferably methyl, ethyl, most preferably be methyl.In addition, as R
2, can enumerate ethylidene, propylidene, butylidene, pentylidene etc., wherein preferred propylidene.As the organic group that formula is (iii) represented, can enumerate for example trimethoxysilylethylgroup group, trimethoxy-silylpropyl, triethoxysilyl ethyl, triethoxysilylpropyltetrasulfide etc.Be preferably trimethoxy-silylpropyl, triethoxysilylpropyltetrasulfide.
R in the organic group of (iv) representing as formula
3Example, can enumerate methylene radical, ethylidene, propylidene etc.As formula organic group (iv), can enumerate 2,3-epoxypropyl, 3,4-epoxy butyl, 4,5-epoxy amyl group etc.Wherein preferred 2, the 3-epoxypropyl.
The isocyanuric acid ester of formula (7) expression can obtain the organic isocyanate cyclisation of following formula (9) expression through using the such basic catalyst of for example phosphine, alkali alcoholate or organic tin salt.
T-NCO (9)
(definition of T as stated)
Wherein, has Q-R
3The isocyanuric acid ester of-Ji can through the such peracid of peroxyformic acid for example, peroxy acetic acid with following formula (10) expression, obtained by the carbon-to-carbon double bond oxidation substituted isocyanuric acid ester of unsaturated group of aliphatic series K, among the group K.
In the formula, K representes simple function property thiazolinyl, can be for as the described simple function thiazolinyl of T.L can be identical with K, or expression is selected from the group of the T beyond the simple function thiazolinyl.
Have formula group, (R (iii)
1O)
3Si-R
2-isocyanuric acid ester can make as follows: the silicoorganic compound that make formula (11) expression react in the presence of platinum catalyst with the isocyanuric acid ester that following formula (10) is represented.
(R
1O)
3Si-R
2-H (11)
(in the formula, R
1, R
2Same as described above)
(C) isocyanuric acid ester can finish the back isolation of target substances in reaction, also can use the reaction mixture of only having removed unreacted reactant, by product and catalyzer.
As (C) isocyanuric acid ester, the compound that the following structural formula of can giving an example is represented.In the following formula, Ph representes phenyl.Also can use the mixture of these compounds.
With respect to 100 weight parts (A) organopolysiloxane, use level (C) is in the scope of 0.1～2 weight part, preferably in the scope of 0.2～1 weight part.Use level is during less than above-mentioned lower value, the closing force of siloxanes tunicle improved insufficient, on the other hand, as surpassing above-mentioned higher limit, then hinders the solidified nature of (A) organopolysiloxane sometimes.
Above-mentioned (B) and (C) can be matched with (A) organopolysiloxane be that known any stripping film of principal constituent is with in the silicone composition.In this known silicone composition, have through addition reaction solidified type and through condensation reaction solidified type 2 types.
For through the addition reaction cured silicone composition, (A) organopolysiloxane is represented with following formula (1) for having the organopolysiloxane of 2 thiazolinyls in (A1) 1 molecule at least.
In the formula, R
12Be thiazolinyl, R
11For not having the monovalence alkyl of unsaturated link(age), X
1The group of representing for following structural formula.
A1, b1, c1, d1, e1 be selected from the viscosity that makes under 25 ℃ of the organopolysiloxane be 0.1Pas or more than, the viscosity under 25 ℃ in 30% toluene solution is 70Pas or following positive number, b1, c1, d1, e1 can be 0.α and β are 0 or 1～3 integer.
R
11Be the monovalence alkyl of not fatty family unsaturated link(age), be preferably carbonatoms 1～20,1～8 group more preferably.For example be selected from following organic group: the alkyl of carbonatomss 1～12 such as methyl, ethyl, propyl group, butyl; The naphthenic base of carbonatomss such as cyclohexyl 4～20; The aryl of carbonatoms such as phenyl, tolyl 6～20; Be bonded to the part of the Wasserstoffatoms on the carbon atom of these groups or all by groups such as substituted chloromethyl such as halogen atom, cyanic acid, trifluoro propyl, cyano ethyls; The alkoxyl group of carbonatomss 1～12 such as methoxyl group, oxyethyl group, propoxy-, methoxyethoxy; And the epoxy group(ing) of carbonatoms 2～20 etc.Consider the whole contained R of preferred (A1) organopolysiloxane from the characteristic of the curing tunicle that obtains
11At least 80% be methyl.
