CN100513485C - Silicon rubber composition for electrode circuit protection, electrode circuit protection material and electric, electronic parts - Google Patents
Silicon rubber composition for electrode circuit protection, electrode circuit protection material and electric, electronic parts Download PDFInfo
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- CN100513485C CN100513485C CNB2004100852991A CN200410085299A CN100513485C CN 100513485 C CN100513485 C CN 100513485C CN B2004100852991 A CNB2004100852991 A CN B2004100852991A CN 200410085299 A CN200410085299 A CN 200410085299A CN 100513485 C CN100513485 C CN 100513485C
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Abstract
A silicone rubber composition for protecting the electrode circuits is characterized by containing (A) 100 pts. mass of a curable silicone rubber composition and (B) 0.1 to 50 pts. mass of an inorganic ion exchanger as essential components. The silicone rubber composition has low elasticity, can be cured by a low temperature heating treatment, a room temperature leaving treatment or a UV light irradiation treatment, and has excellent sulfuration resistance, and is therefore useful as a coating material for protecting liquid crystal electrodes, PDP electrodes and plasma display electrodes, and as a coating material for protecting various electric/electronic parts.
Description
Technical field
The present invention relates to be used for protecting metal electric, the electronic component telegraph circuit not to be subjected to the silicon rubber composition for electrode circuit protection of sulfide corrosion, electrode circuit protection material and electric, electronic component.
Background technology
In recent years, in electric, electronic component, the metal electrode circuit has been become big problem by sulfurations such as the vulcanizing agent of the sulfide in the atmosphere, rubber item, emission gases.
In this case; as protecting materials; metal-powders such as alkaline inorganic fillers such as interpolation lime carbonate or copper powder (patent documentation 1,2: the spy opens 2003-096301 communique, special former 2003-324171 number) have been proposed so far; but adopt this protecting materials in the past; exist preventing the corrosion of metal electrode circuit, prevent the inadequate problem in sulfuration aspect.
Patent documentation 1: the spy opens the 2003-096301 communique
Patent documentation 2: special former 2003-324171 number
Summary of the invention
Therefore, though problem of the present invention be to provide in the presence of sulfide also can the guard electrode circuit metal not be protected by sulfuration, corrosive silicon rubber composition for electrode circuit protection, electrode circuit protection material and telegraph circuit not cure, corrosive is electric, electronic component.
The present inventor has carried out research with keen determination in order to solve above-mentioned problem; it found that: for curable silicone rubber composition; by cooperating inorganic ion exchanger; particularly inorganic anion exchanger composed or inorganic zwitter-ion permutoid (amphoteric exchanger); in the presence of sulfide, can prevent the sulfuration of metal; corrosion; in this case; as operable curable silicone rubber composition; can use and to make it the solidified Thermocurable silicone rubber composition by the siloxanes that contains vinyl is reacted under the platinum family series catalysts with the siloxanes that contains the hydrogenation silyl; in the presence of condensation catalyst, make the siloxanes that contains silanol group and alkoxyl group carry out condensation reaction and solidified room temperature curing type rubber composition; and in substituting group, has a ultraviolet hardening rubber composition that has added Photoepolymerizationinitiater initiater in the polymkeric substance of acryl; the organic peroxide curing type rubber composition, thus the present invention finished.
Therefore, the invention provides silicon rubber composition for electrode circuit protection, it is characterized in that: with
(A) curable silicone rubber composition 100 mass parts,
(B) inorganic ion exchanger 0.1～50 mass parts
Be necessary component.In addition, the invention provides electrode circuit protection material that the cured article by above-mentioned silicon rubber composition for electrode circuit protection constitutes and electric, the electronic component that coats the guard electrode circuit with the cured article of this silicon rubber composition for electrode circuit protection.
Rubber composition of the present invention is because low elasticity; under low-temperature heat, room temperature placement or uviolizing, solidify and anti-sulphur corrosion excellence, therefore useful for the protection coating agent and the various protection coating agent electric, electronic component of for example liquid crystal electrode, PDP electrode, plasma display electrode.
Embodiment
Silicon rubber composition for electrode circuit protection of the present invention has cooperated inorganic ion exchanger in curable silicone rubber composition, but this curable silicone rubber composition uses known material.
Specifically, as the rubber composition that uses among the present invention, can enumerate the organopolysiloxane composition of addition curable, ultraviolet hardening, electron(beam)curing type, organic peroxide curing type, condensation cured type etc.As the addition curable rubber composition, for example can enumerate to make in the middle of molecular chain two ends, the molecular chain in the presence of the platinum family series catalysts or to have the straight chain shape diorganopolysiloxaneand of alkenyl such as vinyl in the middle of molecular chain two ends and the molecular chain and organic hydride polysiloxane reaction (hydrosilylation addition reaction) and the addition curable rubber composition that obtains.As the ultraviolet hardening rubber composition, it can be made of any consolidated structures for using the ultraviolet energy solidified rubber composition of wavelength 200～400nm basically.Specifically; be included in the acryl type siloxane that added Photoepolymerizationinitiater initiater in the organopolysiloxane with acryl or methacryloyl, in the organopolysiloxane that contains sulfydryl and organopolysiloxane, added with alkenyls such as vinyl Photoepolymerizationinitiater initiater sulfydryl-vinyl addition polymerization class, used the platinum family series catalysts identical with the Thermocurable addition reaction-type the addition reaction class, have in the organopolysiloxane of epoxy group(ing) and added cationoid polymerisation class of salt catalyst etc., can use any.As electron(beam)curing type rubber composition, can use having the organopolysiloxane irradiation electron rays of free-radical polymerised group, make any rubber composition of its solidified by radical polymerization.In addition, as the organic peroxide curing type rubber composition, can be set forth in organo-peroxide and have the rubber composition that makes the above-mentioned straight chain shape diorganopolysiloxaneand that contains alkenyl carry out radical polymerization down and obtain.As condensation cured type rubber composition, for example can enumerate and in the presence of condensation catalysts such as organotin series catalysts, make the end capped diorganopolysiloxaneand of two terminal silanol groups and organic hydride polysiloxane or tetraalkoxysilane, the reaction of water-disintegrable silane such as organotrialkoxysilane or its partial hydrolysis condenses and the rubber composition that obtains, in the presence of condensation catalysts such as organotin series catalysts, make the two terminal tri-alkoxy siloxyies of using, the organic siloxy-of dialkoxy, tri-alkoxy silicomethane oxygen ethyl, the organic silicomethane oxygen of dialkoxy ethyl etc. contains the siloxy-of alkoxyl group or contains the reaction of the end capped diorganopolysiloxaneand of alkoxy silicane oxyalkyl and the rubber composition that obtains etc.
