CN103298885A - Highly transparent, thermally conductive silicone composition and cured material - Google Patents
Highly transparent, thermally conductive silicone composition and cured material Download PDFInfo
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- CN103298885A CN103298885A CN2011800643710A CN201180064371A CN103298885A CN 103298885 A CN103298885 A CN 103298885A CN 2011800643710 A CN2011800643710 A CN 2011800643710A CN 201180064371 A CN201180064371 A CN 201180064371A CN 103298885 A CN103298885 A CN 103298885A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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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
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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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
Abstract
Provided is a thermally conductive silicone composition capable of producing a cured material, the material combining thermal conductivity, transparency, and flame resistance. This composition includes a hydrophobized surface-treated silica comprising: matrix silica composed of SiO1/2 units (Q units), and a surface treatment agent applied and bonded to the surface of the matrix silica. The surface treatment agent is an organosilicon compound represented by general formula (X) (in the formula, R<1> either is a monovalent organosiloxane group optionally having a trifunctional branch but not having a tetrafunctional branch, the end group bonded to a silicon atom in the organosiloxane group being blocked by an oxygen atom, or is a substituted or unsubstituted monovalent hydrocarbon group; R<2> is an alkyl group; and x is an integer 1 to 3). The molar ratio (p/q) of the number (p) of silicon atoms constituting the surface treatment agent bonded to the surface of the matrix silica in relation to the number (q) of the Q units is in the range 0.01 to 0.3.
Description
Technical field
The present invention broadly relates to the excellent heat-conductive silicone material of the transparency at the heating interface that can be installed on the needs transparency.
Background technology
LSI chip for the CPU that in electronicss such as PC, digital video disk and mobile phone, uses, driver IC, storer etc., along with high performance, high speed, miniaturization, highly integrated, himself can produce a large amount of heat, because these heat, the temperature of chip rises, and then causes the bad and breaking-up of running of chip.Therefore, many heat dissipating methods that rise for the temperature of the chip that suppresses running and the thermal component that is used for it have been proposed.But the thermal component that proposes up to now is composition or its cured article that cooperates the thermal conductivity inorganic filling material to form in resin, is opaque.Owing to be opaque, be encapsulated in the electronic unit after, in order to confirm component names or parts number, must specially take out from electronic unit.In order to address this problem, the real public clear 62-28769 communique of Japan (patent documentation 1) has proposed, and for box-like thermal component, the formation of otch or window is set in the one side of box.But have the problem that can't obtain the electrical insulating property of part that cuts out, Japanese kokai publication hei 8-17977 communique (patent documentation 2) has proposed to have concurrently the electronic unit box of the transparency and electrical insulating property.Wherein, the window part that is cut out is made by transparent silicon rubber.But in this case, have following shortcoming: the thermal conductivity of transparent silicon rubber part is compared remarkable reduction with other parts, causes producing hot spot in this part.In addition, if in the part of box window is set, then when mounting box, the part of the part with window and the parts number of having put down in writing parts etc. must be matched, so the efficient of fitting operation is poor.Be transparent and also have thermal conductivity as compartmentalized box for holding assorted fruits and candies integral body, then install in any case and can confirm parts number, and can not produce hot spot.
On the other hand, the development of liquid crystal flat panel display (LCD), photodiode (LED) etc. is advanced by leaps and bounds in recent years.Liquid crystal flat panel display slimming all the more, LED be high brightness all the more then.Even also there is the problem of heating in this field, its present situation is distributed the back side at substrate for the heat of sending from LCD and LED.In addition, though on the picture of LCD lamination several layers of protective membrane etc., do not have the layer of heat dispersion.If can stackedly have the layer of heat dispersion, then also can dispel the heat from indicating meter portion, therefore more can suppress dull and stereotyped temperature and rise.But need when having thermal diffusivity, also have the transparency for this reason.In addition, if heat dispersion also can be given LED element sealing material, reflector material, then can not reduce brightness and be conducive to long lifetime.Also need when having thermal diffusivity, also have the transparency for this reason.
The prior art document
Patent documentation
Patent documentation 1: the real public clear 62-28769 communique of Japan
Patent documentation 2: Japanese kokai publication hei 8-17977 communique.
Summary of the invention
Therefore, the objective of the invention is to, a kind of heat-conductive silicone composition and cured article thereof of giving the cured article that has thermal conductivity, the transparency and flame retardant resistance concurrently is provided.
The inventor is contained by use and has been implemented specific hydrophobic surface-treated silicon-dioxide, develops finally can highly to fill, keep the transparency, and heat-conductive silicone composition and the cured article thereof of thermal conductivity, excellent in flame retardance.
That is, the invention provides a kind of heat-conductive silicone composition, it is for comprising:
(α) hydrophobization surface treatment silicon-dioxide, it is made of following substances: by SiO
1/2The base material silicon-dioxide that unit (Q unit) constitutes and handle on its surface and combination surface treatment agent; And
(β) organopolysiloxane composition
Heat-conductive silicone composition, it is characterized in that,
Described surface treatment agent is the silicoorganic compound shown in the general formula (X):
In the formula, R
1For having 3 functionality side chains but do not have 4 functionality side chains and the organo-siloxane base of 1 valency that stops with Sauerstoffatom with the end of silicon atom bonding; Perhaps be the alkyl of replacement or unsubstituted 1 valency, R
2Be alkyl, x is 1～3 integer,
The mol ratio (p/q) of the quantity (p) of the Siliciumatom of the surface treatment agent of the surface bonding of formation and base material silicon-dioxide and the quantity (q) of described Q unit is in 0.01～0.3 scope.
Heat-conductive silicone composition of the present invention can be given the cured article that has thermal conductivity, the transparency and flame retardant resistance concurrently.Therefore, can use as thermal component at the heating part of the needs transparency.
Embodiment
-about M, D, T, Q unit-
Organopolysiloxane constitutes by inorganic Si-O-Si key with the organic group of silicon atom bonding, and the kind of the structure by changing skeleton, the polymerization degree, organic group etc. can access the various materials with various features.Here, for structure and the explanation of the present invention of simplifying organopolysiloxane, use following symbol conventionally known to one of skill in the art, habitual.Can think, in each unit with Siliciumatom in abutting connection with and the Sauerstoffatom of bonding be assumed to the Sauerstoffatom that forms siloxane bond (Si-O-Si), clip this Sauerstoffatom two Siliciumatoms each have 1/2.
The D unit:
The T unit:
The Q unit:
Wherein, in these unit, R is expressed as the substituting group of monovalence.
-(α) surface treatment silicon-dioxide-
Base material silicon-dioxide:
Base material silicon-dioxide namely, though untreated silica in fact only is made of the Q unit, has a plurality of hydroxyls (silanol base) usually from the teeth outwards, and the surface is wetting ability.
Surface treatment agent:
Surface treatment silicon-dioxide used in the present invention is handled base material silicon-dioxide and is made surface-hydrophobicized obtaining with the specific surface treatment agent shown in the described general formula (X).The hydroxyl that base material silicon-dioxide has originally and surface treatment agent react and make surface-hydrophobicized.Therefore, surface treatment silicon-dioxide has the state of surface treatment agent with the surface bonding of base material silicon-dioxide and exists.
In general formula (X), R
1For having 3 functionality side chains but do not have 4 functionality side chains, and the organo-siloxane base of 1 valency that stops with Sauerstoffatom with the end of silicon atom bonding; It perhaps is the alkyl of replacement or unsubstituted 1 valency.Here, 3 functionality side chains are the T font side chain that forms by the existence of above-mentioned T unit in the main chain of organopolysiloxane; 4 functionality side chains are the cruciform side chain that forms by the existence of above-mentioned Q unit in this main chain.
R
1Under the situation for the poly organo alkyl of described 1 valency, its organopolysiloxane chain is made of M unit, D unit, T unit or their combination more than two kinds.
Silicoorganic compound shown in the general formula (X) particularly can be represented with following general formula (1)～(3).
In formula (1)～(3), R
1And R
2For with general formula (X) in narrate identical.
R
1Under the situation that is the poly organo alkyl, usually the main chain part is common practice by what the repeating unit of described D unit (wherein, R is the organic group of 1 valency) constituted basically.But also can be the branched structure that in the part of main chain part, comprises the T font that contains described T unit (wherein, R is the organic group of 1 valency).