R
12Be preferably the thiazolinyl of carbonatomss 2～6 such as vinyl, allyl group, crotonyl, preferred vinyl in the industry.
(A1) thiazolinyl that is had in organopolysiloxane 1 molecule be 2 or more than, preferably be 0.001～0.1 mole amount with respect to the content of every 100g (A1) organopolysiloxane.Selecting type (1) and substituent X
1In a1, b1, c1, d1, e1, the thiazolinyl that 1 molecule is had is counted c1+b1 * (1+e1+ β)+2 α in 2～1,500 scope.
(A1) backbone structure of organopolysiloxane can be straight chain, also can contain b1 and be not 0 o'clock branched structure.
As with the compound of above-mentioned (A1) organopolysiloxane addition reaction, use the organohydrogensiloxanes that gathers of the Wasserstoffatoms (SiH) that has at least 3 Direct Bonding on Siliciumatom in (D1) 1 molecule.(D1) represent with following composition formula (12).
R
11 fH
gSiO
(4-f-g)/2 (12)
(in the formula, R
11Meaning the same, f satisfies 0≤f≤3, g satisfies 0＜g≤3, preferred 0.2≤g≤1, wherein, f+g satisfies 1≤f+g≤3)
(D1) molecular structure can for straight chain shape, branched or cyclic any one.Viscosity gets final product in the scope of number mPas～tens thousand of mPas.Gather the example of organohydrogensiloxanes as (D1), can enumerate following organopolysiloxane.
In following formula, Y is the group that following formula is represented,
Z is the group that following formula is represented,
In addition, in said structure formula and composition formula, h～w is the integer of following ranges.H, l, n are 3～500; M, p, s are 1～500; I, j, k, o, q, r, t, u, v, w are 0～500.
Above-mentioned (D1) gathers organohydrogensiloxanes and is equivalent in (A1) 1～5 times amount of contained thiazolinyl total mole number with contained SiH base mole number and uses.(D1) solidified nature is insufficient down in limited time less than above-mentioned for contained SiH base mole number in, even and surpass the above-mentioned upper limit and cooperate, solidified nature also can obviously not increase, moreover, separability also can reduce sometimes.Gather organohydrogensiloxanes for typical (D1), the amount of above-mentioned scope is for being 0.1～20 mass parts with respect to 100 mass parts (A1) organopolysiloxane.
Catalyzer (E1) as (A1) organopolysiloxane during with the addition reaction that (D1) gathers organohydrogensiloxanes can use known all catalyzer at present.Can enumerate for example platinum black, Platinic chloride, Platinic chloride-alkene complex, Platinic chloride-pure coordination compound, rhodium, rhodium-alkene complex etc.Usually with respect to (A1), (B), (C) and gross weight (D1); Amount in platinum or rhodium; Cooperate 5～1000ppm (mass ratio) above-mentioned (E1) catalyzer can form sufficient curing tunicle, but can be according to reactive or desired suitable the increasing and decreasing of curing speed of each composition.
For the processing that improves compsn of the present invention is bathed stability and to coating, adjustment glue spread and the viscosity of various base materials, can also be contained (F) organic solvent.Can use for example toluene, YLENE, ETHYLE ACETATE, acetone, ethyl methyl ketone, hexane etc.
Compsn of the present invention can through homogeneous mix above-mentioned (A1), (B), (C), (D1), (E1) and as required the various compositions of blended (F) easily make, in order to ensure sufficient working life, (E1) catalyzer preferably adds before coating and mixes.In addition, when using (F) organic solvent, be dissolved in (A1) homogeneous in (F) after, it is favourable mixing other compositions.
Can cooperate additives such as pigment, flow agent, bath plating life extender in the compsn of the present invention as required.
When using compsn of the present invention to be coated with; Can be coated with machine, roller coating machine, reverse coating machine, gravure roll coating machine, Kohler coater and in the coating of filming, have known coating processes such as high-precision hectograph coating machine, multi-stage type roller coating machine through rod, coat on the base material such as plastics.
The glue spread of compsn of the present invention on base material is different because of the kind of substrate material, and the amount of solids component is preferably at 0.05～5g/m
2Scope.Base material through using above-mentioned the whole bag of tricks to be coated with compsn of the present invention heated 60～5 seconds down at 80～150 ℃, can form at substrate surface and solidify tunicle, thereby obtain stripping film.
