CN101027330A - Silica-containing silicone resin composition and its molded product - Google Patents
Silica-containing silicone resin composition and its molded product Download PDFInfo
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- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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Abstract
This invention provides a silica-containing silicone resin composition which can impart high heat resistance, high transparency, and high dimensional stability and is suitable, for example, for optical applications such as lenses, optical disks, optical fibers, and flat panel display substrates, and window materials for automobiles. This silica-containing silicone resin composition is produced by incorporating 1 to 70% by weight of silica fine particles into a silicone resin composition prepared by mixing a silicone resin, which is represented by [RSiO<SUB>3/2</SUB>]<SUB>n</SUB> wherein R represents an (meth)acryloyl-containing organic functional group; and n is 8, 10 or 12, and is composed mainly of polyorganosilsesquioxane having a basket structure in its structural units, and an unsaturated compound, which contains in its molecule at least one unsaturated group represented by -R<SUP>3</SUP>-CR<SUP>4</SUP>=CH<SUB>2</SUB> or -CR<SUP>4</SUP>=CH<SUB>2</SUB> wherein R<SUP>3</SUP> represents an alkylene group, an alkylidene group, or group -OCO-; and R<SUP>4</SUP> represents hydrogen or an alkyl group, and is radically copolymerizable with the silicone resin at a weight ratio of 1 : 99 to 99 : 1.
Description
Technical field
The present invention relates to contain the organosilicon resin composition of silicon-dioxide and as the resin-formed body of three-dimensional cross-linked body.
Background technology
Unorganic glass has the high transparency and thermotolerance, dimensional stability, so as the compartment but see through visible light and do not hinder the structure of visibility, obtaining utilizing in the industrial field widely since ancient times.Though be the unorganic glass with these advantageous feature, proportion weighs more than 2.5 and the easy fragmentation of not shock resistance is two big shortcomings.Especially in recent years carry out light weight, thin-walled property and so on and reduce the result of size in all industrial fields, it is surging day by day that customer requirements improves the cry of above-mentioned shortcoming.
As the material that meets from the requirement of these industrial communitys, people have focused on expectation on transparent thermoplasticity, the thermosetting resin.Wherein, as transparent thermoplastics, can enumerate PMMA (polymethylmethacrylate), PC (polycarbonate) etc.Wherein, PMMA is also referred to as synthetic glass, and is excellent as the transparency, and it is noticeable to have overcome the material of two big shortcomings of glass.Yet the thermotolerance of these transparent plasticss and linear thermal expansion ratio be significantly than unorganic glass difference, the problem that exists purposes to be restricted.
On the other hand, as transparent thermosetting resin, can enumerate Resins, epoxy, curing (methyl) acrylate resin, silicone resin etc., these thermosetting resines generally have the thermotolerance higher than above-mentioned thermoplastics.Though wherein the Resins, epoxy cure shrinkage is little and formability is excellent, and the low and crisp shortcoming of shock resistance of forming composition is arranged.In addition, curing (methyl) though the balance excellence of the rerum natura of acrylate resin thermotolerance and formability, forming composition etc., the size changing rate that water-intake rate causes and to be subjected to thermogenetic linear expansivity be greatly shortcoming.
Silicone resin so be the problem that solves above-mentioned each plastics, substitutes the highest material of possibility of unorganic glass owing to excellence aspect thermotolerance, weathering resistance and water tolerance in the thermosetting resin.Especially the organic poly sesquisiloxane of ladder structure, the crowd knows the thermotolerance that demonstrates not second to polyimide.
The document in advance that the present invention is correlated with has following document.
Patent documentation 1: special public clear 40-15989 communique
Patent documentation 2: the spy opens clear 50-139900 communique
Patent documentation 3: the spy opens the 2003-137944 communique
Patent documentation 4: the spy opens the 2004-12396 communique
Patent documentation 5: the spy opens the 2004-143449 communique
Non-patent literature 1:J.Polymer Sci.PartC, No.1, PP.83-97 (1963)
Non-patent literature 2: Japanization association will, 571-580 (1998)
Example as such organic poly sesquisiloxane, in patent documentation 1,2, the non-patent literature 1 manufacturing being disclosed: in organic solvent the phenyl-trichloro-silicane hydrolysis is become the phenyl ortho-siliformic acid, use alkalescence rearrangement and condensation catalyst this hydrolysis resultant to be heated the cage modle octaphenyl silsesquioxane that makes it to dewater polycondensation and obtain in anhydrous solvent; Separate this cage modle octaphenyl silsesquioxane, reuse that alkalescence is reset and condensation catalyst heated polymerizable and the low phenyl siloxane prepolymer of limiting viscosity that obtains; Or re-use the method for the high phenyl silsesquioxane polymkeric substance of alkalescence is reset and condensation catalyst obtains these heated polymerizables limiting viscosity.
Yet the silicone resin that contains this organic poly sesquisiloxane must increase cross-linking density because the flexibility of siloxane bond is big in order to make structure present required Young's modulus.But cure shrinkage increased significantly when cross-linking density increased, because forming composition fragilityization and not preferred.In addition, because the residual stress that cure shrinkage produces increase, so arrive the forming composition of wall thickness scarcely ever.Because this reason, the big silicone resin of cross-linking density is only limited to the coating purposes, the employed low silicon rubber of cross-linking density that stays in of moulding purposes at present.Non-patent literature 2 discloses the method with the acrylic resin copolymerization of forming process excellence, for example, as non-ladder type silicone resin, use side chain to have the acrylate copolymer of alkoxysilyl, by making itself and organoalkoxysilane copolymerization, formation is organic composition with the acrylate copolymer, is the technology of the mixture of inorganic components with the polysiloxane.Yet, because silicone resin is original and the consistency of acrylate resin is insufficient, so even no problem occasion such as physical strength also often optical characteristics such as light penetration destroyed.
