CN1803925A - Flame-retardant heat-conductive silicone former and method of producing thereof - Google Patents
Flame-retardant heat-conductive silicone former and method of producing thereof Download PDFInfo
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- CN1803925A CN1803925A CN 200610051332 CN200610051332A CN1803925A CN 1803925 A CN1803925 A CN 1803925A CN 200610051332 CN200610051332 CN 200610051332 CN 200610051332 A CN200610051332 A CN 200610051332A CN 1803925 A CN1803925 A CN 1803925A
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Abstract
The invention provides a flame-retardant/heat-conductive silicone molded article which has low hardness and improved handleability, and to provide a method for producing the same. This flame-retardant/heat-conductive silicone molded article is characterized by comprising a molded article comprising the cured product of a composition which comprises (a) 100 pts.mass of an organopolysiloxane having alkenyl groups bound to silicon atoms, (b) 200 to 5,000 pts.mass of a heat-conductive filler, (c) an SiH group-having organohydrogenpolysiloxane in an amount of 0.1 to 5.0 moles of the SiH groups in the component (c) per mole of the alkenyl groups in the component (a), and (d) an effective amount of a platinum group metal-based addition reaction catalyst, and a surface layer formed on the surface of the molded article and comprising (e) an SiH group-having organohydrogenpolysiloxane and (f) a flame retardant, wherein an addition reaction product is produced between the component (e) and the component (a).
Description
Technical field
[0001]
The present invention relates to a kind ofly be effective as fire-retardant, the heat-conductive silicone former that is used to make electronic unit refrigerative heat-transfer matcrial, and a kind of like this production method of molding and use this molding to make electronic unit refrigerative method.
Background technology
[0002]
For example CPU, driver IC and memory chip improvement, the size of proceeding performance and speed reduces the LSI chip that for example uses in Personal Computer, digital video video disc machine and the portable telephone etc. along with electronics and integrated horizontal improves, and the heat that these chips took place increases considerablely.Such chip temperature rising that heating took place can cause that chip is malfunctioning or depleted.As a result, the heat dissipation method that many inhibition run duration chip temperatures raise has been proposed, and the various heat dissipation element that uses in these class methods.
[0003]
Usually, used the high metal sheet of thermal conductivity level for example the scatterer of aluminium or copper be used to suppress the rising of run duration chip temperature always.These scatterers conduct the heat that this chip takes place, and utilize that the temperature difference makes this heat radiate from spreader surface between this scatterer and the outside atmosphere.
[0004]
In these cases, be transported to this scatterer expeditiously in order to ensure the heat that this chip took place, this scatterer must closely adhere on this chip, but the height of each chip and and the difference of the tolerance levels aspect that interrelates of assembling process mean the molding or the grease of a kind of favourable flexibility of configuration between this chip and scatterer usually, therefore, heat from this chip to the conduction of this scatterer through molding or grease take place thus.
[0005]
Shaping prod provides than grease excellent operation energy, and especially, the heat conductance shaping adult (being heat conductance silicone rubber molding) of formation such as use heat conductance silicone rubber is used for miscellaneous field.
[0006]
These heat conductance moldinies better have low-level hardness in the hope of the adhesion level of improvement with this chip and scatterer, and better are configured as fine sheet.Yet the heat conductance molding of soft shows intensive viscosity degree, means that they can be difficult to separate with hand during on the parts that are installed to the needs heat radiation by hand, and often installs and can need a lot of time.In addition, when drawing this heat conductance molding carrying out when this breaks away from hand, then this heat conductance molding can extend.Like this, fully discerned the bad processing property of heat conductance molding.Carried out about by in this molding, mixing the test that strongthener solves the elongation of this type of heat conductance molding, but this causes that heat dispersion reduces.Patent documentation 1 has proposed to produce a surface that a kind of multilayered structure prevents this molding delamination and give this molding with non-binding property by form a soft layer on enhancement layer top, thereby improves the method for processing property.Yet, in order to produce this molding, need many steps, comprise enhancement layer forming step and soft layer forming step, and production cost has improved also.Patent documentation 2 has proposed by forming a hard non-bonding coat on the surface that a kind of linking agent is administered to this molding and on the molding surface.The molding of having used a kind of linking agent in its surface according to patent documentation 2 can significantly suppress any reduction of heat dispersion.Yet, confirm that use the flame retardant resistance of preceding this molding with this linking agent and compare, the flame retardant resistance of this molding has worsened.The heat conductance molding often needs the heat conductance and the flame retardant resistance of favourable level, but the molding of patent documentation 2 can not address that need.
[patent documentation 1] Japanese patent gazette No.2,536,120
[patent documentation 2] Japanese patent gazette No.3,280,224
Summary of the invention
The problem that the present invention is intended to solve
[00071
The present invention has considered above-described problem, and purpose provides a kind ofly to be had soft but demonstrate fire-retardant, the heat-conductive silicone former of the processing property of improvement, and a kind of like this production method of molding and use the method for this molding cooling electronic components.