More specifically say, as the addition curable rubber composition, can enumerate particularly by
(a) contain more than 2 organopolysiloxane with Siliciumatom bonded alkenyl in 1 molecule,
(b) have more than 2 and organic hydride polysiloxane Siliciumatom bonded hydrogen atom (being the SiH yl) in 1 molecule, wherein, with Siliciumatom bonded hydrogen atom be 0.1～5.0 with respect to the mol ratio in (a) component with Siliciumatom bonded alkenyl,
(c) the addition curable rubber composition of the platinum family series catalysts of catalytic amount formation.
Be used for containing in 1 molecule (a) component of addition curable rubber composition more than 2 organopolysiloxane with Siliciumatom bonded alkenyl, be known organopolysiloxane as the stock polymer of addition curable rubber composition, weight-average molecular weight is generally about 3000～300000, has 100～1000000mPas under the preferred normal temperature (25 ℃), the organopolysiloxane that especially preferably has 200～100000mPas left and right sides viscosity can use the organopolysiloxane shown in the following average group accepted way of doing sth (1).
R
1aSiO
(4-a)/2?(1)
(in the formula, R
1Be the C that is same to each other or different to each other
1～10, preferred C
1-8Non-replacement or 1 valency alkyl of replacement, a is 1.5～2.8, the positive number of preferred 1.8～2.5, more preferably 1.95～2.05 scopes.)
As above-mentioned R
1Shown and 1 valency alkyl non-replacement of Siliciumatom bonded or replacement, can enumerate for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, cyclohexyl, octyl group, nonyl, alkyl such as decyl, phenyl, tolyl, xylyl, aryl such as naphthyl, benzyl, styroyl, aralkyl such as hydrocinnamyl, vinyl, allyl group, propenyl, pseudoallyl, butenyl, hexenyl, cyclohexenyl, alkenyls such as octenyl, part or all of the hydrogen atom of these groups is by fluorine, bromine, halogen atoms such as chlorine, the group that cyano group etc. replace, for example chloromethyl, chloropropyl, bromotrifluoromethane, trifluoro propyl, cyanoethyl etc.
In this case, necessarily, R
1In at least 2 (be preferably C especially for alkenyl
2～ 8Group, C more preferably
2～6Group).In addition, the content of alkenyl preferably with the whole organic groups of Siliciumatom bonded in (be in the above-mentioned average group accepted way of doing sth (1) as R
1Non-replacement or 1 valency alkyl of replacement in) be 0.01～20 mole of %, be preferably 0.1～10 mole of % especially.This alkenyl can combine with the Siliciumatom of molecule chain end, also can combine with molecular chain intermediary Siliciumatom, can also combine with both, but from the curing speed of composition, the aspects such as rerum natura of cured article, the organopolysiloxane that uses among preferred the present invention contains the Siliciumatom bonded alkenyl with molecule chain end at least.
The structure of above-mentioned organopolysiloxane is generally main chain by diorganosiloxane repeating unit ((R
1)
2SiO
2/2The unit) constitute, molecule chain end is by three organic radical siloxy-((R
1)
3SiO
1/2The unit) the end capped diorganopolysiloxaneand that has straight chain structure basically, but also can be partly for containing R
1SiO
3/2Unit and SiO
4/2Unitary branch-like structure, ring texture etc.
The substituting group of Siliciumatom is essentially above-mentioned any group, as alkenyl, and preferred vinyl, as other substituting group, preferable methyl, phenyl.
As the example of (a) component, can enumerate the compound shown in the following general formula etc.
R in the above-mentioned general formula and R
1Identical, but do not contain alkenyl.M, n are the integer of m 〉=1, n 〉=0, and m+n is that to make the molecular weight of this organopolysiloxane or viscosity be the number of above-mentioned value.
(b) the organic hydride polysiloxane of component is to have more than 2 and organic hydride polysiloxane Siliciumatom bonded hydrogen atom (SiH yl) in 1 molecule.Here, (b) component and (a) component reaction, play the effect of linking agent, there is no particular restriction for its molecular structure, can use in the past the material of for example wire made, ring-type, branch-like, tridimensional network various structures such as (arborescens), but must in 1 molecule, have more than 2 with Siliciumatom bonded hydrogen atom (SiH yl), preferably have 2～200, more preferably have 3～100.As the organic hydride polysiloxane, can use material shown in the following average group accepted way of doing sth (2).
R
2 bH
cSiO
(4-b-c)/2 (2)
In following formula (2), R
2Be C
1-10Non-replacement or 1 valency alkyl of replacement, as this R
2, can enumerate with above-mentioned formula (1) in R
1Identical group.In addition, b is 0.7～2.1, and c is 0.001～1.0, and for b+c satisfies 0.8～3.0 positive number, preferred b is 1.0～2.0, and c is 0.01～1.0, and b+c is 1.5～2.5.
At least contain 2, preferred 3 above SiH bases in 1 molecule, can be positioned at molecule chain end, any position of molecular chain intermediary, or be positioned at this two kinds of positions.In addition, the molecular structure of this organic hydride polysiloxane can be for straight chain shape, ring-type, branch-like, tridimensional network any, but wish that it is that Siliciumatom number (or polymerization degree) in 1 molecule is generally 2～300, the room temperature (25 ℃) that is preferably about 4～150 is the organic hydride polysiloxane of liquid down.
Organic hydride polysiloxane as formula (2), particularly, for example can enumerate 1,1,3, the 3-tetramethyl disiloxane, 1,3,5, the 7-tetramethyl-ring tetrasiloxane, three (hydrogenation dimethylsilane oxygen base) methyl-monosilane, three (hydrogenation dimethylsilane oxygen base) phenyl silane, the hydrogenated methyl cyclopolysiloxane, hydrogenated methyl siloxanes-dimethyl siloxane cyclocopolymer, the end capped hydrogenated methyl polysiloxane of two terminal trimethylsiloxy, two terminal trimethylsiloxy end-blocking dimethyl siloxane-hydrogenated methyl silicone copolymers, the end capped dimethyl polysiloxane of two terminal dimethyl hydrogenation siloxyies, the end capped dimethyl siloxane of two terminal dimethyl hydrogenation siloxyies-hydrogenated methyl silicone copolymers, the end capped hydrogenated methyl siloxanes of two terminal trimethylsiloxy-diphenyl siloxane multipolymer, the end capped hydrogenated methyl siloxanes-diphenyl siloxane of two terminal trimethylsiloxy-dimethylsiloxane copolymer, the end capped hydrogenated methyl siloxanes-methylphenyl siloxane of two terminal trimethylsiloxy-dimethylsiloxane copolymer, the end capped hydrogenated methyl siloxanes-dimethyl siloxane of two terminal dimethyl hydrogenation siloxyies-diphenyl siloxane multipolymer, the end capped hydrogenated methyl siloxanes-dimethyl siloxane of two terminal dimethyl hydrogenation siloxyies-methylphenyl siloxane multipolymer, by (CH
3)
2HSiO
1/2Unit and (CH
3)
3SiO
1/2Unit and SiO
4/2The multipolymer that the unit constitutes, by (CH
3)
2HSiO
1/2Unit and SiO
4/2The multipolymer that the unit constitutes, by (CH
3)
2HSiO
1/2Unit and SiO
4/2Unit and (C
6H
5)
3SiO
1/2The multipolymer that the unit constitutes etc.