R
1Under the situation of poly organo alkyl that is 1 valency, the repeat number of siloxane unit (its polymerization degree) is preferably 3～50.The lower limit of this polymerization degree is preferably more than 3, and the upper limit is more preferably below 20.If repeating unit surpasses 50, organosilicon covering substrates silica sphere then, and then be difficult to carry out and the dehydrating condensation that is present in the silanol base on the base material silica sphere.In addition, the particle diameter of resulting surface treatment silicon-dioxide is also excessive easily.
R
1Under the situation for the 1 valency alkyl that do not replace or replace, the silicon composition shown in the general formula (X) is organoalkoxysilane.As this 1 valency alkyl that does not replace or replace, can exemplify out, for example alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl; Cycloalkyl such as cyclopentyl, cyclohexyl, suberyl, aryl such as phenyl, tolyl, xylyl, naphthyl, xenyl, alkyl such as aralkyl such as benzyl, phenylethyl, phenyl propyl, methyl-benzyl; And with part or all of the hydrogen atom of the carbon atom bonding of these alkyl by the substituted hydrocarbon radical that halogen atoms such as fluorine, chlorine, bromine, cyano group etc. replace, for example, can list chloromethyl, 2-bromotrifluoromethane, 3-chloropropyl, 3,3,3-trifluoro propyl, chloro-phenyl-, fluorophenyl, cyano ethyl, 3,3,4,4,5,5,6,6,6-, nine fluorine hexyls etc.In the middle of these, representative groups is the group of carbonatoms 1～10, special representative's property be the group of carbonatoms 1～6, be preferably methyl, ethyl, propyl group, chloromethyl, bromotrifluoromethane, 3, the phenyl that the alkyl that does not replace or replace of carbonatomss such as 3,3-trifluoro propyl, cyano ethyl 1～3 and phenyl, chloro-phenyl-, fluorophenyl etc. do not replace or replace.
Alkoxyl group (OR
2) R
2Be the alkyl of carbonatoms 1～6, be preferably the alkyl of carbonatoms 1 or 2.Can list, for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl.
Silicon bonded alkoxy group (OR with end
2) be to get final product more than one.In addition, the kind of organoalkoxysilane can be from selecting more than a kind or a kind.Further, use terminally when having the organoalkoxysilane of two above alkoxyl groups, can further handle by other organoalkoxysilane, thereby obtain having the surface treatment silicon-dioxide of high hydrophobicity.The degree that it is processed for example can be obtained by following: make potassium hydroxide act on surface treatment silicon-dioxide, cut off siloxane bond and make its whole Ethoxysilaneizations, thereby calculated by the area ratio of vapor-phase chromatography.(calculating by this method among the application's the embodiment).
Concrete example as the surface treatment agent shown in general formula (1)～(3) can list following compound.
Surface treatment agent shown in the above-mentioned general formula (X) can a kind uses separately, also can be used in combination more than 2 kinds.
Surface treatment silicon-dioxide:
For the ratio of the base material silicon-dioxide that is constituted by the Q unit with the described surface treatment agent that is present in the surface, the Siliciumatom number (p) of the surface treatment agent of formation base material silica sphere institute combination and the mol ratio (p/q) of the Q unit number (q) that constitutes described base material silicon-dioxide are in 0.01～0.3 scope.The more big surface treatment agent that then exists on the surface of silicon-dioxide of this p/q value is more many, can be described as the high silicon-dioxide of processing degree.If p/q is littler than 0.01, then degree of processing is insufficient, and fillibility, bad dispersibility can not keep the transparency.In addition, because the T unit is bigger than the volume of M unit, so the T unit is more many more can protect silica sphere.For example, even finish surface-treated silica sphere residual silicon alcohol radical, the T unit is also covered by the silanol base, therefore can access the hydrophobization effect.In addition, above-mentioned mol ratio surpasses at 0.3 o'clock, and it is big that the particle diameter of silicon-dioxide becomes, and can't guarantee the transparency.
The value of the median size of surface treatment silicon-dioxide for using laser diffraction and scattering method (micro-track method) to measure.This median size need be preferably below the above 150nm of 20nm below the above 200nm of 20nm, more preferably below the above 120nm of 20nm.Its reason is, if median size is excessive, even then fully disperse, can not guarantee the transparency in organosilicon.In addition, if median size is little, though then the transparency uprises, because the surface-area of silicon-dioxide becomes big, the fillibility reduction is difficult to realize good thermal conductivity.
Representational manufacture method as surface treatment silicon-dioxide, to-oxyl silane, be hydrolyzed condensation and obtain wetting ability sol-gel silicon dioxide microparticle as the tetramethoxy-silicane of typical example, make the silicoorganic compound shown in the general formula (X) as described surface treatment agent act on this particulate, thereby obtain.
-silicon composition-
Heat-conductive silicone composition of the present invention, it is for comprising:
(α) hydrophobization surface treatment silicon-dioxide, it is made of following substances: by SiO
1/2The base material silicon-dioxide that unit (Q unit) constitutes and handle on its surface and combination surface treatment agent; And
(β) organopolysiloxane composition
Heat-conductive silicone composition, it is characterized in that,
Described surface treatment agent is the silicoorganic compound shown in the general formula (X):
(in the formula, R
1For having 3 functionality side chains but do not have 4 functionality side chains and the organo-siloxane base of 1 valency that stops with Sauerstoffatom with the end of silicon atom bonding; Perhaps be the alkyl of replacement or unsubstituted 1 valency, R
2Be alkyl, x is 1～3 integer.）。
The mol ratio (p/q) of the quantity (p) of the Siliciumatom of the surface treatment agent of the surface bonding of formation and base material silicon-dioxide and the quantity (q) of described Q unit is in 0.01～0.3 scope.
This silicon composition must composition as other except the described surface treatment silicon-dioxide of this (α) composition, also contains (β) organopolysiloxane composition.Be included in the said composition, with respect to as total organopolysiloxane composition (surface treatment agent that does not comprise formation (α) composition) 100 mass parts of (β) composition, (α) addition of the described surface treatment silicon-dioxide of composition, from the transparency, thermal conductivity and flame retardant resistance good viewpoint all, be preferably 100～500 mass parts.The lower limit of this addition is more preferably more than 200 mass parts, more preferably more than 300 mass parts.In addition, the upper limit of this addition is more preferably below 400 mass parts, more preferably below 350 mass parts.In addition, if too much, then the excess stickiness of composition uprises, lack formability.
Heat-conductive silicone composition of the present invention is solidified nature, according to the type of curing reaction, selects the organopolysiloxane composition of (β) composition.In addition, cooperate solidifying agent, catalyzer as required.Below, to the curing reaction type detailed description of each composition.
Kind according to the curing type of silicon composition
The curing type of heat-conductive silicone composition of the present invention does not have special restriction.Can use known curing type.As concrete example, can list the silicon composition of organo-peroxide solidified nature, addition curing, radiation-curable and condensation cured property.It is preferably addition curing.
As the radiation-curable silicon composition, can exemplify out ultra-violet solidified silicon composition and electrocuring organic silicon composition.
As the reactive silicon composition of addition curing, can exemplify out, for example by in the presence of above-mentioned straight chain shape organopolysiloxane with thiazolinyl, poly-organohydrogensiloxanes and platinum metals series catalysts, reacting (hydrogenation silylanizing addition reaction), thus the silicon composition that solidifies.
As organo-peroxide solidified nature silicon composition, can exemplify out, the straight chain shape organopolysiloxane by having thiazolinyls such as vinyl any one party or the both sides of molecule chain end (side end or a both-side ends) and the non-end of molecular chain for example, in the presence of organo-peroxide, carry out radical polymerization, thus the silicon composition that solidifies.
As ultra-violet solidified silicon composition, can list, for example the silicon composition that is cured of the ultraviolet energy by wavelength 200～400nm.At this moment, there is not special restriction for curing mechanism.As concrete example, can list and contain organopolysiloxane with acrylic or methacrylic acid group and the vinylformic acid silicon-type silicon composition of Photoepolymerizationinitiater initiater; Containing the organopolysiloxane with sulfydryl, the organopolysiloxane with thiazolinyls such as vinyl and the sulfydryl-vinyl addition polymerization of Photoepolymerizationinitiater initiater is silicon composition; Using the addition reaction of the platinum metals series catalysts identical with heat cured addition reaction-type is silicon composition; Containing organopolysiloxane with epoxy group(ing) and the cationoid polymerisation of salt catalyst is silicon composition etc.These can use as the reactive silicon composition of ultraviolet curing.
As the reactive silicon composition of electrocuring, also can use by the organopolysiloxane with free-radical polymerised base being carried out the electron beam irradiation, thereby cause radical polymerization and any silicon composition of solidifying.