The means of dealing with problems
[0008]
As the result of the invention research that is intended to achieve the above object, inventor of the present invention finishes the present invention finally.In other words, the invention provides
A kind of fire-retardant, heat-conductive silicone former comprises
From the molding that a kind of cured product of composition forms, said composition comprises
(a) a kind of organopolysiloxane that contains with the alkenyl of silicon atom bonding of 100 mass parts,
(b) a kind of heat conductive filler of 200～5000 mass parts,
(c) a kind of organic hydrogen polysiloxanes that contains with the hydrogen atom of silicon atom bonding, its quantity be enough to for the every 1mol key thiazolinyl in the described composition (a) provide 0.1～5.0mol and silicon atom bonding in the described composition (c) hydrogen atom and
(d) platinum metals of significant quantity is an addition reaction catalyst; With
A upper layer that forms on described molding surface, this upper layer comprises
(e) a kind of contain with the organic hydrogen polysiloxanes of the hydrogen atom of silicon atom bonding and
(f) a kind of fire retardant, wherein
The addition reaction product is to take place between the described organopolysiloxane of the described organic hydrogen polysiloxanes of described composition (e) and described composition (a).
And then the present invention also provides a kind of like this production method of fire-retardant, heat-conductive silicone former.
In addition, the present invention also provides and uses this molding to make electronic unit refrigerative method.
The invention effect
[0009]
Fire-retardant, heat-conductive silicone former of the present invention is very submissive, thereby easily deformation and be obedient to the profile of the object that needs heat radiation, thereby provide favourable heat dissipation characteristics, a upper layer is arranged on the surface of this molding, thereby the excellent operation energy is provided, and shows excellent flame.Therefore, this shaping physical efficiency is effective as heat-transfer matcrial and is disposed at heat-generating electronic part and heat dissipation element for example between scatterer or the circuit card, in the hope of making this electronic unit cooling.
Embodiment
[0010]
More detailed description of the present invention is as follows.
[0011]
Composition (a)
Composition (a) is a kind of organopolysiloxane that contains with the alkenyl of silicon atom bonding.This organopolysiloxane of composition (a) can be straight chain otherwise ring texture, and can comprise branched structure at this intramolecularly under any one situation therein, although with regard to physicals for example better is a kind of linear chain structure basically with regard to the physical strength of cured product, and preferably a kind of its main chain comprises the straight chain diorganopolysiloxanecompositions of two organo-siloxane repeating units.Position for these one or more alkenyls is not particularly limited.Those wherein composition (a) be under a kind of situation of linear chain structure, this alkenyl can only be present in molecular chain-end or be present in non-chain end position, perhaps also may reside in this two kinds of positions.The two ends of straight chain diorganopolysiloxanecompositions all have three organo-siloxane bases usually.
[0012]
The specific examples of composition (a) comprises the organopolysiloxane of general formula shown below (1)～(3) representative:
X-Si(R
1)
2-[OSi(R
1)
2]
a-[OSi(R
1)(X)]
b-X (1)
X-Si(R
1)
2-[OSi(R
1)
2]
a-[OSi(R
1)(X]
c-R
1 (2)
R
1-Si(R
1)
2-[OSi(R
1)
2]
a-[OSi(R
1)(X)]
d-R
1 (3)
(each R in the formula
1All represent one not have the monovalence alkyl that replaces or replacement is arranged independently, the not fatty family of this alkyl unsaturated link(age), and better contain 1～12 even better 1～10, best 1～6 carbon atom, X represents an alkenyl that better contains 2～8 even better 2～5 carbon atoms, a and b represent 0 or bigger integer, and c and d represent 1 or bigger integer).These organopolysiloxanes can or use separately, or two or more different compounds are used in combination.When using two or more organopolysiloxanes, the viscosity of these two kinds of materials can be different.
[00131
R
1Example comprise alkyl, for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, heptyl, octyl group, nonyl, decyl and dodecyl; Cycloalkyl, for example cyclopentyl, cyclohexyl and suberyl; Aryl, for example phenyl, tolyl, xylyl, naphthyl and xenyl; Aralkyl, for example benzyl, styroyl, hydrocinnamyl and methyl-benzyl; And such group, wherein, at least one hydrogen atom is by a halogen atom for example fluorine atom, chlorine atom or bromine atoms or a cyano group replaces, comprises chloromethyl, 2-bromotrifluoromethane, 3-chloropropyl, 3 in the above-mentioned alkyl, 3,3-trifluoro propyl, chloro-phenyl-, fluorophenyl, cyano ethyl and 3,3,4,4,5,5,6,6,6-nine fluorine hexyls.The nothing of 1～3 carbon atom replaces or substituted alkyl for example methyl, ethyl, propyl group, 3,3 is arranged in these groups, and 3-trifluoro propyl and cyano ethyl and phenyl are preferably, and methyl and phenyl are special ideal.R wherein
1At least the 80mol% of group is that the compound of methyl is good especially.And then, this R
1Group can be identical or different.
[0014]
The example of group x comprises vinyl, allyl group, propenyl, pseudoallyl, butenyl, hexenyl and cyclohexenyl.In these groups, low-grade alkenyl for example vinyl and allyl group is preferably, and vinyl is special ideal.