Addition that should (b) component, for Siliciumatom bonded hydrogen atom be 0.1～5.0 normal amount with respect to the mol ratio in 1 (a) component with Siliciumatom bonded alkenyl, preferred 0.5～3.0 equivalent, more preferably 0.8～2.0 normal scope.When than 0.1 equivalent after a little while, it is low that cross-linking density became, to the thermotolerance generation detrimentally affect of solidified silicon rubber.In addition, when for a long time,, also thermotolerance is produced detrimentally affect owing to dehydrogenation reaction produces the problem of foaming than 5.0 equivalents.
(c) the platinum family series catalysts of component is as promoting (a) component and (b) catalyzer of the curing addition reaction (hydrosilylation) of component.The platinum family series catalysts can use known material, but preferably uses platinum or platinic compound.Platinic compound can be enumerated the complex compound etc. of pure modifier, chlorination platinic acid and alkene, aldehyde, vinylsiloxane or the acetylene series alcohols etc. of platinum black, platinum chloride, chlorination platinic acid, chlorination platinic acid.
The use level of this platinum family series catalysts can suitably increase and decrease according to desirable curing speed, and for (a) component, the platinum amount is generally 0.1～1000ppm, the scope of preferred 1～200ppm.
As the ultraviolet hardening rubber composition, particularly, can enumerate
(d) ultraviolet reactive organopolysiloxane,
(e) the ultraviolet hardening rubber composition of Photoepolymerizationinitiater initiater formation.
(d) the ultraviolet reactive organopolysiloxane of component, in the ultraviolet hardening rubber composition, play a role as stock polymer usually, be not particularly limited, at least have 2 in preferred 1 molecule, more preferably have 2～20, especially preferably have the organopolysiloxane of 2～10 ultraviolet reactive groups.In addition, in above-mentioned polymer molecule, exist a plurality of above-mentioned ultraviolet reactive groups can be all identical, also can be different.
Organopolysiloxane with above-mentioned ultraviolet reactive group, in the middle of its molecule chain end and/or the molecular chain, preferably molecular chain two ends have ultraviolet reactive group at least.As this ultraviolet ray reactive group; can enumerate for example alkenyloxies such as vinyl, allyl group, propenyl, vinyloxy group, allyloxy, propenyloxy group, different propenyloxy group; unsaturated group of aliphatic series such as acryl, methacryloyl; sulfydryl; epoxy group(ing); the hydrogenation silyl, preferred acryl, methacryloyl, sulfydryl, epoxy group(ing), hydrogenation silyl, more preferably acryl, methacryloyl.
The viscosity of above-mentioned organopolysiloxane is not particularly limited, and is down that more preferably 100～10000000mPas is preferably 100～100000mPas especially more than the 25mPas at 25 ℃ preferably.
The preferred main chain of this organopolysiloxane is made of the diorganosiloxane repeating unit basically, molecular chain two is terminal with end capped straight chain structures of three organic radical silyl substituted alkyls such as three organic radical siloxyies or three organic radical silyl ethyls, also can partly contain trifunctional siloxane unit or SiO
2Branch-like structures such as unit.
As a preferred configuration of (d) component, can enumerate for example following general formula (3a)
[in the formula, R
3Identical or different, be 1 valency alkyl of non-replacement or replacement, R
4Identical or different, for having the group of ultraviolet reactive group, R
5For having the group of ultraviolet reactive group, m is 5～1000 integer, and n is 0～100 integer, and p is 0～3 integer, and q is 0～3 integer, p+q+n 〉=2.]
Or following general formula (3b)
[in the formula, R
3, R
4And R
5Identical or different separately, with middle define identical of above-mentioned formula (3a), definition is identical in m, n, p and q and the above-mentioned formula (3a), and k is 2～4 integer, and r and s are respectively 1～3 integer, pr+qs+n 〉=2.]
Shown organopolysiloxane with at least 2 ultraviolet reactive groups.
Above-mentioned formula (3a) and (3b) in, R
3For not having ultraviolet reactive group, be generally C
1～20, preferred C
1～10, more preferably C
1-81 valency alkyl.As R
31 shown valency alkyl, can enumerate for example methyl, ethyl, propyl group, butyl, sec.-propyl, isobutyl-, the tertiary butyl, hexyl, the 2-ethylhexyl, the 2-ethyl-butyl, alkyl such as octyl group, cyclohexyl, cycloalkyl such as cyclopentyl, alkenyls such as hexenyl, phenyl, tolyl, xylyl, naphthyl, aryl such as xenyl, benzyl, aralkyl such as styroyl, with part or all of the carbon atom bonded hydrogen atom of these groups by halogen atom, cyano group, amino, the group that carboxyl etc. replace, or has a group of above-mentioned functional group, chloromethyl for example, trifluoro propyl, the 2-cyanoethyl, 3-cyanogen propyl group etc., preferable methyl, phenyl, more preferably methyl.In addition, can be at above-mentioned R
3Have alkylsulfonyl more than a kind or 2 kinds, ehter bond (-O-), carbonyl etc. in the skeleton of 1 shown valency alkyl.