Below the silicone composition of the solidified type through condensation reaction is described.For said composition, (A) organopolysiloxane contains at least 2 hydroxyls in (A2) 1 molecule, has the organopolysiloxane of the structure of formula (2) expression.
In the formula, R
13Be hydroxyl, R
14For with above-mentioned R
11Identical monovalence alkyl can contain the aliphatics unsaturated link(age).X
2The group of representing for following formula.
A2, b2, c2, d2, e2 be selected from the viscosity that makes under 25 ℃ of the organopolysiloxane be 0.1Pas or more than, the viscosity in 30% toluene solution under 25 ℃ is 70Pas or following positive number, b2, c2, d2, e2 can be 0.γ and δ are 0 or 1 integer.
In following formula, as R
14, except above-mentioned R
11Outside the described group, also can enumerate the thiazolinyl of carbonatomss 2～6 such as vinyl, allyl group, propenyl.With above-mentioned R
11Identical, (A2) the whole contained R of organopolysiloxane
14At least 80% be thought of as preferably from the characteristic aspect for the situation of methyl.
(A2) hydroxyl that is had in organopolysiloxane 1 molecule be 2 or more than, preferably the content with respect to every 100g (A2) is 0.0001～0.1 mole.Amount of hydroxyl groups is as less than above-mentioned lower value, and then solidified nature reduces, and then takes place to shorten working life as surpassing above-mentioned higher limit, the situation of difficult treatment.Selecting type (2) and substituent X
2In a2, b2, c2, d2, e2, make hydroxyl value c2+b2 * (e2+ δ)+2 γ that 1 molecule had in 2～150 scope.
(A2) range of viscosities under 25 of organopolysiloxane ℃ be 0.1Pas or more than, the viscosity in 30 quality % toluene solutions is 70Pas or following.Viscosity is as less than above-mentioned lower value, the coating of compsn difficulty then, surpass above-mentioned higher limit then operability reduce.Selecting type (2) and substituent X
2In a2, b2, c2, d2, e2, make polymerization degree a2+c2+b2 * (d2+e2+1)+2 50～20,000 scope.
(A2) backbone structure of organopolysiloxane can be straight chain, also can contain b2 and be not 0 o'clock branched structure.
Make the organopolysiloxane that has at least 3 SiH or hydrolization group in (A2) organopolysiloxane and (D2) 1 molecule carry out condensation reaction.When having the organopolysiloxane of SiH, can use identical material with above-mentioned (D1).(D2) so that the mole number of contained SiH group or hydrolization group is that 5～200 times amount is used with respect to the mole number of hydroxyl contained in (A2).Under the situation of typical organopolysiloxane, with respect to (A2) 100 mass parts, this amount is in the scope of 0.1～30 mass parts.When the mole number of (D2) contained SiH base etc. during less than above-mentioned lower value, the cross linkage amount that the chemical reaction of hydroxyl and SiH etc. produces is insufficient, the tendency that has separability to reduce.On the other hand, cooperate, do not see that also separability improves the remarkable increase of effect, have on the contrary and reduce the compsn tendency of working life even surpass above-mentioned higher limit.
In addition, have the organopolysiloxane of hydrolization group, can use the compound of following chemical formulation as (D2).
R
11 fW
gSiO
(4-f-g)/2
(in the formula, R
11With above-mentioned R
11Identical, W representes hydrolization group, and f satisfies 0≤f≤3, and g satisfies 0＜g≤3, and f+g satisfies 1≤f+g＜3)
(D2) it is any that molecular structure can be straight chain shape, branched or cyclic.Viscosity gets final product in the scope of number mPas～tens thousand of mPas.
As hydrolization group W, can enumerate and have and alkoxyl groups such as the methoxyl group of Si direct bonding, oxyethyl group, propoxy-, butoxy, methoxyethoxy, isopropoxy; Acyloxy such as acetoxyl group; Amino such as ethylamino; Carboxamido-group; Oximidos such as ethyl-methyl fourth oxime; The group of halogen atom such as chlorine, bromine.Can use for example following organopolysiloxane.