In addition, patent documentation 3, the 4 disclosed organosilicon resin composition of the silicone resin that does not contain silanol group and the silicone resin formed bodys of having used demonstrate excellent thermotolerance, optical characteristics, water absorption character.Yet, in the presence of alkalescence rearrangement and condensation catalyst, make cage modle organic poly sesquisiloxane and sily oxide compound carry out the silicone resin that equilibration reaction is made with reactive functional groups, the reactive functional groups number of per 1 molecule is few, 1.1 of average out to are inferred to participate in formed body in the three-dimensional crosslinking structure and are lacked.Promptly, when making the ratio increase of the silicone resin that helps thermotolerance, weathering resistance and water tolerance feature, the absolute number of the reactive functional groups number in the formed body reduces, cross-linking density reduces and can not constitute sufficient three-dimensional crosslinking structure body, and the result forms the formed body of thermotolerance, mechanical characteristics reduction.
On the other hand, the method as reducing linear expansivity has and add mineral filler usually in resin, make the method for the ratio increase of inorganic components in the resin, but added the occasion of mineral filler, had the transparency that loses formed body, because of the uneven problem that becomes in the bad dispersibility resin.Disclose relevant use silane compound among JP5-209027A, JP10-231339A, the JP10-298252A, colloid silica has been dispersed in the transparency in the free-radical polymerised vinyl compounds such as methyl methacrylate and the curing composition of excellent rigidity.Yet these mainly are at the composition of hard coat with design, are not the suitable compositions that uses with material that substitutes as glass.In addition, the disclosed complex body cured article of being made up of ester ring type (methyl) acrylate, silicon dioxide microparticle, silane compound, tertiary amine compound keeps the transparency, low linear expansion excellence among the JP2003-213067A.But for linear expansivity is reduced to less than 40ppm/K, must add silicon dioxide microparticle more than the 70 weight % with respect to the ester ring type acrylate, must use a large amount of silicon dioxide microparticles and make it to disperse equably, in addition because use silicon dioxide microparticle in large quantities so the viscosity of composition increases the manufacturing difficulty of formed body.
With (RSiO
3/2)
nThe cage modle organic poly sesquisiloxane of expression is known in above-mentioned patent documentation 5, has also put down in writing it and can use with other mixed with resin.In the formula, R is the organo-functional group that contains acryl etc., and n is 8,10,12 or 14.
Summary of the invention
Therefore, the characteristic that the object of the present invention is to provide optical characteristics, thermotolerance, weathering resistance and so on silicone resins such as keeping the transparency to possess, only a small amount of organosilicon resin composition that contains silicon-dioxide that cooperates silicon dioxide microparticle just can give the silicone resin formed body that contains silicon-dioxide of dimensional stabilizing (low linear expansion) property excellence.
The present inventor is in order to finish the result that above-mentioned problem is studied repeatedly, find by in the silicone resin of the unsaturated compound of free redical copolymerization and cage modle, cooperating silicon dioxide microparticle by specific ratios, can be applicable to the transparent silicone resin formed body that contains silicon-dioxide of the unorganic glass purposes of alternative low heat expansion property, transparency excellence, thereby finish the present invention.
The present invention relates to contain the organosilicon resin composition of silicon-dioxide, it is characterized in that: will be with general formula (1)
[RSiO
3/2]
n (1)
Shown in (in the formula, R is the organo-functional group with (methyl) acryl, and n is 8,10 or 12), the organic poly sesquisiloxane that has cagelike structure in the structural unit is to contain at least 1-R in the silicone resin of main component and the molecule
3-CR
4=CH
2Or-CR
4=CH
2(in the formula, R
3Expression alkylidene group, alkylidene or-the OCO-base, R
4The expression hydrogen or alkyl) unsaturated group shown in, the silicon dioxide microparticle that the use silane compound of cooperation 1～70 weight % was handled can be carried out in the organosilicon resin composition that free-radical polymerized unsaturated compound cooperates by 1: 99～99: 1 part by weight with aforementioned silicone resin.
Use therein silicone resin preferably makes general formula (3) in the presence of polar solvent and basic catalyst
RSiX
3 (3)
(R is the organo-functional group with (methyl) acryl; X represents hydrolization group) shown in the silicon compound reaction that is hydrolyzed; make the part condensation simultaneously; make the hydrolysis resultant that obtains condensation and the silicone resin made again in the presence of non-polar solvent and basic catalyst again; preferably the Siliciumatom number equates with (methyl) acryloyl radix in its molecule, and has the silicone resin of cagelike structure.
Be blended in the unsaturated compound of the free redical copolymerization in the above-mentioned organosilicon resin composition, preferably comprise following general formula (4)
The unsaturated compound with hydroxyl of (in the formula, R is the organo-functional group with (methyl) acryl, and X is hydrogen or has the organo-functional group of (methyl) acryl that n is 0 or 1 integer) expression.
In addition, add the silicon dioxide microparticle in the above-mentioned organosilicon resin composition to, preferably the median size of silicon dioxide microparticle is 1～100nm, and using with respect to silicon dioxide microparticle is the following general formula (5) of 0.1～80 weight %
RmSiA
nX
4-m-n (5)
(in the formula; R is the organo-functional group with (methyl) acryl; A is an alkyl; X is alkoxyl group or halogen atom; it is 1～3 integer that m and n satisfy m+n; m is 0 or 1, and n is 0～3 integer) shown in the silicon dioxide microparticle handled of silane compound, the use level of silicon dioxide microparticle is 1～70 weight % with respect to organosilicon resin composition.