[0015]
Above-mentioned a is 0 or bigger integer, better is one and satisfies the integer of 10≤a≤10,000 even be more preferably one and satisfy the integer of 50≤a≤2,000 and integer that satisfies 100≤a≤1,000 preferably.Above-mentioned b is one 0 or bigger integer, better is an integer that satisfies 0≤b/ (a+b)≤0.5, even being more preferably one, to satisfy be the integer of 0≤b/ (a+b)≤0.1.Above-mentioned c is one 1 or bigger integer, better is an integer that satisfies 0≤c/ (a+c)≤0.5, even is more preferably an integer that satisfies 0≤c/ (a+c)≤0.1.Above-mentioned d is one 1 or bigger integer, better is an integer that satisfies 0≤d/ (a+d)≤0.5, even is more preferably an integer that satisfies 0≤d/ (a+d)≤0.1.
[0016]
Composition (b)
Composition (b) is a kind of heat conductive filler.The mean particle size of composition (b) is more fortunately in 0.1～100 μ m even better 0.5～50 μ m, best 0.5～30 mu m range.At this, mean particle size means the definite weight-average value (or middle several diameter) of particle size distribution device of using the laser diffraction method by a kind of.
[0017]
Can use the material that typically is used as heat conductive filler as composition (b), the specific examples of suitable material comprises for example non-magnetic copper of metal and aluminium; Oxide compound is aluminum oxide, silicon-dioxide, magnesium oxide, red iron oxide, beryllium oxide, titanium oxide and zirconium white for example; Nitride is aluminium nitride, silicon nitride and boron nitride for example; Carbide is silicon carbide for example; With man-made diamond etc.These heat conductive fillers can use separately or two or more different filler combination are used.When using two or more different fillers, its mean particle size can be different.
[0018]
The usage quantity of composition (b) is for per 100 mass parts compositions (a), typically 200～5, in 000 mass parts, better 300～1500 mass parts scopes.If usage quantity is too big, the workability that then comprises the composition of composition (a)～(d) worsens, and makes into the deformation difficulty, and if usage quantity is too little, then can't obtain the silicone molding of desired heat conductance level.
[0019]
Composition (c)
Composition (c) is that a kind of each intramolecularly contains at least two, better three or more organic hydrogen polysiloxanes with the hydrogen atom (being the Si-H yl) of silicon atom bonding.The organic hydrogen polysiloxanes of composition (c) can be a kind of straight chain or ring texture, and therein under any one situation, can comprise branched structure at this intramolecularly.Position to the Si-H base is not particularly limited.Those wherein composition (c) be under a kind of situation of linear chain structure, the Si-H base can only be present in molecule chain end or non-terminal position, perhaps also may reside in this two kinds of positions.
[0020]
The specific examples of composition (c) comprises the organic hydrogen polysiloxanes of general formula shown below (4)～(6) representative:
R
2-Si(R
2)
2-[OSi(R
2)
2]
e-[OSi(R
2)(H)]
f-OSi(R
2)
2-R
2 (4)
R
2-Si(R
2)
2-[OSi(R
2)
2]
e-[OSi(R
2)(H)]
g-OSi(R
2)
2-H (5)
H-Si(R
2)
2-[OSi(R
2)
2]
e-[OSi(R
2)(H)]
h-OSi(R
2)
2-H (6)
(in the formula, each R
2All represent one not have the monovalence alkyl that replaces or replacement is arranged independently, this alkyl does not contain the aliphatics unsaturated link(age) and better contains 1～12 even better 1～10, best 1～6 carbon atom, e and h represent 0 or bigger integer, and f and g represent 1 or bigger integer).These organic hydrogen polysiloxanes can or use separately, or two or more different compounds are used in combination.
[0021]
R
2Example comprise alkyl, for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, heptyl, octyl group, nonyl, decyl and dodecyl; Cycloalkyl, for example cyclopentyl, cyclohexyl and suberyl; Aryl, for example phenyl, tolyl, xylyl, naphthyl and xenyl; Aralkyl, for example benzyl, styroyl, hydrocinnamyl and methyl-benzyl; And such group, wherein, at least one hydrogen atom is by a halogen atom for example fluorine atom, chlorine atom or bromine atoms or a cyano group replaces, comprises chloromethyl, 2-bromotrifluoromethane, 3-chloropropyl, 3 in the above-mentioned alkyl, 3,3-trifluoro propyl, chloro-phenyl-, fluorophenyl, cyano ethyl and 3,3,4,4,5,5,6,6,6-nine fluorine hexyls.The nothing of 1～3 carbon atom replaces or substituted alkyl for example methyl, ethyl, propyl group, 3,3 is arranged in these groups, and 3-trifluoro propyl and cyano ethyl and phenyl are preferably, and methyl and phenyl are special ideal.And then, this R
2Group can be identical or different.