Above-mentioned formula (3a) and (3b) in, as R
4And R
5Shown in have the ultraviolet reactive group that group contained of ultraviolet reactive group; can enumerate for example alkenyloxies such as vinyl, allyl group, propenyl, vinyloxy group, allyloxy, propenyloxy group, different propenyloxy group; unsaturated group of aliphatic series such as acryl, methacryloyl; sulfydryl, epoxy group(ing), hydrogenation silyl etc.; preferred acryl, methacryloyl, sulfydryl, epoxy group(ing), hydrogenation silyl, more preferably acryl, methacryloyl.Therefore, R
4And R
5Shown in have the group of ultraviolet reactive group; can be above-mentioned illustrative 1 valency group with ultraviolet reactive group; can enumerate for example vinyl; allyl group; 3-glycidoxy propyl group; 2-(3; the 4-epoxycyclohexyl) ethyl; the 3-methacryloxypropyl; 3-acryloxy propyl group; 3-mercapto propyl group; two (2-methacryloxy oxyethyl group) the methyl-silicane bases of 2-{ } ethyl; 2-{ (2-methacryloxy oxyethyl group) dimetylsilyl } ethyl; two (2-acryloyl-oxy base oxethyl) the methyl-silicane bases of 2-{ } ethyl; 2-{ (2-acryloyl-oxy base oxethyl) dimetylsilyl } ethyl; 2-{ two (1; 3-dimethyl allene acyloxy-2-propoxy-) methyl-silicane base } ethyl; 2-{ (1; 3-dimethyl allene acyloxy-2-propoxy-) dimetylsilyl } ethyl; two (1-acryloxy-3-methacryloxy-2-propoxy-) the methyl-silicane bases of 2-{ } ethyl; 2-{ (1-acryloxy-3-methacryloxy-2-propoxy-) dimetylsilyl } ethyl etc.; preferred 3-methacryloyl propyl group; 3-acryloxy propyl group; two (2-methacryloxy oxyethyl group) the methyl-silicane bases of 2-{ } ethyl; 2-{ (2-methacryloxy oxyethyl group) dimetylsilyl } ethyl; two (2-acryloyl-oxy base oxethyl) the methyl-silicane bases of 2-{ } ethyl; 2-{ (2-acryloyl-oxy base oxethyl) dimetylsilyl } ethyl; 2-{ two (1; 3-dimethyl allene acyloxy-2-propoxy-) methyl-silicane base } ethyl; 2-{ (1; 3-dimethyl allene acyloxy-2-propoxy-) dimetylsilyl } ethyl; two (1-acryloxy-3-methacryloxy-2-propoxy-) the methyl-silicane bases of 2-{ } ethyl; 2-{ (1-acryloxy-3-methacryloxy-2-propoxy-) dimetylsilyl } ethyl; more preferably 3-acryloxy propyl group; two (2-methacryloxy oxyethyl group) the methyl-silicane bases of 2-{ } ethyl; 2-{ (2-methacryloxy oxyethyl group) dimetylsilyl } ethyl; 2-{ (2-acryloyl-oxy base oxethyl) dimetylsilyl } ethyl; two (1,3-dimethyl allene acyloxy-2-propoxy-) the methyl-silicane bases of 2-{ } ethyl; two (1-acryloxy-3-methacryloxy-2-propoxy-) the methyl-silicane bases of 2-{ } ethyl.Above-mentioned R
4And R
5Can be identical, also can be different.
In above-mentioned formula (3a) with (3b), m is preferably 10～800, more preferably 50～500 integer.N is preferably 0～50, more preferably 0～20 integer.In above-mentioned formula (3b), k is preferably 2 or 3.P is preferably 0～2 integer, and more preferably 1 or 2.Q is preferably 0～2 integer, and more preferably 1 or 2.R and s are preferably 1 or 2 respectively.In addition, above-mentioned formula (3a) and (3b) shown in organopolysiloxane, as mentioned above,, therefore in formula (3a), must make p+q+n 〉=2 owing to have at least 2 above-mentioned ultraviolet reactive groups, in formula (3b), must make pr+qs+n 〉=2.
As above-mentioned formula (3a) or the concrete example of the organopolysiloxane (3b), can enumerate material for example shown below.
[in the formula, R
690% be methyl, 10% is phenyl]
(e) Photoepolymerizationinitiater initiater of component has the photopolymerisable effect that promotes above-mentioned (d) component middle-ultraviolet lamp reactive group.Be not particularly limited as this Photoepolymerizationinitiater initiater; can enumerate for example methyl phenyl ketone; Propiophenone; benzophenone; キ サ Application ト-Le; Off Le オ レ イ Application; phenyl aldehyde; anthraquinone; triphenylamine; the 4-methyl acetophenone; 3-amylbenzene ethyl ketone; the 4-methoxyacetophenone; the 3-bromoacetophenone; 4-allyl benzene ethyl ketone; to diacetyl benzene; the 3-methoxy benzophenone; 4-methyldiphenyl ketone; the 4-chlorobenzophenone; 4; 4 '-dimethoxy-benzophenone; 4-ammonia-4 '-benzyl benzophenone; 3-chlorine xanthone; 3; 9-diamino xanthone; 3-chlorine 8-nonyl xanthone; bitter almond oil camphor; benzoin methyl ether; the bitter almond oil camphor butyl ether; two (4-dimethylaminophenyl) ketone; benzyl methoxyl group acetal; the 2-clopenthixal ketone; the diethylbenzene ethyl ketone; the 1-hydroxycyclohexylphenylketone; 2-methyl-(4-(methylthio group) phenyl)-2-morpholinyl-1-propane; 2; 2-dimethoxy-2-phenyl methyl phenyl ketone; diethoxy acetophenone etc.; preferred benzophenone; the 4-methoxyacetophenone; 4-methyldiphenyl ketone; diethoxy acetophenone; 1-hydroxycyclohexylphenylketone, more preferably diethoxy acetophenone; the 1-hydroxycyclohexylphenylketone.
Above-mentioned Photoepolymerizationinitiater initiater can use a kind separately, also can more than 2 kinds and use.(e) use level of component is not particularly limited, and with respect to (d) component 100 mass parts, is generally 0.01～10 mass parts, preferred 0.1～3 mass parts, more preferably 0.5～3 mass parts.If this use level is 0.01～10 mass parts, the solidification compound that then makes preparation solidifies and physical property excellences such as the intensity of the curing rubber that obtains and tensile strength.
As the organic peroxide curing type rubber composition, particularly, can enumerate by
(f) contain in 1 molecule more than 2 with the organopolysiloxane of Siliciumatom bonded alkenyl,
(g) the organic peroxide curing type rubber composition of organo-peroxide composition.
As (f) component of organic peroxide curing type rubber composition main component (stock polymer), be a following average group accepted way of doing sth (4)
R
7 dSiO
(4-d)/2 (4)
(in the formula, R
7Expression replaces or unsubstituted 1 valency alkyl, R
70.0001～10 mole of % be alkenyl, and 80 moles of % above be methyl.D is 1.9～2.4 positive number.) shown in 1 molecule on average have the organopolysiloxane of 2 alkenyls at least.
Here, R
7Be the C that is same to each other or different to each other
1～10, preferred C
1～8The 1 valency alkyl that does not replace or replace, d is 1.9～2.4, and is preferred 1.95～2.05, more preferably the positive number of 1.98～2.02 scopes.As above-mentioned R
7The shown 1 valency alkyl that does not replace or replace with the Siliciumatom bonded is with the R of an above-mentioned average group accepted way of doing sth (1)
1Identical, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, cyclohexyl, octyl group, nonyl, alkyl such as decyl, phenyl, tolyl, xylyl, aryl such as naphthyl, benzyl, styroyl, aralkyl such as hydrocinnamyl, vinyl, allyl group, propenyl, pseudoallyl, butenyl, hexenyl, cyclohexenyl, alkenyls such as octenyl, part or all of the hydrogen atom of these groups is by fluorine, bromine, halogen atoms such as chlorine, the group that cyano group etc. replace, for example chloromethyl, chloropropyl, bromotrifluoromethane, halogen-substituted alkyls such as trifluoro propyl or cyanoethyl etc.