In addition, the present invention relates to make the above-mentioned described organosilicon resin composition that contains silicon-dioxide to carry out free-radical polymerized and the silicone resin formed body that contains silicon-dioxide that obtain.In addition, the invention still further relates to the following and total light penetration of linear expansivity 40ppm/K more than 85%, the silicone resin formed body that contain silicon-dioxide of second-order transition temperature more than 300 ℃.
Embodiment
The organosilicon resin composition that contains silicon-dioxide of the present invention is with silicone resin and can be main component with the unsaturated compound and the silicon dioxide microparticle of this silicone resin copolymerization.The silicone resin multipolymer that contains silicon-dioxide of the present invention makes this organosilicon resin composition that contains silicon-dioxide carry out free-radical polymerized and makes.Formed body of the present invention maybe contains this silicone resin multipolymer moulding of silicon-dioxide with this organosilicon resin composition forming and hardening that contains silicon-dioxide and obtains.The silicone resin multipolymer that contains silicon-dioxide of the present invention is a cross-linked polymer, and this occasion can adopt the forming and hardening method same with thermosetting resin.
The silicone resin that uses among the present invention, with by shown in the above-mentioned general formula (1), the organic poly sesquisiloxane (being also referred to as the cage modle organic poly sesquisiloxane) that has cagelike structure in the structural unit is main component.
In the general formula (1), R is the organo-functional group with (methyl) acryl, and n is 8,10 or 12, but the organo-functional group that preferred R is following general formula (9) expression.In the general formula (9), m is 1～3 integer, R
1Be hydrogen atom or methyl.
No matter silicone resin in the past is ladder type, non-ladder type, and is low with the consistency of the organic compound with the functional group as acrylic resin, can not obtain transparent formed body by their composition.Yet, above-mentioned silicone resin, outstanding with the reactive functional groups that the consistency of organic compound is high to the outside of cage, otherwise partly enter the inboard of cage with the low siloxane backbone of the consistency of organic compound, form accurate micellar structure, so can mix with ratio arbitrarily with unsaturated compounds such as Acrylic Acid Monomer, oligopolymer.
Has reactive functional groups on the Siliciumatom of cage modle organic poly sesquisiloxane in molecule of above-mentioned general formula (1) expression.Be the concrete structure of 8,10,12 cage modle organic poly sesquisiloxane as the n in the general formula (1), can enumerate the cagelike structure body shown in following structural formula (6), (7) and (8).Moreover, the R in the following formula represent with general formula (1) in the identical meaning of R.
The cage modle organic poly sesquisiloxane of general formula (1) expression can adopt described method manufacturings such as patent documentation 5.For example, can make the reaction that in the presence of polar solvent and basic catalyst, is hydrolyzed of the silicon compound of above-mentioned general formula (3) expression, make the part condensation simultaneously, make the condensation and obtaining again in the presence of non-polar solvent and basic catalyst of the hydrolysis resultant that obtains again.In the general formula (3), R is the organo-functional group with (methyl) acryl, and X represents hydrolization group, and preferred R is the group of aforementioned formula (9) expression.If enumerate the concrete example of preferred R, can enumerate 3-methacryloxypropyl, methacryloxy methyl, 3-acryloxy propyl group.
In the general formula (3), hydrolization group X does not then have particular determination so long as have water-disintegrable group, can enumerate alkoxyl group, acetoxyl group etc., preferably alkoxyl group.As alkoxyl group can enumerate methoxyl group, oxyethyl group, just reach isopropoxy, just, different and tert.-butoxy etc.The high methoxyl group of preferred reactive wherein.
As if preferred compound in the silicon compound of enumerating general formula (3) expression, can enumerate methacryloxy Union carbide A-162, methacryloxy methyltrimethoxy silane, 3-methacryloxypropyl trichlorosilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxyl silane, 3-acryloxy propyl trimethoxy silicane, 3-acryloxy propyltrichlorosilan.Wherein, the 3-methacryloxypropyl trimethoxy silane of preferably using raw material to obtain easily.
Basic catalyst as the hydrolysis reaction use, can enumerate alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, cesium hydroxide, or ammonium hydroxide salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, hydroxide benzyl TMA (TriMethylAmine), hydroxide benzyl three second ammoniums.Among these, consider, preferably use tetramethylammonium hydroxide from the aspect that catalytic activity is high.Basic catalyst uses as the aqueous solution usually.
Relevant hydrolysis reaction condition, preferred 0～60 ℃ of temperature of reaction, more preferably 20～40 ℃.When temperature of reaction was lower than 0 ℃, speed of response was slack-off, and hydrolization group left behind with unreacted state, and the result spends the reaction times in a large number.On the other hand, when higher than 60 ℃, because speed of response is too fast, so complicated condensation reaction is carried out, the result promotes the polymer of hydrolysis resultant to quantize.In addition, the reaction times is preferred more than 2 hours.The reaction times less than is in the time of 2 hours, and hydrolysis reaction carries out deficiently, becomes hydrolization group with the remaining state of unreacted state.
Must there be water in hydrolysis reaction, and this water can be supplied with by the aqueous solution of basic catalyst, and the water that also can be used as other approach adds.The amount of water is to satisfy more than the amount that hydrolization group is hydrolyzed, preferably 1.0～1.5 of theoretical amount times of amounts.In addition, organic polar solvent must be used during hydrolysis, alcohols such as methyl alcohol, ethanol, 2-propyl alcohol can be used as organic polar solvent, or other organic polar solvent.Preferably deliquescent C is arranged with glassware for drinking water
1-6Lower alcohols, more preferably use the 2-propyl alcohol.Reaction system does not reach evenly when using non-polar solvent, and hydrolysis reaction carries out deficiently, and unreacted alkoxyl group is remaining and not preferred.