[0022]
Above-mentioned e is 0 or bigger integer, and better be 0～500 in addition better 5～100 scopes in integer.Above-mentioned f be 1 or bigger integer and better be 1～100 in addition better 2～50 scopes in integer.Above-mentioned g is 1 or bigger integer, and better be 1～100 in addition better 1～50 scope in integer.Above-mentioned h is 0 or bigger integer, and better be 0～100 in addition better 0～50 scope in integer.
[0023]
The usage quantity of composition (c) typically is enough to provide 0.1～5.0mol, better 0.3～3mol even better 0.5～2mol Si-H base in the composition (c) for the every 1mol alkenyl in the composition (a).If the quantity of composition (c) is lower than the lower limit of this scope, then the curing of said composition may be insufficient, resulting cured product possibly can't be operated as molding, and if this quantity surpasses its upper limit, then thermal conductivity may worsen, thereby this otherwise be to cause the cause that the bondability with the object that needs heat radiation reduces too firmly because the molding that forms from the cured product of said composition becomes, thereby or be since during the thermoforming foaming cause the cause that the cavity takes place in this molding.
[0024]
Composition (d)
The platinum metals of composition (d) is the function that solidifying agent has the addition reaction (hydrosilylation reaction) between the Si-H base of the alkenyl of acceleration composition (a) and composition (c) and composition (e).Composition (d) can use in the usual hydrosilylation catalyzer any.The specific examples of this catalyzer comprises platinum metals for example platinum (comprising platinum black), rhodium and palladium; Platinum chloride is H for example
2PtCl
4NH
2O, H
2PtCl
6NH
2O, NaHPtCl
6NH
2O, KHPtCl
6NH
2O, Na
2PtCl
5NH
2O, K
2PtCl
4NH
2O, PtCl
4NH
2O, PtCl
2And Na
2HPtCl
4NH
2O (n represents 0～6 integer in the formula, and better is 0 or 6); Platinic chloride, platinichloride and pure modification Platinic chloride (seeing U.S. Patent No. 3,220,972); The complex compound of Platinic chloride and alkene (seeing U.S. Patent No. 3,159,601, No.3,159,662 and No.3,775,452); The platinum metals of carrier band on carriers such as aluminum oxide, silicon-dioxide or charcoal be platinum black or palladium for example; Rhodium-alkene complex; Chlorine three (triphenyl phosphine) rhodium (Wei Erjinsenshi catalyzer); With platinum chloride, Platinic chloride or platinichloride and contain vinylsiloxane, especially contain the complex compound of vinyl cyclosiloxane.
[0025]
It is the effective active of addition reaction catalyst as the platinum metals that the usage quantity of composition (d) only needs sufficient to guarantee, and can increase or reduce according to desirable curing speed.Specifically, as the usage quantity of the platinum metals Mass Calculation for the total mass of composition (a), more fortunately in the scope of 0.1～1000ppm even better 0.5～200ppm, best 1.0～100ppm.
[0026]
Composition (e)
Composition (e) is a kind of composition that is similar to composition (c), and is a kind of organic hydrogen polysiloxanes of the Si-H of containing base.The organic hydrogen polysiloxanes of composition (e) can be straight chain or ring texture, and can comprise branched structure at this intramolecularly under any one situation therein.Position for the Si-H base is not particularly limited.Those wherein composition (e) be under the situation of linear chain structure, this Si-H base can only be present in molecule chain end or non-terminal position, perhaps also can all exist on these two kinds of positions.
[0027]
The specific examples of composition (e) comprises the organic hydrogen polysiloxanes of general formula shown below (7)～(9) representative:
R
3-Si(R
3)
2-[OSi(R
3)
2]
i-[OSi(R
3)(H)]
j-OSi(R
3)
2-R
3 (7)
R
3-Si(R
3)
2-[OSi(R
3)
2]
i-[OSi(R
3)(H)]
k-OSi(R
3)
2-H (8)
H-Si(R
3)
2-[OSi(R
3)
2]
i-[OSi(R
3)(H)]
1-OSi(R
3)
2-H (9)
(in the formula, each R
3All represent one not have the monovalence alkyl that replaces or replacement is arranged independently, this alkyl does not contain the aliphatics unsaturated link(age) and better contains 1～12 even better 1～10, best 1～6 carbon atom, i and 1 represents 0 or bigger integer, and j and k represent 1 or bigger integer).These organic hydrogen polysiloxanes can or use separately, or two or more different compounds are used in combination.
[0028]
R
3Example comprise alkyl for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, heptyl, octyl group, nonyl, decyl and dodecyl; Cycloalkyl is cyclopentyl, cyclohexyl and suberyl for example; Aryl is phenyl, tolyl, xylyl, naphthyl and xenyl for example; Aralkyl is benzyl, styroyl, hydrocinnamyl and methyl-benzyl for example; And such group, at least one hydrogen atom comprises chloromethyl, 2-bromotrifluoromethane, 3-chloropropyl, 3 by for example fluorine atom, chlorine atom or bromine atoms or the cyano group replacement of a halogen atom in the wherein above-mentioned alkyl, 3,3-trifluoro propyl, chloro-phenyl-, fluorophenyl, cyano ethyl and 3,3,4,4,5,5,6,6,6-nine fluorine hexyls.In the middle of these, the nothing of 1～3 carbon atom replaces or substituted alkyl for example methyl, ethyl, propyl group, chloromethyl, bromotrifluoromethane, 3 is arranged, 3,3-trifluoro propyl and cyano ethyl, and do not have and replace or substituted-phenyl is arranged for example phenyl, chloro-phenyl-and fluorophenyl are special ideal.And then, R
3Group can be identical or different.