In this case, R
7In at least 2 be necessary for alkenyl (preferred C
2～8Alkenyl, more preferably C
2～6Alkenyl).In addition, the content of alkenyl is preferably at whole organic radicals (being the above-mentioned 1 valency alkyl that does not replace or replace) R
7In be 0.0001～10 mole of %, be preferably 0.001～5 mole of % especially.This alkenyl can combine with the Siliciumatom of molecule chain end, also can combine with molecular chain intermediary Siliciumatom, perhaps combines with both.
There is no particular restriction for the polymerization degree, can use under the normal temperature to aqueous that mean polymerisation degree is 50～20000 usually so that give birth to gelationus material, preferred 100～10000, and more preferably about 100～2000.
In addition, the structure of this organopolysiloxane is that main chain is by diorganosiloxane repeating unit (R basically
7 2SiO
2/2) constitute, have molecular chain two ends by three organic radical siloxy-(R
7 3SiO
1/2) or hydroxyl two organic radical siloxyies ((HO) R
7 2SiO
1/2) end capped straight chain structure, can partly be branch-like structure, ring texture etc. also.
As the organo-peroxide of (g) component, in the organic peroxide curing type organopolysiloxane composition, can use known substances in the past for catalyzer as the crosslinking reaction that promotes (f) component.Can enumerate for example benzoyl peroxide, peroxidation 2,4-dichloro-benzoyl, peroxidation are to toluyl, peroxidation o-methyl-benzene formyl, 2,4-two cumene peroxide, 2,5-dimethyl-two (2, the 5-t-butyl peroxy) hexane, ditertiary butyl peroxide, t-butylperoxyl benzoate, 1,1-two (t-butyl peroxy carboxyl) hexane etc., but be not limited to these materials.
In addition, the addition of organo-peroxide is a catalytic amount, can suitably select according to curing speed, is generally 0.1～10 mass parts, the scope of preferred 0.2～2 mass parts for (f) component 100 mass parts.
As condensation cured type rubber composition, particularly, can enumerate by
(h) in 1 molecule preferably molecular chain two ends have at least 2 silanol groups (being that Siliciumatom is in conjunction with hydroxyl) or Siliciumatom in conjunction with the organopolysiloxane of hydrolization group,
(i) as the water-disintegrable silane of any component or its partial hydrolysis condenses,
(j) the condensation cured type rubber composition of forming as the condensation catalyst of any component.
(h) component is the stock polymer of condensation cured type rubber composition, molecular chain two ends have silanol group or with the organopolysiloxane of Siliciumatom bonded hydrolization group in, as the hydrolization group beyond the silanol group, can enumerate for example acetoxyl group, hot acyloxy, acyloxy such as benzoyloxy, the dimethyl ketone oximido, the methyl ethyl ketone oximido, ketoxime bases (being inferior aminooxy) such as metacetone oximido, methoxyl group, oxyethyl group, alkoxyl groups such as propoxy-, methoxy ethoxy, ethoxy ethoxy, alkoxyl group alkoxyl groups such as methoxy propoxy, vinyloxy group, different propenyloxy group, 1-ethyl-alkenyloxies such as 2-ethylene methacrylic oxygen base, dimethylamino, diethylin, fourth amino, amino such as hexamethylene amino, the diformazan aminooxy, aminooxy such as diethyl aminooxy, N-methylacetamide base, N-ethyl acetamide base, amide group such as N-methyl-benzamide base.
Preferred these hydrolization groups, for example with the tri-alkoxy siloxy-, dialkoxy organic radical siloxy-, three acyloxy siloxyies, two acyloxy organic radical siloxyies, Sanya aminooxy siloxy-(being triketone oximido siloxy-), two inferior aminooxy organic radical siloxyies, three alkenyloxy siloxyies, two alkenyloxy organic radical siloxyies, tri-alkoxy siloxy-ethyl, dialkoxy organic radical siloxy-ethyl etc. contains the siloxy-of 2 or 3 hydrolysis decomposability groups or contains the forms such as silicomethane oxyalkyl of 2 or 3 hydrolysis decomposability groups, is positioned at molecular chain two ends of straight chain shape diorganopolysiloxaneand.
As with other Siliciumatom bonded 1 valency alkyl, can enumerate with above-mentioned addition curable rubber composition in as R in (a) component average group accepted way of doing sth (1) of stock polymer
1The 1 valency alkyl that does not replace or replace that shown group is identical.
As the concrete example of this organopolysiloxane, can enumerate for example end capped dimethyl polysiloxane of molecular chain two terminal silanol groups, the end capped dimethyl siloxane of molecular chain two terminal silanol groups-methylphenyl siloxane multipolymer, the end capped dimethyl siloxane of molecular chain two terminal silanol groups-diphenyl siloxane multipolymer, the end capped dimethyl polysiloxane of molecular chain two terminal trimethoxy siloxyies, the end capped dimethyl siloxane of molecular chain two terminal trimethoxy siloxyies-methylphenyl siloxane multipolymer, the end capped dimethyl siloxane of molecular chain two terminal trimethoxy siloxyies-diphenyl siloxane multipolymer, the end capped dimethyl polysiloxane of molecular chain two terminal methyl group dimethoxy siloxyies, the end capped dimethyl polysiloxane of molecular chain two terminal triethoxy-silicane oxygen bases, the dimethyl polysiloxane of molecular chain two terminal 2-trimethoxy siloxy-ethyl cappings etc.These can use a kind separately, also can be used in combination more than 2 kinds.
(i) contain (promptly at least 1 of at least 3 silane that combine hydrolization group with Siliciumatom or its partial hydrolysis condenses in 1 molecule of component, the remaining organopolysiloxane of preferred hydrolization group more than 2) for playing the component of solidifying agent effect, when the stock polymer of (h) component contains at least 2 silanol groups in 1 molecule beyond with Siliciumatom bonded hydrolization group the time, can be omitted in the cooperation in the composition.As above-mentioned silane, preferred formula: R
8 eSiX
4-e(in the formula, R
8Be to replace or unsubstituted 1 valency alkyl, X is a hydrolization group, and e is 0 or 1) shown in silane.As above-mentioned R
8, alkyl such as special preferable methyl, ethyl, alkenyls such as vinyl, allyl group, propenyl, aryl such as phenyl.As above-mentioned X, can enumerate with above-mentioned (h) component in as and the identical group of the illustrative group of Siliciumatom bonded hydrolization group, can enumerate for example alkoxyl group, alkenyloxy, ketoxime base, acyloxy, amino, aminooxy etc.