W representes CH in the following formula
3COO-, CH
3(C
2H
5) C=NO-, (C
2H
5)
2N-, CH
3CO (C
2H
5) N-, CH
2=(CH
3) hydrolization group such as CO-, x, y, z are the integer of 0～500 scope.
(D2) organopolysiloxane that has hydrolization group is also to use with the same amount of the organopolysiloxane of the above-mentioned SiH of having group.In addition, also can use and have the two organopolysiloxane of hydrolization group and SiH group on a part.
(A2) and (D2) (E2) condensation catalyst that uses during reaction is used to promote condensation reaction to make it crosslinked, improves the separability and the weather resistance of cured film.As above-mentioned (E2) condensation catalyst, can enumerate acids such as hydrochloric acid, phosphoric acid, methylsulfonic acid, tosic acid, toxilic acid, trifluoroacetic acid; Bases such as sodium hydroxide, Pottasium Hydroxide, sodium ethylate, tetraethylammonium hydroxide; Salts such as ammonium chloride, ammonium acetate, Neutral ammonium fluoride, yellow soda ash; Organometallic compounds such as the organic acid salt of metals such as magnesium, aluminium, zinc, iron, zirconium, cerium, titanium, tin, alkoxide, chelate compound.Can enumerate for example two zinc octoates, titanium tetraisopropylate, three aluminium butoxides, tetra-acetylated zirconium acetate, two sad dioctyl tins.
With respect to (A2), (B), (C) and total mass (D2), in effective constituent, (E2) condensation catalyst cooperates 0.1～5% (mass ratio) usually, can carry out suitable increase and decrease according to the reactive or desired curing speed of each composition.
For the condensed type silicone composition, its can cooperate aspect (F) organic solvent and any composition, identical with above-mentioned add-on type compsn on preparation method and the coating process.
Embodiment
Below, with embodiment and comparative example the present invention is specified, but the present invention does not receive the qualification of following embodiment.
[synthetic example]
The three neck round-bottomed flasks that will have TM, magnetic stirrer, reflux condensing tube and a nitrogen ingress pipe with nitrogen replacement after; 2 moles of 1 mole of allyl ether compound, the γ-Qiu Jibingjisanjiayangjiguiwans, 2 that add following formula (13) expression; Two (2-methylbutyronitrile) 0.5g of 2 '-azo; With mixture heating up to 80 ℃, react.In the reaction process, after the peak disappearance of gc affirmation γ-Qiu Jibingjisanjiayangjiguiwan, heated 5 hours.Then, impurity is removed in distillation under 160 ℃/20mmHg, obtains the affixture 1 of following formula (14) expression.
Affixture 1
[synthetic example 2]
Except that the allyl ether compound that uses 1 mole of following formula (13) expression and 2 moles the Trimethoxy silane,, obtain the affixture 2 of following formula (15) expression according to the same method of synthetic example 1.
Affixture 2
Embodiment 1
The following material of uniform mixing obtains compsn:
The organopolysiloxane that 100 mass parts following formulas are represented (25 ℃ down the viscosity in 30% toluene solution be 10Pas, contents of ethylene be 0.03 mole/100g) as (A1),
Reaction product 2 conducts (B) that the synthetic example 2 of 2 mass parts obtains,
The isocyanuric acid ester of the following structure of 1 mass parts is as (C);
The polymethyl hydrogen siloxane that 5 mass parts (SiH that contains 2 times of thiazolinyl mole numbers that are equivalent to A1 composition and B composition) following formula is represented (viscosity under 25 ℃ is 25mPas, H content=1.5 mole/100g) as (D1),
With respect to the total mass of (A1), (B), (C), (D1), platinum-vinylsiloxane complex compound of counting 100ppm with platinum is as (E1) catalyzer; And
2052 mass parts toluene are as (F) composition.
Embodiment 2
The following material of uniform mixing obtains compsn:
The organopolysiloxane that 100 mass parts following formulas are represented (25 ℃ down the viscosity in 30% toluene solution be 10Pas, silanol group content=0.0005 mole/100g) as (A2);
The affixture 1 that the synthetic example 1 of 2 mass parts obtains is as (B);
The identical isocyanuric acid ester that 1 mass parts and embodiment 1 uses is as (C);
The polymethyl hydrogen siloxane that 1 mass parts (SiH that contains 30 times of hydroxyl mole numbers that are equivalent to the A2 composition) following formula is represented (viscosity under 25 ℃ is 25mPas, H content=1.5 mole/100g) as (D2);
5 mass parts, two sad dioctyl tins are as (E2) catalyzer; And
2071 mass parts toluene are as (F).