[0029]
Above-mentioned i is 0 or bigger integer, and better be 0～500 in addition better 5～100 scopes in integer.Above-mentioned j is 1 or bigger integer, and better be 3～100 in addition better 5～50 scopes in integer.Above-mentioned k is 1 or bigger integer, and better be 3～100 in addition better 5～50 scopes in integer.Above-mentioned 1 is 0 or bigger integer, and better be 3～100 in addition better 5～50 scopes in integer.
[0030]
The organic hydrogen polysiloxanes of the organic hydrogen polysiloxanes of composition (e) and composition (c) can be identical or different.
[0031]
Composition (f)
Composition (f) is a kind of fire retardant.Composition (f) is mixed with composition (e), and be administered on the surface of the molding that forms from the cured product of the composition that contains composition (a)～(d).Therefore, composition (f) better is a kind of demonstrate favourable and common deliquescent fire retardant composition (e).Composition (f) better is the no pigment fire retardant type of typically adding in the silicon-ketone composition.The example of composition (f) comprises nitrogenous compound, amino-modified silicone oil, sulfocompound and P contained compound, and these central compound nitrogen series for example nitrogen-containing heterocycle compound are preferably.Specific examples comprises nitrogenous compound for example benzotriazole and derivative, benzoglyoxaline and triazine and derivative thereof; Although with P contained compound for example trimethyl phosphite 99, triethyl phosphate and triphenyl phosphine nitrogenous compound be preferably, and nitrogen-containing heterocycle compound is special ideal.Benzotriazole based compound (benzotriazole and derivative thereof) is best.
[0032]
For per 100 mass parts compositions (e), the quantity of composition (f) is more fortunately in 0.001～5.0 mass parts even better 0.005～1.0 mass parts scope in the mixture of composition (e) and composition (f).As long as this quantity falls in this scope, just can reach the satisfactory improvement of flame retardant resistance, and the generation of the addition reaction product between composition (e) and the composition (a) is not subjected to big inhibition, this means relatively easily to form upper layer.
[0033]
Other composition
As required, also can in the composition that comprises composition (a)～(d), add various other additives, as long as such interpolation do not damage effect of the present invention, and the example of such additive comprise this heat conductive filler surface treatment agent, be used for regulating curing speed the reaction retarding agent, be used to increase pigment or dyestuff, the flame retardant resistance imparting agent of color and be used to improve the inner pattern releasing agent applicable of said composition from the model or the separating film demoulding.
[0034]
Shape
Shape fire-retardant, thermal conductivity silicone molding of the present invention is not particularly limited, and this shape can be selected according to the purpose purposes, although film or sheet material are preferably.Upper layer is only to form as the lip-deep film of the molding that forms at the cured product from the composition that comprises composition (a)～(d), thereby shape fire-retardant, heat-conductive silicone former of the present invention is not made significant difference.Therefore, this shape is decided by the shape of the molding that forms from the cured product of said composition basically.For example, by said composition being solidified and being configured as film or sheet material, shape fire-retardant, heat-conductive silicone former of the present invention also can be shaped to film or sheet material.Under these circumstances, the thickness of this molding is in 0.1～10mm even better 0.3～5mm scope.And then the thickness of the upper layer that forms on this molding surface better is not more than 100 μ m.Lower limit to the thickness of this upper layer is not particularly limited, as long as this upper layer forms on the whole surface of this molding, but this layer better is about 0.1 μ m or bigger.
[0035]
Use
Fire-retardant, heat-conductive silicone former of the present invention can advantageously for example, be used as the heat-transfer matcrial of electronic unit.This makes this electronic unit effectively to cool off.Under these circumstances, the shape of this molding can be aforesaid film or sheet material.This electronic unit can cool off by this molding is configured between this electronic unit and the heat dissipation element.The example of this electronic unit comprises heat-generating electronic part for example LSI chip, CPU, driver IC, storage chip and transistor.The example of heat dissipation element comprises scatterer and circuit card.
[0036]
Production method
Fire-retardant, heat-conductive silicone former of the present invention can be administered on the surface of the molding that forms from the cured product of the composition that comprises composition (a)～(d) by the mixture with composition (e) and composition (f), make this mixture solidified form upper layer (following this method abbreviates " production method 1 " as) then produces.And then, fire-retardant, heat-conductive silicone former of the present invention also can be by used a kind of its surface coated composition (e) and composition (f) the model or the separator of mixture the composition that comprises composition (a)～(d) is solidified and shaping, thereby obtain a kind of molding that forms from the cured product of said composition, and a upper layer of formation (following this method abbreviates " production method 2 " as) is produced on the surface of this molding.