After hydrolysis reaction finishes, divide dried up or contain the reaction solvent of water.Water or the separation that contains the reaction solvent of water can be adopted methods such as reduction vaporization.In order to remove moisture, other impurity fully, can adopt and add non-polar solvent and make the dissolving of hydrolysis reaction resultant, use these solution of washing such as salt solution, use siccative such as anhydrous magnesium sulfate to carry out methods such as drying then.If adopt method separation non-polar solvents such as evaporation, then can reclaim the hydrolysis resultant of reaction, if but non-polar solvent can be used as the non-polar solvent use of using in next reaction, then do not need to separate non-polar solvent.
In the hydrolysis reaction of the present invention, the condensation reaction that produces hydrolyzate with hydrolysis.With the hydrolysis resultant that the condensation reaction of hydrolyzate is accompanied, become the colourless viscous liquid of number-average molecular weight 1400～5000 usually.The hydrolysis resultant is different because of reaction conditions, becomes the oligopolymer of number-average molecular weight 1400～3000, the major part of the hydrolization group X shown in the general formula (3), is preferably roughly all replaced the major part of this OH base, preferred 95% above condensation in addition by OH base.The structure of hydrolysis resultant is the silsesquioxane of multiple cage modle, ladder type, random, the compound with cagelike structure, and the ratio of cagelike structure is few fully, and the structure of the incomplete cage modle of the part of opening of cage is main.Therefore, heat so that siloxane bond condensation (being called condensation again), thereby optionally make the silsesquioxane of cagelike structure by the hydrolysis resultant that in the presence of basic catalyst, in the organic solvent this hydrolysis is obtained again.
After dividing dried up or containing the reaction solvent of water, in the presence of non-polar solvent and basic catalyst, carry out condensation reaction again.The reaction conditions of relevant condensation reaction again, the scope that temperature of reaction is preferred 100～200 ℃, more preferably 110～140 ℃.In addition, when temperature of reaction is too low, can not obtain for condensation reaction is again carried out motivating force fully, not react.When temperature of reaction is too high, owing to might cause the auto-polymerization reaction by (methyl) acryl, thus necessary inhibited reaction temperature, or add stopper etc.Preferred 2～12 hours of reaction times.The usage quantity of non-polar solvent can be the amount that is enough to dissolve the hydrolysis reaction resultant, and the usage quantity of basic catalyst is the scope of 0.1～10 weight % with respect to the hydrolysis reaction resultant.
As non-polar solvent, can be not have solvability or almost do not have deliquescent solvent, the preferred hydrocarbons series solvent with water.As described hydrocarbon system solvent, low-boiling non-polar solvents such as toluene, benzene, dimethylbenzene are arranged.Wherein preferably use toluene.As basic catalyst, can use the basic catalyst that uses in the hydrolysis reaction, can enumerate alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, cesium hydroxide, or ammonium hydroxide salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, hydroxide benzyl TMA (TriMethylAmine), hydroxide benzyl three second ammoniums, but preferred tetra-allkylammonium etc. are to the catalyzer of non-polar solvent solubility.
In addition, the hydrolysis resultant of condensation use preferably makes the hydrolysis resultant after washing with water, dewater, concentrating again, but also can not wash, dewaters and use.Also can there be water during this reaction, but do not need to add on one's own initiative water, can stay in the moisture degree of bringing into by the base catalysis agent solution.Moreover, the occasion that the hydrolysis of hydrolysis resultant is carried out deficiently, the moisture more than the required theoretical amount of need being hydrolyzed to remaining hydrolization group, but the reaction that is hydrolyzed fully usually.After the condensation reaction, washing is removed catalyzer and is concentrated, and obtains silesquioxane mixture again.
The silsesquioxane that makes like this is different because of the state of reaction conditions, hydrolysis resultant, in the constituent, multiple cage-type silsesquioxane is whole more than 70%, in the constituent of multiple cage-type silsesquioxane, the T8 of general formula (6) expression is 20～40%, the T10 of general formula (7) expression is 40～50%, and other composition is the T12 of general formula (8) expression.T8 can separate by mixture of siloxanes is made it to separate out in placement below 20 ℃ and as acicular crystallization.The silicone resin that uses among the present invention can be the mixture of T8～T12, also can by its separation or concentrated T8 etc. 1 or 2 kind obtain.In addition, the silicone resin that uses among the present invention is not limited to the silicone resin that above-mentioned method for making makes.
In the organosilicon resin composition that contains silicon-dioxide of the present invention, the unsaturated compound that uses with silicone resin is to comprise at least 1-R in the molecule
3-CR
4=CH
2Or-CR
4=CH
2Shown unsaturated group, can carry out free-radical polymerized unsaturated compound with aforementioned silicone resin.In the formula, R
3Expression alkylidene group, alkylidene or-the OCO-base, as alkylidene group and alkylidene, preferred C
1-6Low-grade alkylidene and alkylidene.R
4Expression hydrogen or alkyl, preferably hydrogen or methyl.As preferred unsaturated group, can enumerate at least a kind that is selected from acryl, methacryloyl, allyl group and vinyl.As preferred unsaturated compound, except that the unsaturated compound with hydroxyl of general formula (4) expression, also has A
1-(R
3-CR
4=CH
2)
nOr A
2-(CR
4=CH
2)
nThe unsaturated compound of expression.In the formula, A
1And A
2C preferably
1-20, the n valency aliphatic alkyl or aromatic hydrocarbyl, aliphatic alkyl also can be the ring type aliphatic alkyl, but does not preferably have two keys of alkene.N is 1～8 integer preferably.In addition, do not have Si in the preferred molecule of this unsaturated compound.