Comparative example 1
Except mismatch (B) and (C), with the same operation of embodiment 1 compositions formulated.
Comparative example 2
Except mismatch (B) and (C), with the same operation of embodiment 2 compositions formulated.
Comparative example 3
Except mismatching (B), and add 3 mass parts (C) in addition, same with embodiment 1
The operation compositions formulated.
Comparative example 4
Except mismatching (C), and add 3 mass parts (B) in addition, with embodiment 1 same operation compositions formulated.
Evaluation method
Estimate compsn according to following method.The result is shown in table 1.
1) solidified nature
Silicone composition through 10 minutes is coated on polyethylene terephthalate (PET) film (thick 38 μ m) behind the catalyzer with adding with the scraper spreader, and making solids component is 0.5g/m
2,, measure the time of solidifying tunicle until being completed into 80 ℃ heated air circulation type drying machine heat treated specified time.Carry out whether completely crued judgement as follows: be to rub and solidify the tunicle surface, do not occur sending out the mist and the moment that comes off on the tunicle surface with finger.
2) peeling force
Silicone composition through 10 minutes behind the interpolation catalyzer is coated on the PET film (38 μ m), and making solids component is 0.5g/m
2, with 100 ℃ heated air circulation type drying machine heat treated 30 seconds, form and solidify tunicle, make and estimate with diaphragm (separator).
With the diaphragm of processing at 25 ℃, the condition held of 50%RH after 1 day, solidifying tunicle surface coated acrylic acid or the like Solvent Adhesive (オ リ バ イ Application BPS-5127, Japan イ Application キ make (strain) system), 100 ℃ of following thermal treatments 3 minutes.Then; Applying PET film on this binder layer (38 μ m); With the roller of 2kg reciprocal 1 time with this PET film laminating on binder layer, at 25 ℃ down after aging 20 hours, it is wide that sample is cut into 5cm; Use tensile testing machine with the paper that the peeling rate of 180 ° angle, 0.3m/ minute stretches and fits, measure the needed power (N) of peeling off.
3) adaptation
Will be with 2) PET film (38 μ m) the base material diaphragm processed equally and with base material change biaxial stretch-formed polypropylene (OPP) film (40 μ m) into and according to 2) diaphragm processed of identical method is 25 ℃, the condition held of 50%RH; Rub curing tunicle surface with finger, study the fate of sending out mist and coming off in the discovery of tunicle surface.
[table 1]
| Solidified nature (second) | Peeling force (N) | Adaptation PET (fate) | Adaptation OPP (fate) | |
| Embodiment 1 | 20 | 0.50 | More than 100 | More than 100 |
| Embodiment 2 | 30 | 0.20 | More than 100 | More than 100 |
| Comparative example 1 | 20 | 0.45 | 5 | 20 |
| Comparative example 2 | 30 | 0.20 | 10 | 30 |
| Comparative example 3 | 20 | 0.46 | 30 | 25 |
| Comparative example 4 | 20 | 0.48 | 10 | 50 |
Can know that by table 1 cured film that is obtained by compsn of the present invention has significantly good adaptation.Can know that this adaptation can not obtain (comparative example 4 and 3) with (C) isocyanuric acid ester through containing (B) affixture respectively in a large number, (B) affixture and (C) isocyanuric acid ester have synergy.
Industrial applicability
Compsn of the present invention can form the good separability layer of adaptation, can be applicable to various stripping films.