[0037]
In this manual, said composition can mix according to usual method by each composition that will constitute said composition and produce.Can produce by using conventional method make said composition solidify and be shaped from the molding that the cured product of said composition forms.For example, for said composition being solidified and being configured as film or sheet material, can use and usual addition reaction cure silicone rubber composition be solidified and be configured as those identical conditions that film or sheet material adopt.Said composition even also can solidify and be configured as film or sheet material satisfactorily in room temperature is although can heat when needs.
[0038]
Above-mentioned upper layer is that the surface of the molding that forms at the cured product from the composition that comprises composition (a)～(d) forms.This upper layer comprises composition (e) and composition (f), and between the organopolysiloxane of the organic hydrogen polysiloxanes of composition (e) and composition (a) a kind of addition reaction product takes place.This addition reaction product be by residual component (a) in the base of the Si-H in the composition (e) and this molding thus alkenyl generation addition reaction forms the covalent linkage generation.
[0039]
In production method 1, be administered to the quantity 0.1～100g/m more fortunately of the mixture of lip-deep composition of this molding (e) and composition (f)
2, even better 0.2～20g/m
2, best 1.0～10g/m
2Scope in.Employed application process is not particularly limited, the method that is suitable for comprises that brushing, spraying, rod such as are coated with at directly coating process, with the transfer coating method, wherein this mixture is administered on the another kind of film (for example PET sheet material etc.), then it is pasted on this molding.
[0040]
In production method 2, be administered to the quantity 0.1～100g/m more fortunately of the mixture of composition (e) on this model or the separator and composition (f)
2, even better 0.2～20g/m
2, best 1.0～10g/m
2In the scope.Employed application process is not particularly limited, and the method that is suitable for comprises that brushings, spraying and rod such as are coated with at direct coating process.
Embodiment
[0041]
The following more detailed description of the present invention that is based on embodiment and a series of comparative examples is although in any case the present invention is not limited to the following embodiment that provides." Me " this term represent methylidene.
[0042]
Embodiment 1
To a kind of two ends of a Shinagawa multi-usage mixing machine (Shinagawa Machinery WorksCo., Ltd. makes) middle adding 100 mass parts ethenyl blocking and 25 ℃ of viscosity being arranged all is 600mm
2The dimethyl polysiloxane of/S, a kind of mean particle size of 400 mass parts are that aluminum oxide and a kind of BET specific surface area of 1.0 mass parts of 4 μ m is 68m
2Acetylene black, and with resulting combined hybrid 60 minutes.Then, the mixture that obtains so further mixes with a triple-roller mill, produces a kind of uniform liquid.In this liquid of 501 mass parts, add 0.2 mass parts a kind of 2% (quality) Platinic chloride 2-Ethylhexyl Alcohol solution and 0.2 mass parts a kind of 50% (quality) ethynylcyclohexanol toluene solution, then,, obtain a kind of uniform liquid resulting combined hybrid.Subsequently, add the organic hydrogen polysiloxanes of a kind of general formulas shown below of 5.0 mass parts (10) representative,
Me-Si(Me)
2-[OSi(Me)
2]
24-[OSi(Me)(H)]
4-OSi(Me)
2-Me (10)
With resulting liquid uniform mixing, obtain composition a.
[0043]
Zhi Bei composition a is administered on a kind of surface of PET film with the thickness of 1.0mm like this, is cured in 10 minutes 120 ℃ of heating then.Simultaneously, the mixing liquid by obtaining in the organic hydrogen polysiloxanes that 0.1 mass parts benzotriazole is dissolved in a kind of general formulas shown below of 100 mass parts (II) representative
Me-Si(Me)
2-[OSi(Me)
2]
75-[OSi(Me)(H)]
25-OSi(Me)
2-Me (11)
With 5g/m
2Quantity be administered on a kind of surface of independent PET film.Then, the coating surface of these two kinds of PET films is sticked together, left standstill 30 minutes at 80 ℃ then.Subsequently, these two kinds of PET films are peelled off, obtained sheet material A.Measure processing property, thermotolerance and the flame retardant resistance of sheet material A.
[0044]
Processing property
Any distortion does not take place during this PET film is peeled off or slight deformation takes place but not having any using under the situation that tension force just recovers original sheet form at those these sheet materials, this sheet material is evaluated as " good ".Otherwise, during peeling off, this PET film takes place significantly to be out of shape and not use tension force and just can not recover under the situation of original sheet form at those these sheet materials, and this sheet material is evaluated as " bad ".Assessment result is listed in the table 1.
[0045]
Thermotolerance
A well heater is embedded this transistor of replacement in the transistorized aluminum hull of TO-3, and use resulting structure as the model well heater.Then, this model well heater is installed in a scatterer (name of product Flat 60F 230 * 70mm, LEX (Marusan ElectricCo., Ltd. makes)) and (surface-area 7cm is installed
2) on.To cut into and the part of the sheet material A that the installation of this model well heater surface is identical shaped is clamped between this model well heater and this scatterer, use 300gf/cm then
2Load press sticking.The electric power of 28W is added on this model well heater, with the temperature T 1 of this model well heater of thermocouple measurement and the temperature T 2 of this scatterer.Calculate the thermotolerance of sheet material with following formula:
Thermotolerance R=(T1-T2)/28
The results are shown in Table 1.