The organosilicon resin composition of silicon-dioxide that contains of the present invention is with A) silicone resin and B) have unsaturated group, can be main component with the unsaturated compound of silicone resin copolymerization.Both mixture ratios are 1: 99～99: 1 scopes, with silicone resin content be designated as A, when unsaturated compound content is designated as B, preferably 10/90≤A/B≤80/20 is more preferably 20/80≤A/B≤60/40.The silicone resin ratio was less than 10% o'clock, so physics values such as the thermotolerance of the formed body after the curing, the transparency, water-absorbent reduce not preferred, and the silicone resin ratio is greater than 80% o'clock, because the viscosity of composition increases, the manufacturing of the formed body difficulty that becomes is not preferred yet.
This unsaturated compound is divided into the unsaturated compound with hydroxyl of above-mentioned general formula (4) expression and does not have the unsaturated compound of hydroxyl.In the general formula (4), R is the organo-functional group with (methyl) acryl, and X is hydrogen or has the organo-functional group of (methyl) acryl.N is 0 or 1 integer.In order to obtain the good formed body of the transparency, the unsaturated compound of preferred hydroxyl.This is considered to hydroxyl suppresses silicon dioxide microparticle with being present in the silanol group effect of silica particle surface cohesion, improves the dispersiveness of silicon dioxide microparticle in resin.And for the unsaturated compound that does not have hydroxyl, when cooperating silicon dioxide microparticle in large quantities, because cohesion and be dispersed in the resin transparency deterioration sometimes unevenly.In addition, consider, can roughly be divided into reactive oligomers that repeat number as structural unit is about 2～20 polymkeric substance and lower molecular weight, low viscous reactive monomer to unsaturated compound from other viewpoint.Also can roughly be divided into simple function unsaturated compound with 1 unsaturated group and the multifunctional unsaturated compound that has more than 2.In addition, multifunctional unsaturated compound also can be divided into non-ester ring type unsaturated compound that does not have alicyclic structure in the molecular structure and the ester ring type unsaturated compound with alicyclic structure.In order to obtain good three-dimensional cross-linked body, the multifunctional unsaturated compound that can contain minute quantity (about below 1%), but the occasion of the thermotolerance, intensity etc. of expectation multipolymer, per 1 molecule is average more than 1.1, preferred more than 1.5, more preferably 1.6～5.Therefore, the simple function unsaturated compound can be mixed use with the multifunctional unsaturated compound with 2～5 unsaturated groups, regulate average functional group's number.
As reactive oligomers, can enumerate epoxy acrylate, epoxidized oil acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyenoid/mercaptan, silicone acrylates, polyhutadiene, polymethyl acrylic acid styryl ethyl ester etc.Simple function unsaturated compound and multifunctional unsaturated compound are arranged in these oligopolymer.
As reactive monofunctional monomer, can enumerate vinylbenzene, vinyl acetate, N-vinyl pyrrolidone, butyl acrylate, 2-EHA, the just own ester of vinylformic acid, cyclohexyl acrylate, vinylformic acid ester in the positive last of the ten Heavenly stems, isobornyl acrylate, vinylformic acid dicyclo amylene oxygen base ethyl ester, vinylformic acid phenoxy ethyl, trifluoroethyl methacrylate etc.
As reactive non-ester ring type polyfunctional monomer, can enumerate three polypropyleneglycol diacrylates, 1,6 hexanediol diacrylate, bisphenol A diglycidyl ether diacrylate, Viscoat 335HP, hydroxyl trimethylacetic acid neopentylglycol diacrylate, Viscoat 295, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol six acrylate etc.As the monomer with hydroxyl of general formula (4) expression, can enumerate pentaerythritol triacrylate, glycerine dimethacrylate, vinylformic acid glyceral methacrylate etc. in the reactive non-ring type polyfunctional monomer.These have hydroxyl owing in the molecule, thus can interact with the hydroxyl that is present in silica particle surface, thus the silicon dioxide microparticle in the control resin combination can cooperate in resin equably in large quantities.
As reactive ester ring type polyfunctional monomer, as general formula (2):
(in the formula, Z represent (2a) or (2b) shown in any group, R represents hydrogen or methyl) shown in, the concrete compound when Z is group shown in the formula (2a), can enumerate R is the five rings [6.5.1.1 of hydrogen
3,6.0
2,7.6
9,13] pentadecane dihydroxymethyl diacrylate, the concrete compound when being group shown in the formula (2b) as Z, can enumerate R is dicyclo amyl group dihydroxymethyl diacrylate (or the three ring [5.2.1.0 of hydrogen
2,6] decane dihydroxymethyl diacrylate.
As the unsaturated compound that uses among the present invention, except the above-mentioned compound of enumerating, can use various reactive oligomers, monomer.In addition, these reactive oligomers, monomer can be distinguished use individually, also can mix more than 2 kinds and use.Yet, use A) and silicone resin, B) unsaturated compound and C) when unsaturated compound, monomer beyond these or oligopolymer, can make the weight % that is calculated by C/ (B+C) is below the 50 weight %, below the preferred 20 weight %.