Claims (4)
1. silicone composition, it is characterized in that for being the silicone composition for release film of principal constituent with the organopolysiloxane, contains in fact:
(A) viscosity under 25 ℃ is organopolysiloxane 100 mass parts below the 70Pas in 30 quality % toluene solutions,
(B) contain following formula (I) or (II) expression compound, the diphenyl alkane verivate with have affixture 0.3～3 mass parts of the organic siloxane derivative of at least one organic oxygen base;
Formula (I) and (II) in, R
4Be Wasserstoffatoms or methyl independently of each other, A be independently of each other formula (i) or (ii) the expression group, R
5For being selected from the group in hydroxyl and the methyl, a is 0～2 integer, R
6For carbonatoms 1～10 can substituted monovalence alkyl, R
7For carbonatoms 1～8 can substituted monovalence alkyl, b is 1～3 integer, c is 0 or 1, but b+c is 2 or 3, x is 1～8 integer,
With
(C) at least one in 0.1～2 mass parts isocyanuric acid ester, said isocyanuric acid ester and substituting group nitrogen atom bonding has epoxy group(ing) or trialkoxysilyl,
Said (A) organopolysiloxane is:
(A1) have the organopolysiloxane of at least 2 thiazolinyls in 1 molecule with following formula (1) expression,
In the formula, R
12Be thiazolinyl, R
11For not having the monovalence alkyl of unsaturated link(age), X
1The group of representing for following structural formula,
In the formula, it is more than the 0.1Pas that a1, b1, c1, d1, e1 are selected from the viscosity that makes under 25 ℃ of the organopolysiloxane, and the viscosity under 25 ℃ in 30% toluene solution is the positive number below the 70Pas, and b1, c1, d1, e1 can be 0, and α and β are 0 or 1～3 integer,
Perhaps
(A2) organopolysiloxane that contains at least 2 hydroxyls in 1 molecule that formula (2) is represented,
In the formula, R
13Be hydroxyl, R
14For containing the monovalence alkyl of aliphatics unsaturated link(age), X
2The group of representing for following formula,
In the formula, it is more than the 0.1Pas that a2, b2, c2, d2, e2 are selected from the viscosity that makes under 25 ℃ of the organopolysiloxane, and the viscosity in 30% toluene solution under 25 ℃ is the positive number below the 70Pas, and b2, c2, d2, e2 can be 0, and γ and δ are 0 or 1 integer.
2. the described silicone composition of claim 1, wherein, (A) organopolysiloxane is for having the organopolysiloxane of at least 2 thiazolinyls in (A1) 1 molecule,
Above-mentioned silicone composition also contains:
(D1) have the organohydrogensiloxanes that gathers of 3 SiH base in 1 molecule at least, its amount is equivalent to 1～5 times of contained thiazolinyl total mole number in (A1) for the total mole number of SiH group, and
(E1) the platinum metals class catalyzer of catalytic amount.
3. the described silicone composition of claim 1, wherein, (A) organopolysiloxane is for having the organopolysiloxane of at least 2 hydroxyls in (A2) 1 molecule,
Above-mentioned silicone composition also contains:
(D2) have the organopolysiloxane of at least 3 SiH bases or hydrolization group in 1 molecule, its amount is equivalent to 5～200 times of (A2) middle institute hydroxyl total mole number for the total mole number of SiH group and hydrolization group, and
(E2) condensation catalyst of catalytic amount.
4. any described silicone composition in the claim 1～3, wherein (C) isocyanuric acid ester is with following formula (7) expression,
In the formula, at least one T is the group that following formula is (iii) represented,
(R
1O)
3Si-R
2- (iii)
Formula (iii) in, R
1Be the alkyl of carbonatoms 1～8, R
2Alkylidene group for carbonatoms 2～5;
Or the group (iv) represented of following formula,
Q-R
3- (iv)
Formula (iv) in, Q is an epoxy group(ing), R
3Alkylidene group for carbonatoms 1～3;
Other T is independent mutually, is alkyl, aryl, aralkyl or the simple function property thiazolinyl of carbonatoms 1～8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005-191851 | 2005-06-30 | ||
| JP2005191851A JP4646122B2 (en) | 2005-06-30 | 2005-06-30 | Silicone composition for release film |
| JP2005191851 | 2005-06-30 |
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| CN1944538B true CN1944538B (en) | 2012-06-13 |