As condensation cured reactive silicon composition, can list, for example pass through organopolysiloxane and poly-organohydrogensiloxanes or water-disintegrable silane such as tetraalkoxysilane, organotrialkoxysilane and/or its partial hydrolysis condenses with two terminal silanol end-blockings, thereby in the presence of condensation catalysts such as organotin series catalysts, react the silicon composition that solidifies; Perhaps by with the organopolysiloxane of two ends by institute's end-blockings such as tri-alkoxy, dialkoxy organic group, tri-alkoxy siloxy-ethyl, the organic siloxy-ethyls of dialkoxy, thereby in the presence of the condensation reaction of organotin catalysts etc., react the silicon composition that solidifies etc.
Below, to the typical example detailed description of each reactive silicon composition.
Organo-peroxide curing reaction type silicon composition:
As organo-peroxide curing reaction type silicon composition, particularly, can list, for example except described surface treatment silicon-dioxide (((α) composition)), also contain the organo-peroxide curing reaction type silicon composition of following (α), (b), (c):
(a) contain 2 organopolysiloxane with the thiazolinyl of silicon atom bonding at least;
(b) organo-peroxide, and any composition of conduct
(c) contain 2 poly-organohydrogensiloxanes with the hydrogen atom (being the SiH yl) of silicon atom bonding at least, and with respect to per 1 mole of the thiazolinyl in total solidified nature silicon composition, the amount with hydrogen atom silicon atom bonding in described (c) composition is 0.1～2 mole.
(a) composition
(a) organopolysiloxane of composition is the base polymer (ベ ー ス Port リ マ ー of organo-peroxide curing reaction type silicon composition).(a) polymerization degree of the organopolysiloxane of composition is not particularly limited, as (a) composition, though can use from being the organopolysiloxane of aqueous organopolysiloxane to the untreated rubber shape down at 25 ℃, but mean polymerisation degree is preferably 50～20000, more preferably 100～10000, more preferably about 100～2000.In addition, (a) organopolysiloxane of composition, the angle of the easness that obtains from raw material considers that can be: molecular chain is by two organo-siloxane unit (R basically
4 2SiO
2/2The unit) repeating unit constitutes, and two ends of molecular chain are by three organic siloxy-(R
4 3SiO
1/2) or hydroxyl two organic siloxyies ((HO) R
4 2SiO
1/2The unit) the unbranched straight chain structure of institute's end-blocking; Perhaps that molecular chain is made of the repeating unit of this two organo-siloxanes unit for having, do not have the ring texture of side chain, but also can partly contain trifunctional siloxane unit or SiO
2A chain structure of unit etc.Here, R
4With defined identical in the formula (4) of following explanation.
As (a) composition, for example use shown in the following average group accepted way of doing sth (4) and in a part, have the organopolysiloxane of 2 thiazolinyls at least.
(in the formula, R
4Represent identical or different kind do not replace or replace, carbonatoms is 1～10, more preferably 1～8 monovalence alkyl; R
450～99 moles of % be thiazolinyl; A is 1.5～2.8, more preferably 1.8～2.5, the positive number of more preferably 1.95～2.05 scopes.）。
As above-mentioned R
4Concrete example, can list alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl; Aryl such as phenyl, tolyl, xylyl, naphthyl; Cycloalkyl such as cyclopentyl, cyclohexyl; Thiazolinyls such as vinyl, allyl group, propenyl, pseudoallyl, butenyl; The group that part or all of the hydrogen atom of these alkyl replaced by halogen atoms such as fluorine, bromine, chlorine, cyano group etc., for example chloromethyl, chloropropyl, bromotrifluoromethane, trifluoro propyl, cyano ethyl etc., but consider from highly purified angle, only be preferably and constituted by alkyl.
At this moment, R
4In at least 2 be thiazolinyl (particularly, preferred carbon atom is 2～8, more preferably 2～6 thiazolinyl).Need to prove, the content of thiazolinyl with whole organic groups of silicon atom bonding in (that is R in a described average group accepted way of doing sth (4),
4In the shown whole monovalence alkyl that do not replace or replace) be preferably 50～99 moles of %, be preferably 75～95 moles of % especially.(a) organopolysiloxane of composition has under the situation of straight chain structure, and only either party and silicon atom bonding that this thiazolinyl can be in the part of molecule chain end and non-molecule chain end also can be at these two portions and silicon atom bondings.
(b) composition
(b) composition is in organo-peroxide curing reaction type constituent polyorganosiloxane composition, as for the catalyzer of the crosslinking reaction that promotes (a) composition and the organo-peroxide that uses.As (b) composition, as long as can promote the crosslinking reaction of (a) composition, just can use known organo-peroxide in the past.Can exemplify benzoyl peroxide, peroxidation 2 as its concrete example, 4-dichloro-benzoyl, peroxidation are to toluyl, peroxidation o-methyl-benzene formyl, peroxidation 2,4-diisopropylbenzene(DIPB), 2,5-dimethyl-two (2, the 5-tert-butyl peroxide) hexane, ditertiary butyl peroxide, peroxidized t-butyl perbenzoate, 1, two (tert-butyl hydroperoxide carboxyl) hexanes of 1-etc., but be not defined in these especially.
(b) addition of composition is, as the significant quantity of the catalyzer of the crosslinking reaction that be used for to promote (a) composition.(a) composition 100 mass parts relatively can be preferably 0.1～10 mass parts, the scope of 0.2～2 mass parts more preferably.If this addition (a) composition 100 mass parts relatively is the amount that is less than 0.1 mass parts, then the needed time is long, unfavorable economically till solidifying.In addition, if this addition relatively (a) composition 100 mass parts be amount more than 10 mass parts, then produce the foaming from (b) composition, and then the intensity of this curing reaction thing and thermotolerance can be adversely affected.
(c) composition
Poly-organohydrogensiloxanes as (c) composition of optional member contains at least 2 (common 2～200), be preferably the hydrogen atom (SiH yl) of (common 3～100) and silicon atom bonding more than 3.(a) composition, interpolation (b) composition also can make its curing by heating separately, but by adding (c) composition, and compare under the situation of (a) composition separately since easily with (a) composition reaction, therefore can be in that more low temperature and short period of time be cured.(c) molecular structure of composition is not particularly limited, and for example any poly-organohydrogensiloxanes of in the past making of waiting of wire, ring-type, a chain and three-dimensional netted (arborescens) also can be used as the use of (c) composition.(c) composition has under the situation of linear structure, and only either party and silicon atom bonding that the SiH base can be in the part of the terminal or non-molecule chain end of molecular chain also can be at both sides and silicon atom bondings.In addition, the Siliciumatom number (or polymerization degree) in 1 molecule is generally 2～300, is preferably about 4～150, can preferably use as (c) composition for aqueous poly-organohydrogensiloxanes down in room temperature (25 ℃).
As (c) composition, can use for example poly-organohydrogensiloxanes shown in the following average group accepted way of doing sth (5);
R
5 bH
cSiO
（4-b-c）/2 （5）
(in the formula, R
5For identical or different kind do not replace or replace, not contain aliphatics unsaturated link(age) and carbonatoms be 1～10, more preferably 1～8 monovalence alkyl; B and c are preferably to satisfy 0.7≤b≤2.1,0.001≤c≤1.0 and 0.8≤b+c≤3.0, more preferably satisfy the positive number of 1.0≤b≤2.0,0.01≤c≤1.0 and 1.5≤b+c≤2.5).As above-mentioned R
5For example can list with an above-mentioned average group accepted way of doing sth (4) in R
4Identical group (wherein, except the thiazolinyl).
Concrete example as the poly-organohydrogensiloxanes shown in the above-mentioned average group accepted way of doing sth (5), can list 1,1,3, the 3-tetramethyl disiloxane, 1,3,5,7-tetramethyl-ring tetrasiloxane, three (hydrogen dimethylamino base siloxy-) methyl-monosilane, three (hydrogen dimethylamino base siloxy-) phenyl silane, the methyl hydrogen cyclopolysiloxane, methyl hydrogen siloxane dimethyl siloxane cyclocopolymer, two terminal trimethylsiloxy end-blocking methylhydrogenpolysi,oxane, two terminal trimethylsiloxy end-blocking methyl hydrogen siloxane dimethylsiloxane copolymers, two terminal methyl group hydrogen siloxy-end-blocking dimethyl polysiloxanes, two terminal methyl group hydrogen siloxy-end-blocking methyl hydrogen siloxane dimethylsiloxane copolymers, two terminal trimethylsiloxy end-blocking methyl hydrogen polymer siloxane diphenyl siloxane multipolymers, two terminal trimethylsiloxy end-blocking methyl hydrogen siloxane diphenyl siloxane dimethylsiloxane copolymers, two terminal trimethylsiloxy end-blocking methyl hydrogen siloxane methylphenyl siloxane dimethylsiloxane copolymers, two terminal methyl group hydrogen siloxy-end-blocking methyl hydrogen siloxane diphenyl siloxane dimethylsiloxane copolymers, two terminal methyl group hydrogen siloxy-end-blocking methyl hydrogen siloxane methylphenyl siloxane dimethylsiloxane copolymers, by (CH
3)
2HSiO
1/2Unit and (CH
3)
2SiO
2/2Unit 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.