The silicon dioxide microparticle that contains the organosilicon resin composition of silicon-dioxide of the present invention so long as Si oxide and median size are the silicon-dioxide of 1～100nm scope, does not then have particular determination.Silicon dioxide microparticle can use the exsiccant silicon dioxide microparticle, be dispersed in the colloid silica in the organic solvent.From to organosilicon resin composition, disperseing and use silane compound to handle the silicon dioxide microparticle aspect and consider, the preferred colloid silica that is dispersed in the organic solvent that uses.Organic solvent when being dispersed in colloid silica in the organic solvent as use, the organic solvent of preferred dissolution organosilicon resin composition, can use alcohols, ketone, ester class, glycol ethers solvent, wherein from the processing of using silane compound and the easy degree of the desolventizing after being dispersed in the silicone resin consider, preferably use alcohols such as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols as organic solvent.
Preferred 1～the 100nm of the median size of silicon dioxide microparticle considers from the transparency of the organosilicon resin composition that contains silicon-dioxide and the use level of viscosity and silicon dioxide microparticle and dispersed balance, can more preferably use the silicon dioxide microparticle of 5～50nm.In addition as long as median size in the scope of 1～100nm, then can be used the different silicon dioxide microparticle of multiple median size.The median size of silicon dioxide microparticle is during less than 1nm, owing to cooperate silicon dioxide microparticle, the viscosity that contains the resin combination of silicon-dioxide increases, owing to disperse equably and makes formed body to become difficult, so the use level of silicon dioxide microparticle is restricted.And median size worsens the transparency of formed body when to be 100nm above significantly.
The silicon dioxide microparticle use level that contains the organosilicon resin composition of silicon-dioxide of the present invention, preferably silicon dioxide microparticle is added in the organosilicon resin composition with the scope of 1～70 weight %, consider from the viscosity of the organosilicon resin composition that contains silicon-dioxide, the balance aspect of thermal expansivity, further preferred 5～70 weight % are more preferably 10～50 weight %.If this scope then can obtain the formed body of the excellent easy manufacturing of the low heat expansion property and the transparency.The use level of silicon dioxide microparticle can not present low heat expansion property during less than 1 weight %, and use level is 70 weight % when above, and the viscosity that contains the resin combination of silicon-dioxide increases, the moulding difficulty that becomes.
The viscosity that contains the organosilicon resin composition of silicon-dioxide of the present invention is considered from the viewpoint of formability, 100～120000mPas normally, and preferred 500～90000mPas is more preferably 1000～50000mPas.If this scope, but then the forming composition of setting thickness is made on high efficiency ground.When 100mPas is following,, when 120000mPas is above,, high viscosity reduces significantly because of making production efficiency because viscosity is crossed low and can not be made the forming composition of setting thickness.
Silane compound uses for the surface of handling silicon dioxide microparticle, and to suppressing the cohesion of silicon dioxide microparticle, the viscosity that improves the dispersion stabilization of silicon dioxide microparticle and the organosilicon resin composition that reduction contains silicon-dioxide is effective.The amount of silane compound is the scope of 0.1～80 weight % with respect to silicon dioxide microparticle, preferably with 0.5～50 weight %, more preferably handles with the scope of 0.5～30 weight %.The amount of silane compound loses the effect that suppresses the silicon dioxide microparticle cohesion during less than 0.5 weight %, increases owing to contain the viscosity of the organosilicon resin composition of silicon-dioxide, so that the manufacturing of formed body becomes is difficult.And the amount of silane compound is when to be 50 weight % above, and the effect that cooperates the low-thermal-expansionization of silicon dioxide microparticle reduces and not preferred.Handle the method for silicon dioxide microparticle as using silane compound, cooperate silane compound in the oriented colloid silica that is dispersed in the organic solvent, according to circumstances the limit is stirred the limit to the title complex that has added less water and is heated and make it not produce the method that organic solvent reduces because of heating.
As silane compound, preferably use the compound of above-mentioned general formula (5) expression.
Can enumerate 3-acryloxy propyl-dimethyl methoxy silane particularly, 3-acryloxy propyl group methyl dimethoxysilane, 3-acryloxy propyl group diethyl methoxy silane, 3-acryloxy propyl group ethyl dimethoxy silane, 3-acryloxy propyl trimethoxy silicane, 3-acryloxy propyl-dimethyl Ethoxysilane, 3-acryloxy propyl group methyldiethoxysilane, 3-acryloxy propyl group diethyl Ethoxysilane, 3-acryloxy propyl group ethyl diethoxy silane, 3-acryloxy propyl-triethoxysilicane, 3-methacryloxypropyl dimethyl methyl TMOS, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl diethyl methoxy silane, 3-methacryloxypropyl ethyl dimethoxy silane, the 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl dimethylethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl diethyl Ethoxysilane, 3-methacryloxypropyl ethyl diethoxy silane, 3-methacryloxypropyl triethoxyl silane, methyltrimethoxy silane, dimethyldimethoxysil,ne, Trimethoxy silane, ethyl trimethoxy silane, diethyl dimethoxy silane, the triethyl methoxy silane, propyl trimethoxy silicane, the dipropyl Trimethoxy silane, the tripropyl methoxy silane, the sec.-propyl Trimethoxy silane, diisopropyl dimethoxy silane, the triisopropyl methoxy silane, Union carbide A-162, dimethyldiethoxysilane, triethoxyl silane, ethyl triethoxysilane, the diethyl diethoxy silane, triethyl-ethoxy-silicane alkane, propyl-triethoxysilicane, the dipropyl triethoxyl silane, the tripropyl Ethoxysilane, the sec.-propyl triethoxyl silane, the di-isopropyl diethoxy silane, triisopropyl Ethoxysilane etc.In addition, these may be used alone, two or more kinds can also be used use.