[0046]
Flame retardant resistance
Carry out the flame retardant test of sheet material A according to the UL94 standard of Underwriters Laboratories Inc. formulation.Added up the combustion time of 5 independent revision test mensuration.The results are shown in Table 1.
[0047]
Comparative example 1
The composition a of preparation among the embodiment 1 is administered on a kind of surface of PET film with the thickness of 1.0mm, was cured in 10 minutes 120 ℃ of heating then, thereby obtains sheet material A '.Measure processing property, thermotolerance and the flame retardant resistance of sheet material A '.The results are shown in Table 1.
[0048]
Comparative example 2
The composition a of preparation among the embodiment 1 is administered on a kind of surface of PET film with the thickness of 1.0mm, was cured in 10 minutes 120 ℃ of heating then.Simultaneously, the organic hydrogen polysiloxanes that above general formula (II) is represented is with 5g/m
2Quantity be administered on a kind of surface of independent PET film.Then, the coating surface of these two kinds of PET films is sticked together, left standstill 30 minutes at 80 ℃ then.Subsequently, these two kinds of PET films are peeled away, obtained sheet material A ".Then, measure sheet material A " processing property, thermotolerance and flame retardant resistance.The results are shown in Table 1.
[0049]
Comparative example 3
To a kind of two ends of a Shinagawa multi-usage mixing machine (Shinagawa Machinery WorksCo., Ltd. makes) middle adding 100 mass parts ethenyl blocking and 25 ℃ of viscosity being arranged all is 600mm
2The dimethyl polysiloxane of/s and a kind of mean particle size of 400 mass parts were the aluminum oxide of 4 μ m, with resulting combined hybrid 60 minutes.Then, the mixture that obtains is so further mixed with one 3 roller mill, obtain a kind of uniform liquid.In this liquid of 500 mass parts, add a kind of 2 quality % Platinic chloride 2-Ethylhexyl Alcohol solution of 0.2 mass parts and a kind of 50 quality % ethynylcyclohexanol toluene solutions of 0.2 mass parts,, obtain a kind of uniform liquid then with resulting combined hybrid.Subsequently, add the organic hydrogen polysiloxanes and the uniform mixing of the above general formula of 10.0 mass parts (10) representative, obtain composition b.
[0050]
Zhi Bei composition b is administered on a kind of surface of PET film with the thickness of 1.0mm like this, is cured in 10 minutes 120 ℃ of heating then, thereby obtains sheet material B.Processing property, thermotolerance and the flame retardant resistance of sheet material B have been measured.The results are shown in Table 1.
[0051]
Table 1
| Sheet material | Processing property | Thermotolerance (℃/W) | Flame retardant resistance (second) | |
| Embodiment 1 | A | Good | 1.04 | 16 |
| Comparative example 1 | A′ | Difference | 0.98 | 19 |
| Comparative example 2 | A″ | Good | 0.99 | 51 |
| Comparative example 3 | B | Good | 2.52 | 14 |
Claims (7)
1. fire-retardant a, heat-conductive silicone former comprises
From the molding that a kind of cured product of composition forms, said composition comprises
(a) a kind of organopolysiloxane that contains with the alkenyl of silicon atom bonding of 100 mass parts,
(b) a kind of heat conductive filler of 200～5000 mass parts,
(c) a kind of organic hydrogen polysiloxanes that contains with the hydrogen atom of silicon atom bonding, its quantity be enough to for the every 1mol key thiazolinyl in the described composition (a) provide 0.1～5.0mol and silicon atom bonding in the described composition (c) hydrogen atom and
(d) platinum metals of significant quantity is an addition reaction catalyst; With
A upper layer that forms on described molding surface, this upper layer comprises
(e) a kind of contain with the organic hydrogen polysiloxanes of the hydrogen atom of silicon atom bonding and
(f) a kind of fire retardant, wherein
The addition reaction product is to take place between the described organopolysiloxane of the described organic hydrogen polysiloxanes of described composition (e) and described composition (a).
2. according to fire-retardant, the heat-conductive silicone former of claim 1, wherein said heat conductive filler is select from following composition one group at least a: metal, oxide compound, nitride, carbide, and man-made diamond.
3. according to fire-retardant, the heat-conductive silicone former of claim 1, it is configured as film or sheet material.
4. according to fire-retardant, the heat-conductive silicone former of claim 1, it is intended for the heat-transfer matcrial of electronic unit.
5. according to the production method of fire-retardant, the heat-conductive silicone former of claim 1, comprise the following step: (e) and mixture (f) are administered on the surface of the molding that forms from a kind of cured product of composition:
(e) a kind of contain with the organic hydrogen polysiloxanes of the hydrogen atom of silicon atom bonding and
(f) a kind of fire retardant,
Said composition comprises
(a) a kind of organopolysiloxane that contains with the alkenyl of silicon atom bonding of 100 mass parts,
(b) a kind of heat conductive filler of 200～5000 mass parts,
(c) a kind of organic hydrogen polysiloxanes that contains with the hydrogen atom of silicon atom bonding, its quantity be enough to for the every 1mol key thiazolinyl in the described composition (a) provide 0.1～5.0mol and silicon atom bonding in the described composition (c) hydrogen atom and
(d) platinum metals of significant quantity is an addition reaction catalyst; With
Make described mixture solidified to form described upper layer.