(c) though the addition of composition is amount arbitrarily, relative (a) composition 100 mass parts can preferably be 0～100 mass parts, the scope of 0～50 mass parts more preferably.(a) composition 100 mass parts relatively if this addition is the amount more than 100 mass parts, then produce the foaming from (c) composition, and then the intensity of this curing reaction thing and thermotolerance can be adversely affected.
The reactive silicon composition of ultraviolet curing:
As the reactive silicon composition of ultraviolet curing, specifically can list except containing described surface treatment silicon-dioxide ((α) composition), also contain
(d) ultraviolet reactive organopolysiloxane and
(e) the reactive silicon composition of the ultraviolet curing of Photoepolymerizationinitiater initiater.
(d) composition
(d) the ultraviolet reactive organopolysiloxane of composition works as base polymer in the reactive silicon composition of ultraviolet curing usually.(d) composition is not particularly limited, and preferably has at least 2, more preferably 2～20 in 1 molecule, is preferably the organopolysiloxane of 2～10 ultraviolet reactive groups especially.The a plurality of described ultraviolet curing reactive group that exists in this organopolysiloxane can be all identical, also can be different.
(d) organopolysiloxane of composition considers that from the angle of the easy degree that obtains raw material can be: molecular chain (main chain) is by two organo-siloxane unit (R basically
4 2SiO
2/2The unit) repeating unit constitutes, and molecular chain two ends are by three organic siloxy-(R
4 3SiO
1/2) the unbranched straight chain structure of end-blocking; Perhaps have molecular chain by the repeating unit of described two organo-siloxane unit constitute, unbranched ring texture, but also can partly contain trifunctional siloxane unit, SiO
2A chain structure such as unit.Here, R
4With identical described in the formula (4).(d) organopolysiloxane of composition has under the situation of straight chain structure, can the only either party in the part of molecule chain end and non-molecule chain end have ultraviolet reactive group, also can have ultraviolet reactive group both sides, but preferably have ultraviolet reactive group at molecular chain two ends at least.
As this ultraviolet ray reactive group, can list for example thiazolinyls such as vinyl, allyl group, propenyl; Thiazolinyl oxygen bases such as vinyl oxygen base, allyl group oxygen base, propenyl oxygen base, pseudoallyl oxygen base; Aliphatics unsaturated group beyond the thiazolinyl such as acryl, methacryloyl; Epoxy group(ing); Hydrogen silyl etc.Preferably list acryl, methacryloyl, sulfydryl, epoxy group(ing) and hydrogen silyl.More preferably list acryl and methacryloyl.
The viscosity of described organopolysiloxane is not particularly limited, but preferably is down 100mPa.s～1,000 at 25 ℃, and 000mPa.s, more preferably 200～500, is preferably 200～100,000mPa.s especially at 000mPa.s.
As a preferred form of (d) composition, for example can list the organopolysiloxane that has the ultraviolet reactive group shown in 2 following general formulas (6a) or the following general formula (6b) at least;
[in the formula, R
6Be the monovalence alkyl that does not replace or replace identical or different kind, that do not have ultraviolet reactive group, R
7Be group identical or different kind, that have ultraviolet reactive group, R
8Be group identical or different kind, that have ultraviolet reactive group; M is 5～1,000 integer; N is 0～100 integer; F is 0～3 integer; G is 0～3 integer.Wherein, f+g+n 〉=2]
[R in the formula
6, R
7, R
8, m, n, f and g be identical with above-mentioned general formula (6a) definition, h is 2～4 integer; I and j are respectively 1～3 integer; Wherein, fi+gj+n 〉=2].
At above-mentioned general formula (6a) with (6b), R
6For 1 valency that does not replace or replace identical or different kind, that do not have ultraviolet reactive group, carbonatoms is preferably 1～20, more preferably 1～10, more preferably 1～8 alkyl.As R
6Shown monovalence alkyl for example can list, alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl; Aryl such as phenyl, tolyl, xylyl, naphthyl; Cycloalkyl such as cyclopentyl, cyclohexyl, cyclopentyl; Aralkyl such as benzyl, phenylethyl; They with part or all group that is formed by replacements such as halogen atom, cyano group, carboxyls of alkyl bonded hydrogen atom, for example chloromethyl, chloropropyl, bromotrifluoromethane, trifluoro propyl, cyano ethyl, 3-cyano group propyl group etc., preferably list methyl and phenyl, more preferably list methyl.In addition, above-mentioned R
3Shown monovalence alkyl also can have alkylsulfonyl, ehter bond (O-), carbonyl etc. more than a kind or 2 kinds in its skeleton.
As above-mentioned general formula (6a) with (6b), R
7And R
8The ultraviolet reactive group that contains can list, for example thiazolinyls such as vinyl, allyl group, propenyl; Thiazolinyl oxygen bases such as vinyl oxygen base, allyl group oxygen base, propenyl oxygen base, pseudoallyl oxygen base; Aliphatics unsaturated group beyond the thiazolinyl such as acryl, methacryloyl; Sulfydryl; Epoxy group(ing); Hydrogen silyl etc.Preferably list acryl, methacryloyl, epoxy group(ing) and hydrogen silyl.More preferably list acryl and methacryloyl.Therefore, has R
7And R
8The group of shown ultraviolet reactive group, for example for having the univalent perssad of ultraviolet reactive group illustrated above, as its concrete example, can list vinyl, allyl group, 3-glycidoxy propyl group, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl, the 3-methacryloxypropyl, 3-acryloxy propyl group, 3-sulfydryl propyl group, 2-{ two (2-methacryloxy oxyethyl group) methyl-silicane base } ethyl, 2-{ two (2-acryloyl-oxy base oxethyl) methyl-silicane base } 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, 2-{ two (1-acryloxy-3-methacryloxy-2-propoxy-) methyl-silicane base } ethyl and 2-{ two (1-acryloxy-3-methacryloxy-2-propoxy-) dimetylsilyl } ethyl etc.Preferably list, the 3-methacryloxypropyl, 3-acryloxy propyl group, 2-{ two (2-methacryloxy oxyethyl group) methyl-silicane base } ethyl, 2-{ two (2-acryloyl-oxy base oxethyl) methyl-silicane base } ethyl, 2-{ (2-acryloyl-oxy base oxethyl) dimetylsilyl } ethyl, 2-{ (1,3-dimethyl allene acyloxy-2-propoxy-) dimetylsilyl } ethyl, 2-{ two (1-acryloxy-3-methacryloxy-2-propoxy-) methyl-silicane base } ethyl and 2-{ two (1-acryloxy-3-methacryloxy-2-propoxy-) dimetylsilyl } ethyl.R
7And R
8Can be identical or different separately, R
7And R
8Between can be identical or different.
At above-mentioned general formula (6a) with (6b), m is generally 5～1, and 000, be preferably 10～800, more preferably 50～500 integer; N is generally 0～100, is preferably 0～50, more preferably 0～20 integer; F is 0～3, be preferably 0～2, more preferably 1～2 integer; G is 0～3, be preferably 0～2 integer, more preferably 1 or 2.In the above-mentioned general formula (6b), h is generally 2～4 integer, is preferably 2 or 3.I and j are respectively 1～3 integer, are preferably 1 or 2 integers.And then, above-mentioned general formula (6a) and (6b) shown in organopolysiloxane as previously described owing to have 2 described ultraviolet reactive groups at least, therefore in formula (6a), f+g+n 〉=2, and in formula (6b), fi+gj+n 〉=2.
As above-mentioned formula (6a) with the concrete example of the organopolysiloxane (6b), can list material shown below etc.
[in above-mentioned formula, R
990% be that methyl, 10% is for phenyl].