As the concrete example of this silane or its partial hydrolysis condenses, can enumerate for example Union carbide A-162, vinyltriethoxysilane, vinyltriacetoxy silane, tetraethoxy etc. and their partial hydrolysis condenses.These can use a kind separately, also can be used in combination more than 2 kinds.
In this composition, the content of above-mentioned silane or its partial hydrolysis condenses, usually relative (h) component 100 mass parts are preferably 0.01～20 mass parts, are preferably 0.1～10 mass parts especially.If this contains the lower limit of the above-mentioned scope of quantity not sufficient, then the storage stability of Zhi Bei composition reduces, or has the cementability downward trend, on the other hand, if surpass the upper limit of above-mentioned scope, the tendency that then exists the curing of the composition of preparation significantly to slow down.
In addition, (j) condensation catalyst of component is any composition, when above-mentioned silane or its partial hydrolysis condenses for example have aminooxy, amino, ketoxime base etc., can not use.As this condensation catalyst, can enumerate for example organic titanate such as tetrabutyl titanate, titanium isopropylate; Diisopropoxy two (methyl aceto acetate) closes titanium, diisopropoxy two (ethyl acetoacetic ester) closes organic titanium huge legendary turtle compounds such as titanium; Tri acetylacetonato closes aluminium, three (methyl aceto acetate) and closes organo-aluminium compounds such as aluminium; Four (methyl ethyl diketones) close organic zirconates such as zirconium, tetrabutyl zirconium; Organo-tin compounds such as two sad two fourth tin, dibutyl tin dilaurate, two (2-ethylhexanoate) two fourth tin; The metal-salt of organic carboxyl acids such as naphthenic acid tin, oleic acid tin, butyric acid tin, cobalt naphthenate, Zinic stearas; Amine compound and salt thereof such as hexylamine, phosphoric acid lauryl amine; Quaternary ammonium salts such as benzyl triethyl ammonium ammonium acetate; Alkali-metal lower aliphatic hydrochlorate such as Potassium ethanoate, lithium nitrate; Dialkyl group oxyamines such as dimethyl hydroxyl amine, diethyl oxyamine; Contain the silicoorganic compound of guanidine radicals etc.These can use a kind separately, also can be used in combination more than 2 kinds.
In this composition, when using the condensation catalyst of above-mentioned (j) component, there is no particular restriction for its use level, can be significant quantity as catalyzer, usually with respect to (h) component 100 mass parts, be preferably 0.01～20 mass parts, be preferably 0.1～10 mass parts especially.When using this catalyzer, if the lower limit that contains the above-mentioned scope of quantity not sufficient of this catalyzer, then since the composition that the difference of linking agent kind prepares sometimes can not solidify fully, on the other hand, if surpass the upper limit of above-mentioned scope, then the storage stability of the composition of preparation descends sometimes.
(B) component that contains in the silicon rubber composition for electrode circuit protection of the present invention is an inorganic ion exchanger, is preferably inorganic anion exchanger composed or inorganic zwitter-ion permutoid.
As inorganic ion exchanger, can enumerate for example following compound.Aluminosilicate such as natural zeolite, synthetic zeolite; Metal oxide such as aluminum oxide, magnesium oxide; Oxyhydroxide or hydrous oxides such as oxidizing aqueous titanium, oxidizing aqueous bismuth, oxidizing aqueous antimony; Acid-salt such as zirconium phosphate, titanium phosphate; Basic salt or compound hydrous oxides such as hydrotalcite; Assorted Tripyrophosphoric acid classes such as phospho-molybdic acid antimony; Or six cyano group iron (III) salt or six cyano group zinc etc., wherein, the viewpoint of the ionic impurity under resistance to chemical reagents and the moisture-proof condition can be the oxyhydroxide or the hydrous oxide of metal, preferred oxidizing aqueous titanium, oxidizing aqueous bismuth, oxidizing aqueous antimony etc.
Wherein, preferred anionic exchange and do not contain bismuth system, the aluminium system of antimony, the inorganic ion exchanger of zirconium system.As the preferred concrete example of the inorganic ion exchanger of (B) component, can enumerate the IXE of East Asia synthetic (strain), trade(brand)name comprises IXE500, IXE530, IXE550, IXE700, IXE700F, IXE800 etc.In addition, can illustrative hydrotalcite-based compound as other inorganic ion exchangers, for having the compound that contains magnesium, aluminium of laminate structure, trade(brand)name comprises KW2200, KW2100, DHT-4A, DHT-4B, DHT-4C (consonance chemical industry (strain) system) etc., the corrosion that hydrotalcite produces about sulfide, to compare its patience poor with the oxyhydroxide of the above-mentioned bismuth system of not containing antimony, aluminium system, zirconium system or hydrous oxide.These inorganic ion exchangers preferably use below the 5 μ m in this purposes, are generally 0.01～5 μ m, the median size of preferred especially 0.1～5 μ m.In addition, above-mentioned various inorganic ion exchangers can use a kind separately, also can more than 2 kinds and use.
In addition, this median size for example can be used the particle size distribution device that adopts laser diffractometry etc. etc., obtains as weighed average (or intermediate value footpath) etc.
(B) inorganic ion exchanger of component can add 0.1～50 mass parts with respect to curable silicone rubber composition 100 mass parts as above-mentioned (A) component, can add 0.5～30 mass parts especially.If this use level is very few, then foreign ion absorption capture weak effect reduces if cross the mechanical property of the silicon rubber that this composition is solidified and prepare, and is therefore not preferred.
Can in silicon rubber composition for electrode circuit protection of the present invention, cooperate above-mentioned composition in addition as required.For example be used for the thermal expansivity, physical strength, thermotolerance, resistance to chemical reagents, flame retardant resistance, the combustion coefficient of expansion, gas permeation rate of the cured article of shrinking percentage when solidifying and preparation and (B) precipitation of component prevent to wait the suitably various additives of adjustment.As these any compositions, can enumerate inanimate matter weighting agent, thermotolerance rising agent, platinum control agent (addition reaction control agent), the polymerization in addition of (B) component and forbid agent (prolonging agent working life) etc.In addition, can cooperate to give bonding principal component, for example organoalkoxysilane (for example tetraalkoxysilane and/or its hydrolytic condensate) or following illustrative silane coupling agent etc.