6. according to the production method of fire-retardant, the heat-conductive silicone former of claim 1, comprise the following step: use a kind of its surface to be coated with the model of (e) and mixture (f) or separator and a kind of composition is solidified and be shaped,
(e) a kind of contain with the organic hydrogen polysiloxanes of the hydrogen atom of silicon atom bonding and
(f) a kind of fire retardant,
Said composition comprises
(a) a kind of organopolysiloxane that contains with the alkenyl of silicon atom bonding of 100 mass parts,
(b) a kind of heat conductive filler of 200～5000 mass parts,
(c) a kind of organic hydrogen polysiloxanes that contains with the hydrogen atom of silicon atom bonding, its quantity be enough to for the every 1mol key thiazolinyl in the described composition (a) provide 0.1～5.0mol and silicon atom bonding in the described composition (c) hydrogen atom and
(d) platinum metals of significant quantity is an addition reaction catalyst; With
Thereby obtain molding that a kind of cured product from described composition forms and form described upper layer on the surface of described molding.
7. electronic unit method of cooling comprises following steps:
To be disposed between this electronic unit and the heat dissipation element according to fire-retardant, the heat-conductive silicone former of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005001776 | 2005-01-06 | ||
| JP2005001776A JP4463117B2 (en) | 2005-01-06 | 2005-01-06 | Flame-retardant and heat-conductive silicone molded article and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1803925A true CN1803925A (en) | 2006-07-19 |
Family
ID=36796106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610051332 Pending CN1803925A (en) | 2005-01-06 | 2006-01-05 | Flame-retardant heat-conductive silicone former and method of producing thereof |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4463117B2 (en) |
| CN (1) | CN1803925A (en) |
| TW (1) | TW200632043A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168620B (en) * | 2007-09-04 | 2012-07-25 | 东莞兆舜有机硅新材料科技有限公司 | Heat-conducting anti-flaming liquid silicon rubber and preparation method thereof |
| CN109608886A (en) * | 2018-12-14 | 2019-04-12 | 东莞市佳迪新材料有限公司 | A kind of reinforced organic silicone composite sheet of surface vanishing viscosity |
| CN109627473A (en) * | 2018-12-14 | 2019-04-16 | 东莞市佳迪新材料有限公司 | A kind of preparation process of the reinforced organic silicone composite sheet of surface vanishing viscosity |
| CN115667408A (en) * | 2020-05-26 | 2023-01-31 | 信越化学工业株式会社 | Two-liquid addition curing type silicone rubber composition |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5283346B2 (en) | 2007-04-10 | 2013-09-04 | 信越化学工業株式会社 | Thermally conductive cured product and method for producing the same |
| JP5233325B2 (en) | 2008-02-29 | 2013-07-10 | 信越化学工業株式会社 | Thermally conductive cured product and method for producing the same |
| JP6061463B2 (en) * | 2011-08-08 | 2017-01-18 | 日東電工株式会社 | Adhesive tape or sheet |
| JP6674590B1 (en) * | 2018-05-08 | 2020-04-01 | 富士高分子工業株式会社 | Thermal conductive sheet, mounting method using the same, and bonding method using the same |
-
2005
- 2005-01-06 JP JP2005001776A patent/JP4463117B2/en not_active Expired - Fee Related
-
2006
- 2006-01-05 TW TW095100465A patent/TW200632043A/en not_active IP Right Cessation
- 2006-01-05 CN CN 200610051332 patent/CN1803925A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168620B (en) * | 2007-09-04 | 2012-07-25 | 东莞兆舜有机硅新材料科技有限公司 | Heat-conducting anti-flaming liquid silicon rubber and preparation method thereof |
| CN109608886A (en) * | 2018-12-14 | 2019-04-12 | 东莞市佳迪新材料有限公司 | A kind of reinforced organic silicone composite sheet of surface vanishing viscosity |
| CN109627473A (en) * | 2018-12-14 | 2019-04-16 | 东莞市佳迪新材料有限公司 | A kind of preparation process of the reinforced organic silicone composite sheet of surface vanishing viscosity |
| CN109608886B (en) * | 2018-12-14 | 2021-02-05 | 东莞市佳迪新材料有限公司 | Enhanced organic silicon composite sheet with surface viscosity removal function |
| CN115667408A (en) * | 2020-05-26 | 2023-01-31 | 信越化学工业株式会社 | Two-liquid addition curing type silicone rubber composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200632043A (en) | 2006-09-16 |
| JP4463117B2 (en) | 2010-05-12 |
| JP2006188610A (en) | 2006-07-20 |
| TWI371470B (en) | 2012-09-01 |
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