(e) composition
(e) Photoepolymerizationinitiater initiater of composition has the photopolymerisable effect that promotes the ultraviolet reactive group in described (d) composition.(e) composition is not particularly limited; as its concrete example; can list methyl phenyl ketone; Propiophenone; benzophenone; oxa-anthranol (キ サ Application ト ー Le); fluorenes (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-chloro-4 '-benzyl benzophenone; 3-chlorine xanthone; 3; 9-dichloro xanthone; 3-chloro-8-nonyl xanthone; st-yrax; the st-yrax methyl ether; the st-yrax butyl ether; two (4-dimethylaminophenyl) ketone; benzyl methoxyl group acetal; the 2-clopenthixal ketone; the diethylbenzene ethyl ketone; 1-hydroxy chloride phenyl ketone; 1-hydroxy-cyclohexyl phenyl ketone; 2-methyl-(4-(methylthio group) phenyl)-2-morpholino-1-propane; 2,2 dimethoxys-2-phenyl methyl phenyl ketone; diethoxy acetophenone and 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone etc.Preferably from highly purified viewpoint, list benzophenone, 4-methoxyacetophenone, 4-methyldiphenyl ketone, diethoxy acetophenone, 1-hydroxy-cyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone.More preferably list diethoxy acetophenone, 1-hydroxy-cyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone.These Photoepolymerizationinitiater initiaters can a kind use separately, also can will be used in combination more than 2 kinds.
(e) addition of composition is not particularly limited, but relative (d) composition 100 mass parts, is preferably 0.01～10 mass parts, more preferably 0.1～3 mass parts, 0.5～3 mass parts more preferably.If its addition in this scope, then carries out the curing control of silicon composition easily.
The reactive silicon composition of addition curing:
As the reactive silicon composition of addition curing, specifically can list, for example except described surface treatment silicon-dioxide ((α) composition), also comprise the reactive silicon composition of addition curing of following compositions:
(f) contain at least 2 with the organopolysiloxane of the thiazolinyl of silicon atom bonding,
(g) contain at least 2 poly-organohydrogensiloxanes with the hydrogen atom (being the SiH yl) of silicon atom bonding, with respect to the thiazolinyl in total solidified nature silicon composition per 1 mole, with the amount of the hydrogen atom of silicon atom bonding in this (g) composition be 0.1～5 mole amount, and
(h) the platinum metals series catalysts of significant quantity.
(f) composition
(f) organopolysiloxane of composition is the base polymer of the reactive silicon composition of addition curing, contains 2 thiazolinyls with silicon atom bonding at least.As (f) composition, can use known organopolysiloxane.The weight-average molecular weight of the organopolysiloxane of (f) composition of measuring by gel permeation chromatography (being designated hereinafter simply as " GPC ") is preferably 3,000～300 in polystyrene conversion, about 000.Further, (f) organopolysiloxane of composition is preferably 100～1 in the viscosity that places under 25 ℃, and 000,000mPa.s is preferably about 1,000～100,000mPa.s especially.If below the 100mPa.s, then stringiness is low, and it is difficult that the thin footpathization of fiber becomes.If then be difficult to operation more than 1,000, the 000mPa.s.(f) organopolysiloxane of composition considers that from the angle of the easy degree that obtains raw material can be: molecular chain (main chain) is by two organo-siloxane unit (R basically
10 2SiO
2/2The unit) repeating unit formation, molecular chain two ends are by three organic siloxy-(R
10 3SiO
1/2) the unbranched straight chain structure of end-blocking; Perhaps have molecular chain by the repeating unit of this two organo-siloxanes unit constitute, unbranched ring texture, also can be part and contain R
10SiO
3/2Unit, SiO
4/2A chain structure of unit.Here, R
10With the formula (7) of following explanation narrate identical.
As (f) composition, for example can use the organopolysiloxane that has 2 thiazolinyls shown in the following average group accepted way of doing sth (7), in a part at least;
R
10 lSiO
（4-l）/2 （7）
(in the formula, R
10As hereinbefore, for the carbonatoms that does not replace or replace of identical or different kind is 1～10, more preferably 1～8 monovalence alkyl, l is preferably the positive number of 1.5～2.8, more preferably 1.8～2.5, more preferably 1.95～2.05 scope.) as above-mentioned R
10Can list for example R in an above-mentioned average group accepted way of doing sth (4)
4In the illustrated base that goes out.
At this moment, R
10In at least 2 for thiazolinyl (especially carbon atom is preferably 2～8, more preferably 2～6 thiazolinyl).Need to prove, the content of thiazolinyl with whole organic groups of silicon atom bonding in (that is R in a described average group accepted way of doing sth (7),
10In the shown whole monovalence alkyl that do not replace or replace) be preferably 50～99 moles of %, be preferably 75～95 moles of % especially.Organopolysiloxane at (f) composition has under the situation of straight chain structure, and only either party and silicon atom bonding that this thiazolinyl can be in molecule chain end and non-molecular chain terminal portions also can be at both sides and silicon atom bondings.But consider from the angle of the curing speed of composition, the rerum natura of cured article etc., it is desirable to the silicon atom bonding of at least 1 thiazolinyl and molecule chain end.
(g) composition
(g) the poly-organohydrogensiloxanes of composition contains at least 2 (common 2～200), is preferably the hydrogen atom (SiH yl) of (common 3～100) and silicon atom bonding more than 3.(g) composition works as linking agent with the reaction of (f) composition.(g) molecular structure of composition is not particularly limited, and for example the arbitrary poly-organohydrogensiloxanes of in the past making of wire, ring-type, a chain, three-dimensional netted (arborescens) etc. also can be used as the use of (b) composition.(g) composition has under the situation of linear structure, and the SiH base can be at the end of molecular chain and only either party and the silicon atom bonding in the non-molecular chain terminal portions, also can be at both sides and silicon atom bonding.In addition, the Siliciumatom number (or polymerization degree) in 1 molecule is generally 2～300, is preferably about 4～150, can preferably use as (g) composition for aqueous poly-organohydrogensiloxanes down in room temperature (25 ℃).
As (g) composition, for example can use the poly-organohydrogensiloxanes shown in the following average group accepted way of doing sth (8);
R
11 pH
qSiO
（4-p-q）/2 （8）
(in the formula, R
11For identical or different kind do not replace or replace, not have aliphatics unsaturated link(age), carbonatoms be 1～10, more preferably 1～8 monovalence alkyl; P and q are preferably and satisfy 0.7≤p≤2.1,0.001≤q≤1.0 and 0.8≤p+q≤3.0, the positive number of 1.0≤p≤2.0,0.01≤q≤1.0 and 1.5≤p+q≤2.5 more preferably).As above-mentioned R
11, can list, for example the R in an above-mentioned average group accepted way of doing sth (4)
4In the illustrated group that goes out (wherein, except the thiazolinyl.）。
Concrete example as the poly-organohydrogensiloxanes shown in the above-mentioned average group accepted way of doing sth (8), can list, 1,1,3, the 3-tetramethyl disiloxane, 1,3,5,7-tetramethyl-ring tetrasiloxane, three (hydrogen dimethylamino base siloxy-) methyl-monosilane, three (hydrogen dimethylamino base siloxy-) phenyl silane, the methyl hydrogen cyclopolysiloxane, methyl hydrogen siloxane dimethyl siloxane cyclocopolymer, two terminal trimethylsiloxy end-blocking methylhydrogenpolysi,oxane, two terminal trimethylsiloxy end-blocking methyl hydrogen siloxane dimethylsiloxane copolymers, two terminal methyl group hydrogen siloxy-end-blocking dimethyl polysiloxanes, two terminal methyl group hydrogen siloxy-end-blocking methyl hydrogen siloxane dimethylsiloxane copolymers, two terminal trimethylsiloxy end-blocking methyl hydrogen siloxane diphenyl siloxane multipolymers, two terminal trimethylsiloxy end-blocking methyl hydrogen siloxane diphenyl siloxane dimethylsiloxane copolymers, two terminal trimethylsiloxy end-blocking methyl hydrogen siloxane methylphenyl siloxane dimethylsiloxane copolymers, two terminal methyl group hydrogen siloxy-end-blocking methyl hydrogen siloxane diphenyl siloxane dimethylsiloxane copolymers, two terminal methyl group hydrogen siloxy-end-blocking methyl hydrogen siloxane methylphenyl siloxane dimethylsiloxane copolymers, by (CH
3)
2HSiO
1/2Unit and (CH
3)
2SiO
2/2Unit 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.