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| JP (1) | JP4646122B2 (en) |
| KR (1) | KR101225319B1 (en) |
| CN (1) | CN1944538B (en) |
| TW (1) | TWI397556B (en) |
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| KR101348955B1 (en) * | 2007-12-27 | 2014-01-08 | 코오롱인더스트리 주식회사 | Release Film |
| JP4707729B2 (en) * | 2008-03-31 | 2011-06-22 | 信越化学工業株式会社 | Low viscosity UV curable silicone composition for release paper |
| JP4994292B2 (en) * | 2008-04-09 | 2012-08-08 | 信越化学工業株式会社 | Solvent-free silicone release agent composition for film and release film using the same |
| JP5108825B2 (en) * | 2009-04-24 | 2012-12-26 | 信越化学工業株式会社 | Silicone resin composition for optical semiconductor device and optical semiconductor device |
| JP5587148B2 (en) * | 2010-03-09 | 2014-09-10 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Self-adhesive polyorganosiloxane composition |
| JP5387498B2 (en) | 2010-05-07 | 2014-01-15 | 信越化学工業株式会社 | Silicone composition for release film |
| JP5834755B2 (en) * | 2011-10-17 | 2015-12-24 | 信越化学工業株式会社 | Method for forming peelable cured film |
| KR101738602B1 (en) * | 2011-10-17 | 2017-06-08 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Silicone Release Coating Composition of Condensation Reaction Curing Type |
| JP5729253B2 (en) * | 2011-10-17 | 2015-06-03 | 信越化学工業株式会社 | Condensation reaction curable silicone release coating composition |
| JP5810865B2 (en) * | 2011-11-25 | 2015-11-11 | 信越化学工業株式会社 | Condensation reaction curable primer composition for silicone adhesive |
| CA2852130A1 (en) * | 2011-12-02 | 2013-06-06 | Cpfilms Inc. | Catalysts for thermal cure silicone release coatings |
| JP6331956B2 (en) * | 2014-10-17 | 2018-05-30 | 信越化学工業株式会社 | Organopolysiloxane composition for release sheet and release sheet |
| WO2016093383A1 (en) * | 2014-12-09 | 2016-06-16 | 한국생산기술연구원 | Thermosetting alkoxysilyl compound having two or more alkoxysilyl groups, composition and cured product comprising same, use thereof, and method for preparing alkoxysilyl compound |
| JP6691802B2 (en) * | 2016-03-29 | 2020-05-13 | アイカ工業株式会社 | Silicone adhesive composition and adhesive tape |
| JP7283347B2 (en) * | 2019-10-24 | 2023-05-30 | 信越化学工業株式会社 | Room-temperature curing organopolysiloxane composition for long-life coolant seals, cured silicone rubber for cooling coolant oil seals, and cooling coolant oil seals |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6335414B1 (en) * | 1999-03-12 | 2002-01-01 | Shin-Etsu Chemical Co., Ltd. | RTV organopolysiloxane compositions |
| CN1498249A (en) * | 2001-01-26 | 2004-05-19 | GE�ݶ���ɷ�����˾ | Polyorganosiloxane composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57137355A (en) * | 1981-02-17 | 1982-08-24 | Shin Etsu Chem Co Ltd | Organopolysiloxane composition |
| JPS62240363A (en) * | 1986-04-10 | 1987-10-21 | Shin Etsu Chem Co Ltd | Silicone composition for release film |
| JPH07119366B2 (en) * | 1989-07-03 | 1995-12-20 | 東芝シリコーン株式会社 | Adhesive silicone composition |
| JPH08208993A (en) * | 1995-11-27 | 1996-08-13 | Toshiba Silicone Co Ltd | Heat-conductive silicone composition |
| DE10338478A1 (en) * | 2003-08-21 | 2005-03-17 | Wacker-Chemie Gmbh | Self-adhesive addition-curing silicone compositions |
| JP2007002234A (en) * | 2005-05-27 | 2007-01-11 | Shin Etsu Chem Co Ltd | Curable silicone rubber composition and semiconductor device |
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- 2005-06-30 JP JP2005191851A patent/JP4646122B2/en not_active Expired - Fee Related
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- 2006-06-29 KR KR1020060059047A patent/KR101225319B1/en active IP Right Grant
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6335414B1 (en) * | 1999-03-12 | 2002-01-01 | Shin-Etsu Chemical Co., Ltd. | RTV organopolysiloxane compositions |
| CN1498249A (en) * | 2001-01-26 | 2004-05-19 | GE�ݶ���ɷ�����˾ | Polyorganosiloxane composition |
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| CN1944538A (en) | 2007-04-11 |
| TWI397556B (en) | 2013-06-01 |
| JP4646122B2 (en) | 2011-03-09 |
| KR20070003612A (en) | 2007-01-05 |
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| TW200712127A (en) | 2007-04-01 |
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