Here, the inanimate matter weighting agent is a material of giving physical strengths such as hardness that rubber composition is decided and tensile strength.As weighting agent, can be normally used material in the rubber composition.Specifically, can enumerate silica-based weighting agents such as silicon-dioxide that pyrogenic silica (smog matter silicon-dioxide) for example, crystallinity silicon-dioxide (quartz powder), precipitation threshold silicon-dioxide, hydrophobization handle, silicon-dioxide aerosol, can enumerate glass fibre, titanium oxide, lime carbonate, magnesiumcarbonate etc. in addition, these materials can use a kind separately, also can make up more than 2 kinds.As this examples of material, in silica-based weighting agent, as wetting ability silicon-dioxide, can enumerate Aerosil 130,200,300 (Japanese Aerosil society, Degussa society system), CabosilMS-5, MS-7 (Cabot society system), RheorosilQS-102,103 (moral mountain Cao Da society system), NipsilLP (Japanese silicon-dioxide corporate system) etc.In addition, as hydrophobic silica, can enumerate AerosilR-812, R-812S, R-972, R-974 (Degussa society system), RheorosilMT-10 (moral mountain Cao Da society system), NipsilSS series (Japanese silicon-dioxide corporate system), as crystallinity silicon-dioxide, can enumerate Network リ ス ラ イ ト, Minusil, Imisil etc.The use level of weighting agent is preferably 5～300 mass parts with respect to (a) component 100 mass parts, more preferably 20～200 mass parts.
As the thermotolerance rising agent, can use titanium oxide, cerium oxide, cerous hydroxide, ferric oxide (red iron oxide) etc.These components can be used separately or and use.As red iron oxide, preferably use black oxidation iron oxide red (Fe
3O
4), the red (Fe of red iron oxide
2O
3).
These inanimate matter weighting agents can directly use, and can be that coupling agent, dimethyl polysiloxane, stearic acid etc. carry out using after the surface treatment with silane, silazane, titanic acid ester also.
In this case, as silane be, silazane is a coupling agent, can enumerate hexamethyldisilazane, the divinyl TMDS tetramethyldisilazane, organosilicon ammonia alkanes such as six organic radical disilazane such as phenylbenzene TMDS tetramethyldisilazane, vinyltriethoxysilane, vinyltrimethoxy silane, divinyl dimethoxy silane, vinyl three (methoxy ethoxy) silane etc. contains the alkoxyl silicone alkanes of vinyl, organochlorines such as trimethylammonium chlorosilane are for silicane, aminosilane classes such as trimethylammonium aminosilane, glycidoxy-propyltrimethoxy silane, the epoxypropoxy methyldiethoxysilane, (epoxycyclohexyl) ethyl trimethoxy silane etc. contains the alkoxyl silicone alkanes of epoxy functional group, methyl allyl acyloxypropyl trimethoxysilane, methacryloxypropyl triethoxyl silane etc. contains the alkoxyl silicone alkanes of (methyl) acryloxy functional groups, dimethyldimethoxysil,ne, trimethylethoxysilane and aminopropyl trimethoxysilane etc. contain the alkoxyl silicone alkanes of not replacement or halogen-substituted alkyl etc.
In addition; as titanic acid ester is coupling agent, can enumerate titanium isopropylate, tetra-n-butyl titanate, butyl (tetra) titanate dimer, metatitanic acid four stearyl esters, triethanolamine titanate, etheric acid titanium, methyl aceto acetate and close titanium, lactic acid titanium, octylene glycol titanate, sec.-propyl three stearyl-titanic acid ester, sec.-propyl three (dodecyl) benzenesulfonyl titanic acid ester, sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester, two (dioctylphyrophosphoric acid ester) oxo acetic ester titanic acid ester, two (dioctylphyrophosphoric acid ester) ethylidene titanic acid ester etc.
As the addition reaction control agent, can enumerate the organopolysiloxane that the vinyl cyclotetrasiloxane contains vinyl like this, cyanacrylate, the toxilic acid alkyl ester, acetylene series alcohols and silane thereof, silicone-modified thing, hydroperoxide, Tetramethyl Ethylene Diamine, benzotriazole and their mixture etc.
Forbid agent (prolonging agent working life) as polymerization, can enumerate quinhydrones, methoxyl group quinhydrones etc.
There is no particular restriction for the manufacture method of rubber composition of the present invention, can be with known method manufacturing.
Be cured under the corresponding known moulding of kind of composition employing of the present invention and its curable silicone rubber composition, curing, the condition of cure, the cured article of preparation is (H under harsh condition for example
2When S atmosphere) carrying out the electrode test of flat-panel monitor, give very high erosion resistance.
In addition, silicon rubber composition for electrode circuit protection of the present invention for the sulfuration of the metallic circuit that prevents flat-panel monitors such as metallic circuit, particularly LCD, PDP, organic EL etc., corrosion effectively.In this case,, adopt, form 10～1000 μ m, the particularly epithelium of 100～500 μ m, its solidified method at the circuit part coating above-mentioned composition that should protect as guard method.
Embodiment
Below enumerate embodiment and comparative example the present invention is carried out specific description, but the present invention is not limited to following embodiment.In addition, in the following example, " part " expression " mass parts ", Me represents methyl, Et represents ethyl.
Embodiment 1
At following formula (i)
(wherein, add following formula (ii) in 100 parts of the end capped dimethyl polysiloxanes of two terminal ethylenyl groups dimethylsilane oxygen bases shown in L=450)
(wherein, L=10, the octanol modified solution of the organic hydride polysiloxane M=8) and 0.05 part of chlorination platinic acid, it is 1.5 that the amount of organic hydride polysiloxane makes the mol ratio of the vinyl in SiH base and the above-mentioned dimethyl polysiloxane (i) that contains vinyl, in 100 parts of rubber compositions that fully stirs preparation, add 10 parts of IXE500 (East Asia synthetic (strain) system, the bismuth that does not contain antimony is inorganic anion exchanger composed), modulate aqueous rubber composition.Said composition is solidified.
According to JIS K6301 the rerum natura of the cured article of preparation is measured.In addition, hardness adopts spring loaded A type trier.It the results are shown in table 1.
In addition, will be placed on the glass substrate having implemented silver plated substrate on the copper, be coated with the above-mentioned composition of thick 0.3mm in the above, it was solidified 1 hour, make assess sample.This assess sample is put into the encloses container of 2 liters of volumes, in this encloses container, put into (NH simultaneously
4)
2S20g and H
2O10g is producing H
2Under the air-tight state of S gas, place the time shown in the table 2 down, the corrosion production of having implemented silver plated substrate on copper is estimated at 23 ℃.The results are shown in table 2.