(g) addition of composition is, per 1 mole of thiazolinyl in total relatively solidified nature silicon composition, especially relatively per 1 mole of the thiazolinyl with silicon atom bonding in total solidified nature silicon composition, per 1 mole of the thiazolinyl with silicon atom bonding in more specifically relative (f) composition, the amount of the SiH base in this (g) composition is 0.1～5.0 mole, be preferably 0.5～3.0 mole, more preferably 0.8～2.0 mole amount.At this moment, be present in the thiazolinyl in total solidified nature silicon composition relatively, (f) ratio with thiazolinyl silicon atom bonding in the composition is preferably 80～100 moles of %, more preferably 90～100 moles of %.In total solidified nature silicon composition, as the composition with thiazolinyl, when only having (f) composition, relatively the thiazolinyl in (f) composition is per 1 mole, and the amount of the SiH in this (g) composition is 0.1～5.0 mole, be preferably 0.5～3.0 mole, 0.8～2.0 mole amount more preferably.If this addition is the 0.1 mole of amount lacked of amount than above-mentioned SiH, it is long, unfavorable economically then to arrive the time required till solidifying.
In addition, if this addition is the amount of amount more than 5.0 moles than above-mentioned SiH, then solidifies anti-ying at this and answer in the thing owing to dehydrogenation reaction produces foaming, and then the intensity of this curing reaction thing and thermotolerance can be adversely affected.
(h) composition
(h) the platinum metals series catalysts of composition promotes (f) composition and the catalyzer of (g) the addition curing reaction (hydrogenation silylation reactive) of composition to use as being used for.As (h) composition, can use known platinum metals series catalysts, but preferably use platinum or platinic compound.As the concrete example of (h) composition, can list the complex compound of pure modifier, Platinic chloride and alkene, aldehyde, vinylsiloxane or the acetylene alcohols of platinum black, platinum chloride, Platinic chloride, Platinic chloride.
(h) addition of composition is the significant quantity as catalyzer.Increase and decrease according to desirable curing reaction speed in good time and to get final product, but (f) composition relatively is scaled quality standard in the platinum metals, be preferably 0.1～1,000ppm, the scope of 0.2～100ppm more preferably.
Condensation cured response type silicon composition:
As condensation cured response type silicon composition, particularly, can list, for example except described surface treatment silicon-dioxide ((α) composition), also comprise the condensation cured response type silicon composition of following compositions:
(i) contain at least 2 silanol bases (being the silicon atom bonding hydroxyl) or silicon atom bonding hydrolization group, be preferably the organopolysiloxane that contains at molecular chain two ends;
(j) as optional member, water-disintegrable silane and/or its partial hydrolysis condenses; And
(k) as the condensation catalyst of optional member.
(i) composition
(i) composition is the base polymer of condensation cured response type silicon composition for containing the organopolysiloxane of 2 silanol bases or silicon atom bonding hydrolization group at least.(i) organopolysiloxane of composition considers that from the angle of the easy degree that obtains raw material can be: molecular chain (main chain) is by two organo-siloxane unit (R basically
11 2SiO
2/2The unit) repeating unit formation, two ends of molecular chain are by three organic siloxy-(R
11 3SiO
1/2) the unbranched straight chain structure of end-blocking; Perhaps have molecular chain by the repeating unit of described two organo-siloxane unit constitute, unbranched ring texture, but also can partly contain a chain structure.Here, R
11Expression does not replace or replaces, carbonatoms is 1～10, more preferably 1～8 monovalence alkyl.
In the organopolysiloxane of (i) composition, the hydrolization group as beyond the silanol base for example can list acyloxy such as acetoxyl group, hot acyloxy, benzoyloxy; Ketoxime bases (being inferior aminooxy) such as dimethyl ketone oximido (ジ メ チ Le ケ ト オ キ シ system base), methyl ethyl ketone oximido, metacetone oximido; Alkoxyl groups such as methoxyl group, oxyethyl group, propoxy-; Alkoxyl group alkoxyl groups such as methoxy ethoxy, ethoxy ethoxy, methoxy propoxy; Vinyloxy group, pseudoallyl oxygen base, 1-ethyl-thiazolinyl oxygen bases such as 2-methyl ethylene oxygen base; Amino such as dimethylamino, diethylamino, butyl amino, cyclohexyl amino; Aminooxy such as dimethyl aminooxy, diethyl aminooxy; Amide group such as N-methylacetamide base, N-ethyl acetamide base, N-methyl-benzamide base etc.
These hydrolization groups, for example, the tri-alkoxy siloxy-, the organic siloxy-of dialkoxy, three acyloxy siloxyies, the organic siloxy-of two acyloxy, Sanya aminooxy siloxy-(namely, triketone oximido siloxy-), the organic siloxy-of two inferior aminooxy, triolefin oxygen base siloxy-, the organic siloxy-of diene oxygen base, tri-alkoxy siloxy-ethyl, the organic siloxy-ethyl of dialkoxy etc., it is desirable to, with the siloxy-that contains 2 or 3 hydrolization groups or with the form of siloxy-alkyl of containing 2 or 3 hydrolization groups etc., be positioned at two ends of the molecular chain of straight chain shape two organopolysiloxane.
As with other monovalence alkyl of silicon atom bonding, can list, with the R in an above-mentioned average group accepted way of doing sth (4)
4In the illustrated identical monovalence alkyl that does not replace or replace that goes out.
As (i) composition, for example can list,
[in above-mentioned formula, X is the hydrolization group beyond the described silanol base.A be 1,2 or respectively do for oneself 1～1,000 integer of 3, n and m].
Concrete example as (i) composition, can list molecular chain two terminal silanol base end-blocking dimethyl polysiloxanes, molecular chain two terminal silanol base end-blocking dimethyl siloxane methylphenyl siloxane multipolymers, molecular chain two terminal silanol base end-blocking dimethyl siloxane phenylbenzene polysiloxane copolymers, molecular chain two terminal trimethoxy siloxy-end-blocking dimethyl polysiloxanes, molecular chain two terminal trimethoxy siloxy-end-blocking dimethyl siloxane methylphenyl siloxane multipolymers, molecular chain two terminal trimethoxy siloxy-end-blocking dimethyl siloxane phenylbenzene polysiloxane copolymers, molecular chain two terminal 2-trimethoxy siloxy-ethyl capping dimethyl polysiloxanes etc.These can a kind use separately, also can be used in combination more than 2 kinds.
(j) composition
(j) the water-disintegrable silane of composition and/or its partial hydrolysis condenses are optional member, work as solidifying agent.When in 1 molecule, containing the organopolysiloxane of the silicon atom bonding hydrolization group beyond at least 2 silanol bases, can in condensation cured response type silicon composition, add (j) composition as (i) composition of base polymer.As (j) composition, preferably use the silane that in 1 molecule, contains at least 3 silicon atom bonding hydrolization groups and/or its partial hydrolysis condenses (that is, remaining at least 1, be preferably the organopolysiloxane of the hydrolization group more than 2).
As aforementioned silane, for example preferably use the silane shown in the formula (9):
R
12 rSiX
4-r （9）
(in the formula, R
12For do not replace or replace, carbonatoms is 1～10, more preferably 1～8 monovalence alkyl, X is hydrolization group, r is 0 or 1).As aforementioned R
12, especially preferably list alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl; Aryl such as phenyl, tolyl; Thiazolinyl such as vinyl, allyl group.
As the concrete example of (j) composition, for example can list Union carbide A-162, vinyltriethoxysilane, vinyltriacetoxy silane, tetraethyl silicate etc. and their partial hydrolysis condenses.These can a kind use separately, also can be used in combination more than 2 kinds.
Under the situation of the water-disintegrable silane that uses (j) composition and/or its partial hydrolysis condenses, (i) composition 100 mass parts relatively, its addition is preferably 0.01～20 mass parts, is preferably 0.1～10 mass parts especially.Under the situation of using (j) composition, its addition is if in above-mentioned scope, and then the storage stability of composition of the present invention and curing reaction speed are good especially.
(j) composition
(j) condensation catalyst of composition is optional member, has at the water-disintegrable silane of above-mentioned (j) composition and/or its partial hydrolysis condenses under the situation of for example aminooxy, amino, ketoxime base, also can not use.As the condensation catalyst of (k) composition, for example can list organic titanates such as tetrabutyl titanate, titanium isopropylate; Organic titanium inner complexs such as two (methyl ethyl diketone) titaniums of diisopropoxy, two (methyl aceto acetate) titaniums of diisopropoxy; Organo-aluminium compounds such as aluminium tris(acetylacetonate), three (methyl aceto acetate) aluminium; Organic zirconates such as four (methyl ethyl diketone) zirconium, four butyric ester zirconiums; Organo-tin compounds such as sad dibutyl tin, dibutyl tin laurate, two (2 ethyl hexanoic acid) dibutyl 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 basic amine, 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 compounds can a kind use separately, also can be used in combination more than 2 kinds.