The organosilicon resin composition that contains silicon-dioxide of the present invention is by carrying out the free-radical polymerized silicone resin multipolymer that contains silicon-dioxide that makes to it.For the rerum natura of improving the silicone resin multipolymer that contains silicon-dioxide or free-radical polymerized etc., can in the organosilicon resin composition that contains silicon-dioxide of the present invention, cooperate various additives in order to promote.As the additive that promotes reaction, can enumerate thermal polymerization, thermopolymerization promotor, Photoepolymerizationinitiater initiater, light-initiated auxiliary agent, sensitive agent etc.When cooperating Photoepolymerizationinitiater initiater or thermal polymerization, its addition can be the scope of 0.1～5 weight part, the more preferably scope of 0.1～3 weight part with respect to total 100 weight parts of silicone resin and unsaturated compound and silicon dioxide microparticle.When this addition is lower than 0.1 weight part, solidifies and to become insufficient, the intensity of the formed body that obtains, rigidity reduce, and when surpassing 5 weight parts, might produce the problem such as painted of formed body.
The Photoepolymerizationinitiater initiater that uses when making the organosilicon resin composition that contains silicon-dioxide become Photocurable composition preferably uses the compound of methyl phenyl ketone system, bitter almond oil camphor system, benzophenone series, thioxanthone system, acylphosphine oxide system etc.Can enumerate Trichloroacetophenon, diethoxy acetophenone, 1-phenyl-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholino propane-1-ketone, benzoin methylether, benzyldimethylketal, benzophenone, thioxanthone, 2 particularly; 4,6-trimethylbenzoyl diphenyl phosphine oxide, oxoethanoic acid methyl phenyl ester, camphorquinone, benzil, anthraquinone, Michler's keton etc.Can also and use light-initiated auxiliary agent, sensitive agent with Photoepolymerizationinitiater initiater combination performance effect.
Thermal polymerization as using with this purpose can preferably use various organo-peroxides such as ketone peroxide system, ketal peroxide system, hydrogen peroxide system, dialkyl system, peroxidation diacyl system, peroxy dicarbonate system, peroxyester system.Can enumerate cyclohexanone peroxide, 1 particularly, two (the uncle's hexyl peroxy) pimelinketone of 1-, Cumene Hydroperoxide 80, dicumyl peroxide, benzoyl peroxide, peroxidation di-isopropyl, peroxide-2-ethyl hexanoic acid tert-butyl etc., but be not subjected to this any restriction.In addition, these thermal polymerizations may be used alone, can also be 2 or more kinds in combination.
In the organosilicon resin composition that contains silicon-dioxide of the present invention, can add various additives in the scope that does not break away from the object of the invention.As various additives, can enumerate organic/inorganic filler, softening agent, fire retardant, thermo-stabilizer, oxidation inhibitor, photostabilizer, UV light absorber, lubricant, static inhibitor, releasing agent, whipping agent, nucleator, tinting material, linking agent, dispersing auxiliary, resinous principle etc.
By the organosilicon resin composition that contains silicon-dioxide of the present invention is carried out the free-radical polymerized silicone resin multipolymer that makes, in addition, by making the organosilicon resin composition that contains silicon-dioxide become the shape of setting, carry out the free-radical polymerized formed body that makes the silicone resin multipolymer that contains silicon-dioxide.When the silicone resin multipolymer that contains silicon-dioxide that makes is thermoplasticity, can adopt the various methods of forming, but when the number of the reactive substituents of per 1 molecule or unsaturated group greater than 1.0 the time, owing to become multipolymer, so employing forming and hardening usually with three-dimensional crosslinking structure body.Therefore, also be called curing with free-radical polymerized.Suitable employing heating or electron rays, ultraviolet homenergic radiation exposure in free-radical polymerized.
The silicone resin multipolymer that contains silicon-dioxide of the present invention can solidify the organosilicon resin composition that contains silicon-dioxide that contains radical polymerization initiator by employing heating or rayed and make.When utilizing heating to make multipolymer (formed body), its mold temperature is by selecting thermal polymerization and promotor, can select from the wide region about room temperature to 200 ℃.This occasion can access the silicone resin formed body that contains silicon-dioxide of desired shape by make its polymerizing curable in mould, on the steel band.
In addition, when adopting rayed to make interpolymer (formed body), can obtain formed body by the ultraviolet ray of illumination wavelength 10～400nm, the visible rays of wavelength 400～700nm.Used light wavelength does not have particular restriction, especially preferably uses the near-ultraviolet ray of wavelength 200～400nm.The employed lamp in source takes place as ultraviolet ray, can enumerate Cooper-Hewitt lamp (power: 0.4～4W/cm), high pressure mercury vapour lamp (40～160W/cm), extra-high-pressure mercury vapour lamp (173～435W/cm), metal halide lamp (80～160W/cm), xenon flash lamp (80～120W/cm), electrodeless discharge lamp (80～120W/cm) etc.These UV-lamp since separately beam split distribute and to have feature, so select according to the kind of the light trigger of use.
As adopting rayed to make the method for the silicone resin multipolymer (formed body) that contains silicon-dioxide, can enumerate for example by in the mould that has the arbitrary mould cavity shape, constitutes, injecting by transparent materials such as silica glasss, use above-mentioned UV-lamp irradiation ultraviolet radiation to carry out polymerizing curable, thereby the method for the formed body of desired shape is made in the demoulding from mould; When not using mould, for example on the steel band that moves, be coated with the organosilicon resin composition that contains silicon-dioxide of the present invention by the spreader that uses scraper or roller shape, use above-mentioned UV-lamp to make its polymerizing curable, thereby make method of flaky formed body etc.
The silicone resin multipolymer (formed body) that contains silicon-dioxide of the present invention that makes like this, the second-order transition temperature that uses dynamic thermomechanometry device (DMA) to measure is not showing second-order transition temperature below 300 ℃, total light penetration can reach more than 85%, linear expansivity can reach below the 40ppm/K, therefore, can become high heat-resisting, high transparent and have the formed body of high-dimensional stability.