Embodiment 2
In 100 parts of above-mentioned two end capped dimethyl polysiloxanes of terminal ethylenyl groups dimethylsilane oxygen base (i), add above-mentioned organic hydride polysiloxane (ii) and the octanol modified solution of 0.05 part of chlorination platinic acid, it is 1.5 that the amount of organic hydride polysiloxane makes the mol ratio of the vinyl in SiH base and the above-mentioned dimethyl polysiloxane (i) that contains vinyl, in 100 parts of rubber compositions that fully stirs preparation, add 20 parts of IXE530, modulate aqueous rubber composition.Said composition is solidified.
Identical with embodiment 1, the rerum natura and the corrosion test of the cured article of mensuration preparation.
Embodiment 3
In following formula (iii)
(wherein, L=450) add 0.1 part of titanium chelate catalyzer (trade(brand)name TC-750) in 100 parts of the end capped dimethyl polysiloxanes of two terminal trimethoxy siloxyies shown in, in 100 parts of rubber compositions that fully stirs preparation, add 5 parts of IXE500, modulate aqueous rubber composition.
Except solidifying, measure the rerum natura and the corrosion test of cured article similarly to Example 1 at 23 ℃/50%RH, under 24 hours.
Embodiment 4
(iii) add 0.1 part of titanium chelate catalyzer (trade(brand)name TC-750) in 100 parts at the end capped dimethyl polysiloxane of above-mentioned two terminal trimethoxy siloxyies, in 100 parts of rubber compositions that fully stirs preparation, add 30 parts of IXE500, modulate aqueous rubber composition.
Except solidifying, measure the rerum natura and the corrosion test of cured article similarly to Example 1 at 23 ℃/50%RH, under 24 hours.
Embodiment 5
At following formula (iV)
Shown in mix 2 parts of 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2 in 100 parts of the buttery organopolysiloxanes; 4,1 part, 10 parts IXE530 of the partial hydrolysis condenses of 1 part of 6-trimethylbenzoyl phenylbenzene, tetramethoxy-silicane (methoxyl group siloxane oligomer) and following formula V
0.1 part of shown titanium chelate, preparation radiation-curable organopolysiloxane composition.
Except (illumination: 80W/cm in the stove that possesses 2 metal halide mercuryvapour lamps
2), to said composition shine ultraviolet ray in 2 seconds (energy: 800mJ) be cured outside, measure the rerum natura and the corrosion test of cured article in the same manner with embodiment 1.
Comparative example 1
In embodiment 1,, prepare identical aqueous rubber composition except not adding the IXE530.Similarly to Example 1 said composition is tested.
Comparative example 2
In embodiment 3,, prepare identical aqueous rubber composition except not adding the IXE530.Similarly to Example 3 said composition is tested.
Comparative example 3
In embodiment 5,, prepare identical aqueous rubber composition except not adding the IXE530.Similarly to Example 5 said composition is tested.
Table 1
Table 2
Zero: do not have corrosion △: a part of variable color *: become black (corrosion fully)
Claims (7)
1, silicon rubber composition for electrode circuit protection is characterized in that: with
(A) curable silicone rubber composition 100 mass parts,
(B) do not contain the bismuth system of antimony or inorganic ion exchanger 0.1～50 mass parts of zirconium system and be necessary component.
2, the described silicon rubber composition for electrode circuit protection of claim 1, wherein curable silicone rubber composition is
(a) contain more than 2 organopolysiloxane with Siliciumatom bonded alkenyl in 1 molecule,
(b) have more than 2 and organic hydride polysiloxane Siliciumatom bonded hydrogen atom in 1 molecule, wherein, with Siliciumatom bonded hydrogen atom be 0.1～5.0 with respect to the mol ratio in (a) component with Siliciumatom bonded alkenyl,
(c) the addition curable rubber composition of the platinum family series catalysts of catalytic amount formation.
3, the described silicon rubber composition for electrode circuit protection of claim 1, wherein curable silicone rubber composition is
(d) ultraviolet reactive organopolysiloxane,
(e) Photoepolymerizationinitiater initiater
The ultraviolet hardening rubber composition that constitutes.
4, the described silicon rubber composition for electrode circuit protection of claim 1, wherein curable silicone rubber composition is
(f) contain in 1 molecule more than 2 with the organopolysiloxane of Siliciumatom bonded alkenyl,
(g) organo-peroxide
The organic peroxide curing type rubber composition that constitutes.
5, the described silicon rubber composition for electrode circuit protection of claim 1, wherein curable silicone rubber composition is
(h) have at least in 1 molecule two silanol groups or with the organopolysiloxane of Siliciumatom bonded hydrolization group,
(i) as the water-disintegrable silane of any component or its partial hydrolysis condenses,
(j) condensation catalyst of any component of conduct
The condensation cured type rubber composition that constitutes.
6, electrode circuit protection material, its cured article by each described silicon rubber composition for electrode circuit protection of claim 1～5 constitutes.
7, electric, electronic component, wherein telegraph circuit coats protection with the cured article of each described silicon rubber composition for electrode circuit protection of claim 1～5.
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| JP2006206816A (en) * | 2005-01-31 | 2006-08-10 | Ge Toshiba Silicones Co Ltd | Room temperature-curable polyorganosiloxane composition |
| JP4647321B2 (en) * | 2005-01-31 | 2011-03-09 | 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 | Room temperature curable polyorganosiloxane composition |
| JP2006330277A (en) * | 2005-05-25 | 2006-12-07 | Fuji Xerox Co Ltd | Carrier for electrostatic latent image developer and method for manufacturing the same, electrostatic latent image developer, and image forming apparatus |
| JP2007161999A (en) * | 2005-11-17 | 2007-06-28 | Shin Etsu Chem Co Ltd | Addition curing silicone composition for cipg yielding cured product with excellent compression set characteristics and method of reducing compression set of cured product from the composition |
| JP5015476B2 (en) * | 2006-03-01 | 2012-08-29 | 東レ・ダウコーニング株式会社 | Electrode / electric circuit protective agent composition |
| WO2009099099A1 (en) * | 2008-02-07 | 2009-08-13 | Nippon Steel Chemical Co., Ltd. | Silicone resins and manufacturing method thereof, as well as curable resin compositions that comprise said silicone resins |
| US20130032853A1 (en) * | 2010-04-22 | 2013-02-07 | Nippon Kayaku Kabushiki Kaisha | Silver Anti-Tarnishing Agent, Silver Anti-Tarnishing Resin Composition, Silver Anti-Tarnishing Method, And Light-Emitting Diode Using Same |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2005120155A (en) | 2005-05-12 |
| TW200513498A (en) | 2005-04-16 |
| KR101092092B1 (en) | 2011-12-12 |
| TWI335348B (en) | 2011-01-01 |
| CN1621448A (en) | 2005-06-01 |
| KR20050036749A (en) | 2005-04-20 |
| JP4645793B2 (en) | 2011-03-09 |
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