Under the situation of the condensation catalyst that uses (k) composition, its addition is not particularly limited, and for the significant quantity as catalyzer get final product, but relative (i) composition 100 mass parts, is preferably 0.01～20 mass parts, is preferably 0.1～10 mass parts especially.Under the situation of using (k) composition, if its addition in above-mentioned scope, is then considered favourable economically from the angle of set time and solidification value.
The curing of organo-peroxide curing reaction type silicon composition:
By heating organo-peroxide curing reaction type silicon composition, free radical reaction is carried out, and curing reaction carries out, thereby the organo-peroxide silicon composition solidifies.About the temperature condition that the organo-peroxide silicon composition is solidified, as the Heating temperature of this moment, because curing reaction depends on cladding thickness, namely depend on glue spread, thereby be not particularly limited, be preferably 80 ℃～300 ℃, more preferably 150 ℃～250 ℃.In addition, also can carry out 2 times as required solidifies.Temperature condition as this moment is preferably more than 120 ℃, more preferably 150 ℃～250 ℃.Be preferably 10 minutes the set time of this moment～48 hours, more preferably 30 minutes～24 hours.
The curing of the reactive silicon composition of ultraviolet curing:
By to the reactive silicon composition irradiation ultraviolet radiation of ultraviolet curing, the Photoepolymerizationinitiater initiater reaction, curing reaction carries out, and the reactive silicon composition of ultraviolet curing solidifies.For the uviolizing condition, because curing reaction depends on cladding thickness, namely depend on glue spread, thereby be not particularly limited, can use the ultraviolet LED with 365nm emission wavelength, be 5～500mW/cm in illumination
2, be preferably 10～200mW/cm
2, light quantity 0.5～100J/cm
2, be preferably 10～50J/cm
2Condition under carry out uviolizing, make its curing thus.In addition, also can carry out 2 times as required and solidify, the temperature condition as this moment is preferably more than 120 ℃, more preferably 150 ℃～250 ℃.Be preferably 10 minutes the set time of this moment～48 hours, more preferably 30 minutes～24 hours.
The curing of the reactive silicon composition of addition curing:
By the reactive silicon composition of heating addition curing, the hydrogenation silylation reactive is carried out, and the reactive silicon composition of addition curing solidifies.As the Heating temperature of this moment, because curing reaction depends on cladding thickness, namely depend on glue spread, thereby be not particularly limited, be preferably 80 ℃～300 ℃, more preferably 100 ℃～200 ℃.In addition, also can carry out 2 times as required solidifies.Temperature condition as this moment is preferably more than 120 ℃, more preferably 150 ℃～250 ℃.Be preferably 10 minutes the set time of this moment～48 hours, more preferably 30 minutes～24 hours.
The curing of condensation cured response type silicon composition:
By heating condensation cured response type silicon composition, condensation reaction is carried out, and condensation cured response type silicon composition solidifies.For the temperature condition that condensation cured response type silicon composition is solidified, as the Heating temperature of this moment, because curing reaction depends on cladding thickness, namely depend on glue spread, thereby be not particularly limited, be preferably 80 ℃～300 ℃, more preferably 100 ℃～200 ℃.In addition, also can carry out 2 times as required solidifies.Temperature condition as this moment is preferably more than 120 ℃, more preferably 150 ℃～250 ℃.Be preferably 10 minutes the set time of this moment～48 hours, more preferably 30 minutes～24 hours.
Other composition:
Composition of the present invention, irrelevant with the kind of curing mechanism, can cooperate other composition as required.For example, can list dispersed rising agent etc.
As dispersed rising agent, have by being added on and improve the effect that aforementioned surfaces is handled the dispersiveness of silicon-dioxide, improved the flowability of composition in the composition.Particularly can list, hexamethyldisilazane, 1,3-Er Yi Xi Ji ?1,1,3,3-tetramethyl-disilazane, 1,1,3,5, silicoorganic compound such as organosilicon alkanes such as organic amino base silane, organochlorosilane, organoalkoxysilane such as organosilazanes, dimethylamino trimethyl silicane azane, dimethylamino dimethyl vinyl silanes such as 5,5-, seven first base ?3-vinyl, three silazane.
Composition is under the situation of addition curable, as the addition reaction control agent, can add ethynyl methylene radical methyl alcohol, 1-ethynyl-1-hexyl-3-butine etc.
The cured article that composition curing of the present invention is obtained has good thermal conductivity, and thermal conductivity coils method (ホ ッ ト デ ィ ス Network method) according to heat and is preferably more than the 0.3W/mK 25 ℃ measured values, and it is desirable to is more than 0.4.Thermal conductivity then is not suitable for the big heating element of thermal value if be lower than 0.3W/mK.In addition, the transparency of this cured article is excellent, with thickness be the layer state of 1mm when measuring for 20 ℃, the optical transmission rate of wavelength 800nm is preferably more than 60%, more preferably more than 70%.Further, this cured article is the layer state of 1mm when measuring with thickness, has the flame retardant resistance that satisfies the UL94V-1 standard.
Embodiment
Preparation example 1:
-surface treatment silicon-dioxide (C-1) synthetic-
Tetramethoxy-silicane 1165g is added in the mixing solutions of ammoniacal liquor (28 quality %) 50g, water 42g, methyl alcohol 625g and stirred 6 hours.Then add 400g ammoniacal liquor (5.4 quality %) and stirred 4 hours, obtain sol-gel silicon-dioxide.Further add 1200g water, add the 12g trimethoxymethylsila,e and stir after 12 hours, add the 450g methyl iso-butyl ketone (MIBK), water is heated up in a steamer.Then, add the 150g hexamethyldisilazane after stirring 3 hours under 100 ℃, by heating up in a steamer desolventizing and dry, obtain surface treatment silicon-dioxide (C-1).
The mensuration of-surface treatment degree-
Get surface treatment silicon-dioxide and 3g tetraethoxysilane and the 0.085g potassium hydroxide of 0.3g (C-1), 120 ℃ of following heat treated 3 hours.As the standard test specimen of this moment, use three (trimethylsiloxy) methyl-monosilane.Try to achieve from the typical curve that obtains by the dimeric correction value that adds up to triethoxy methyl silicane and triethoxy methyl silicane and tetraethoxysilane the M unit.In addition, the T unit will be by will being that the area ratio of the vapor-phase chromatography of benchmark multiply by mol and tries to achieve than coefficient with the M quantity of units.
The result is expressed as follows with said determination.
M unit: 0.0093 (mol/100g)
T unit: 0.015 (mol/100g).
Because sol-gel silicon-dioxide is made of the Q unit, therefore from totally deduct the M unit that obtains by mensuration, the amount of T unit just can be tried to achieve the Q quantity of units.The M unit of this moment is SiMe
3O
1/2, formula weight is that 81.19, T unit is SiMeO
3/2, formula weight is 67.12, thereby in the 100g surface treatment silicon-dioxide, contains 0.76g M unit and 1.00g T unit.That is, from 100g, deduct M quantity of units and T quantity of units and the 98.24g that obtains to be 100g handle the Q quantity of units that contains in the silicon-dioxide.If it is scaled mole number, be 1.64mol then, in molar basis, p/q=0.015.
-median size-
Measure with the laser diffraction and scattering method, the result is 130nm.
Preparation example 2:
-surface treatment silicon-dioxide (C-2) synthetic-
With handling silicon-dioxide (C-2) with the similar step synthetic surface of preparation example 1, and similarly operational computations goes out p/q=0.03.Median size is determined as 150nm.
Preparation example 3:
-surface treatment silicon-dioxide (C-3) synthetic-
With handling silicon-dioxide (C-3) with the similar step synthetic surface of preparation example 1, and similarly operational computations goes out p/q=0.008.Median size is determined as 160nm.
Preparation example 4:
-surface treatment silicon-dioxide (C-4) synthetic-
With handling silicon-dioxide (C-4) with the similar step synthetic surface of preparation example 1, and similarly operational computations goes out p/q=0.04.Median size is determined as 150nm.
Embodiment 1～5 and comparative example 1～4
Use material:
＜(A) composition＞
Organopolysiloxane shown in the following formula:
(in the formula, X is vinyl, n be following shown in the numerical value of viscosity (25 ℃))
(A-1) viscosity: 100mm
2/ s
(A-2) viscosity: 600mm
2/ s.
＜(B) composition＞
Poly-organohydrogensiloxanes shown in the following formula:
(in the formula, o is that mean value 28, p are mean value 10).
＜(C) composition＞
Silicon-dioxide
(C-1) p/q=0.015 (median size 130nm)
(C-2) p/q=0.03 (median size 150nm)
(C-3) p/q=0.008 (median size 160nm)
(C-4) p/q=0.004 (median size 150nm)
(C-5) untreated silica (AEROSIL 130).
＜(D) composition＞
The addition curing catalyzer
5 quality % Platinic chloride 2-Ethylhexyl Alcohol solution.
＜(E) composition＞
Ethynyl methylene radical methyl alcohol as the addition reaction control agent.
＜(F) composition＞
Hexamethyldisilazane.
Preparation of compositions:
In each embodiment and each comparative example, (A) composition, (C) composition with the specified amount shown in the table 1, were used planetary mixer mixing 60 minutes.Wherein, in comparative example 3, attempted relative organopolysiloxane (A-1) 100 mass parts, mixing 20 mass parts silicon-dioxide (C-5), but this 20 mass parts can not filled equably yet.Then, (D) composition of specified amount shown in the adding table 1 and (E) composition in the mixing thing that obtains, further, add the promotion of significant quantity and separator (the セ パ レ ー タ) demoulding in add after the releasing agent mixing 30 minutes.Further, add (B) composition of specified amount shown in the table 1, mixing 30 minutes, thus obtain composition.
Moulding and curing
The composition of each embodiment and comparative example is cast in 100mm * 100mm * 1mm(degree of depth) mould in, use press-forming machine to handle down at 110 ℃ and carried out moulding in 10 minutes.Under the situation that does not have special record, use the thick sheet material of 1mm that obtains thus to carry out following evaluation.
Evaluating characteristics
Characteristic below measuring is estimated.The results are shown in table 1.
Thermal conductivity:
2 thick sheet materials of 6mm of mould made use 60mm * 60mm * 60mm(degree of depth) are measured thermal conductivity by thermal conductivity instrument (trade(brand)name TPA-501, capital of a country electronic industry Co., Ltd. make).
Transmitance:
Use spectrophotometer (Hitachi's manufacturing) that the thick sheet material of 1mm is measured.
Flame retardant resistance:
Flame retardant test method according to UL94 is tested.
[table 1]
Estimate:
If the p/q value of surface treatment silicon-dioxide is little than 0.01 as comparative example 1, even then filled silicon-dioxide with embodiment 1 equal in quality umber, owing to the dispersiveness reduction, thereby the transmitance reduction.And if reduce as comparative example 2 further surface treatment degree, then dispersiveness becomes poorer, and transmitance also reduces.If use untreated silica as comparative example 3, then fillibility significantly reduces, and 20 mass parts can not filled equably yet, thereby can't obtain uniform composition, can not carry out evaluating characteristics.
Usability on the industry
Heat-conductive silicone composition of the present invention can use at the position that requires thermal conductivity and even thermal diffusivity, flame retardant resistance and the transparency.For example, as the transparent radiating protective film of liquid crystal flat panel display (LCD), and useful as transparent encapsulation material and the transparent reflector material of photodiode (LED) element.
Claims (8)
1. heat-conductive silicone composition, it is for comprising:
(α) hydrophobization surface treatment silicon-dioxide, it is made of following substances: by SiO
1/2The base material silicon-dioxide that unit (Q unit) constitutes and handle on its surface and combination surface treatment agent; And
(β) organopolysiloxane composition
Heat-conductive silicone composition, it is characterized in that,
Described surface treatment agent is the silicoorganic compound shown in the general formula (X):
In the formula, R
1For having 3 functionality side chains but do not have 4 functionality side chains and the organo-siloxane base of 1 valency that stops with Sauerstoffatom with the end of silicon atom bonding; Perhaps be the alkyl of replacement or unsubstituted 1 valency, R
2Be alkyl, x is 1～3 integer,
The mol ratio (p/q) of the quantity (p) of the Siliciumatom of the surface treatment agent of the surface bonding of formation and base material silicon-dioxide and the quantity (q) of described Q unit is in 0.01～0.3 scope.
2. silicon composition as claimed in claim 1 wherein, with respect to organopolysiloxane composition 100 mass parts in this composition, contains described surface treatment silica 1 00～500 mass parts.
3. silicon composition as claimed in claim 1 or 2, wherein, the median size of described surface treatment silicon-dioxide is that 20nm is above and below the 200nm.
4. as each described silicon composition in the claim 1～3, it is the addition reaction curing.
5. organosilicon cured article, it makes in the claim 1～4 each described composition solidify and obtains.
6. organosilicon cured article as claimed in claim 5, its thermal conductivity is more than the 0.3W/mK.
7. as claim 5 or 6 described organosilicon cured articles, be when measuring with 20 ℃ under the layer state of 1mm at thickness, the optical transmission rate of wavelength 800nm is more than 60%, the transparency is high.
8. as each described organosilicon cured article in the claim 5～7, when under thickness is the layer state of 1mm, measuring, has the flame retardant resistance that satisfies the UL94V-1 standard.
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| PCT/JP2011/079907 WO2012093602A1 (en) | 2011-01-07 | 2011-12-22 | Highly transparent, thermally conductive silicone composition and cured material |
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| TWI509024B (en) * | 2012-10-02 | 2015-11-21 | Daxin Materials Corp | Hardenable resin composition, curried article using the same, and semiconductor device |
| CN105264022A (en) * | 2013-05-30 | 2016-01-20 | 住友电木株式会社 | Hydrophobic inorganic particles, resin composition for heat dissipation member, and electronic component device |
| JP6380386B2 (en) * | 2013-05-30 | 2018-08-29 | 住友ベークライト株式会社 | Resin composition for heat dissipation member and electronic component device |
| JP6380387B2 (en) * | 2013-05-30 | 2018-08-29 | 住友ベークライト株式会社 | Resin composition for heat dissipation member and electronic component device |
| JP6052094B2 (en) * | 2013-08-06 | 2016-12-27 | 信越化学工業株式会社 | Method for producing polytetrafluoroethylene powder composition and method for producing resin composition containing the same |
| CN106661439B (en) * | 2014-08-11 | 2019-10-15 | 株式会社I.S.T | The modified liquid crystal liquid crystal property elastomer of the thermal conductivity modifiers and thermal conductivity of elastomer |
| JP6183319B2 (en) * | 2014-08-21 | 2017-08-23 | 信越化学工業株式会社 | Thermally conductive silicone composition and thermally conductive sheet |
| JP6860287B2 (en) * | 2015-10-21 | 2021-04-14 | 株式会社Kri | Thermally conductive filler and transparent thermally conductive resin composition |
| WO2018164231A1 (en) * | 2017-03-09 | 2018-09-13 | 三菱ケミカル株式会社 | Composition, molded body and complex member |
| JP6764376B2 (en) | 2017-06-15 | 2020-09-30 | 信越化学工業株式会社 | Silicone composition and its manufacturing method |
| CN110741048B (en) | 2017-06-15 | 2022-03-22 | 信越化学工业株式会社 | Silicone composition and method for preparing the same |
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| JP2002188010A (en) * | 2000-12-19 | 2002-07-05 | Ge Toshiba Silicones Co Ltd | Polyorganosiloxane composition curable by addition reaction |
| JP2008143725A (en) * | 2006-12-06 | 2008-06-26 | Toda Kogyo Corp | Method for manufacturing surface-treated inorganic particle powder |
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| JP4209608B2 (en) * | 2001-11-14 | 2009-01-14 | 信越化学工業株式会社 | Room temperature curable silicone rubber composition |
| JP4905674B2 (en) * | 2006-11-13 | 2012-03-28 | 信越化学工業株式会社 | Organosilicon compound |
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| JP2002188010A (en) * | 2000-12-19 | 2002-07-05 | Ge Toshiba Silicones Co Ltd | Polyorganosiloxane composition curable by addition reaction |
| JP2008143725A (en) * | 2006-12-06 | 2008-06-26 | Toda Kogyo Corp | Method for manufacturing surface-treated inorganic particle powder |
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| CN103980857A (en) * | 2014-05-21 | 2014-08-13 | 浙江新安化工集团股份有限公司 | Adhesive silicone grease composition and preparation method thereof |
| CN103980857B (en) * | 2014-05-21 | 2018-12-11 | 浙江新安化工集团股份有限公司 | Adhesion type silicone grease composition and preparation method thereof |
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| KR101780526B1 (en) | 2017-10-10 |
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