Embodiment
Below, embodiments of the invention are shown.Moreover the silicone resin that uses among the following embodiment is the silicone resin that adopts the method shown in the following synthesis example 1 to make.
Synthesis example 1
In the reaction vessel that has stirrer, dropping funnel, thermometer, add as 2-propyl alcohol (IPA) 40ml of solvent with as 5% tetramethylammonium hydroxide aqueous solution (the TMAH aqueous solution) of basic catalyst.In dropping funnel, add IPA15ml and 3-methacryloxypropyl trimethoxy silane (the eastern beautiful DOW CORNING organosilicon system SZ-6030 of Co., Ltd.) 12.69g, limit stirring reaction container, limit are at room temperature with the IPA solution that dripped the 3-methacryloxypropyl trimethoxy silane in 30 minutes.Drip after the 3-methacryloxypropyl trimethoxy silane finishes, do not heat and stirred 2 hours.Stir under reduced pressure to remove after 2 hours and desolvate, use 50ml toluene to dissolve.Use saturated aqueous common salt that reaction soln is washed after becoming neutrality, use anhydrous magnesium sulfate to dewater.By the filtering separation anhydrous magnesium sulfate, concentrate and obtain hydrolysis resultant (silsesquioxane) 8.6g.This silsesquioxane is a soluble colourless viscous liquid in various organic solvents.
Then, add the above-mentioned silsesquioxane 20.65g that makes and toluene 82ml and 10%TMAH aqueous solution 3.0g in the reaction vessel that has stirrer, Dean-Stark air water separator, cooling tube, slowly heating is heated up in a steamer and is anhydrated.Be heated to 130 ℃ in addition, under reflux temperature, toluene carried out condensation reaction again.The temperature of the reaction soln of this moment is 108 ℃.Stir behind the refluxing toluene after 2 hours, finish reaction.Use saturated aqueous common salt that reaction soln is washed after becoming neutrality, use anhydrous magnesium sulfate to dewater.By the filtering separation anhydrous magnesium sulfate, concentrate and obtain cage-type silsesquioxane (mixture) 18.77g as object.The cage-type silsesquioxane that makes is a soluble colourless viscous liquid in various organic solvents.
Reactant after the condensation reaction is again carried out mass analysis after liquid chromatography is separated, and results verification is the molion that has ammonium ion in the molecular structure of said structure formula (6), (7) and (8).Component ratio is T8: T10: T12 and other are 2: 4: 1 approximately: 3, and being confirmed to be with the cagelike structure is the silicone resin of main component.Moreover T8, T10, T12 are corresponding with the order of formula (6), (7) and (8).
Embodiment 1
Having stirrer, thermometer, in the reaction vessel of cooling tube, adding is as the Virahol dispersoid silicon dioxide gel (particle diameter 10～20nm of silicon dioxide microparticle, solid or divide 30 weight %, moisture 0.5 weight %, Nissan Chemical Ind Ltd's system: IPA-ST) 150 weight parts (silica solid composition 30 weight parts) and as the 3-methacryloxypropyl trimethoxy silane of silane compound (the eastern beautiful DOW CORNING organosilicon system SZ-6030 of Co., Ltd.) 7.2 weight parts, slowly heating while stirring, after the temperature of reaction soln reaches 68 ℃, carry out heating in 5 hours again, carry out the processing of silicon dioxide microparticle.Mix organosilicon resin composition (the cage modle silicone resin that on all Siliciumatoms, has methacryloyl that in synthesis example 1, makes: 25 weight parts, dipentaerythritol six acrylate: 55 weight parts 75 weight parts) to it then; the solvent flashing composition is removed by decompression bottom slowly heating edge, and this moment, final temperature was 80 ℃.Mixing is as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 weight parts obtain the transparent organosilicon resin composition that contains silicon-dioxide.
Then, use the print roll coating device to carry out curtain coating and make thickness become 0.4mm, use the high pressure mercury vapour lamp of 30W/cm, with 8000mJ/cm
2The cumulative exposure amount make it to solidify, obtain becoming the flaky silicone resin formed body of setting thickness.
Embodiment 2～6
Cooperate the ratio shown in the table 1 that consists of except making, make resin-formed body similarly to Example 1.The physics value of the formed body that makes is summarized in table 2.
Comparative example 1
With the cage modle silicone resin that has methacryloyl on whole Siliciumatoms that makes in the synthesis example 1: 25 weight parts, dipentaerythritol six acrylate: 75 weight parts, as the 1-hydroxycyclohexylphenylketone of Photoepolymerizationinitiater initiater: 2.5 weight parts mix, and make transparent organosilicon resin composition.
Then, use the roller coat device to carry out curtain coating and make thickness become 0.4mm, use the high pressure mercury vapour lamp of 30W/cm, with 8000mJ/cm
2The cumulative exposure amount make it to solidify, make the flaky silicone resin formed body of setting thickness.
Comparative example 2
Consist of the part by weight shown in the table 1 except making to cooperate, similarly to make resin-formed body with comparative example 1.The physics value of the formed body that makes is summarized in table 2.
Shorthand notation in the table is as follows.
A: silica solid composition
B:3-methacryloxypropyl trimethoxy silane (the eastern beautiful DOW CORNING organosilicon system SZ-6030 of Co., Ltd.)
C: the organosilicon resin composition 1 (compound that makes in the synthesis example 1: 25 weight parts, dipentaerythritol six acrylate: 75 weight parts)
D: the organosilicon resin composition 2 (compound that makes in the synthesis example 1: 25 weight parts, pentaerythritol triacrylate: 75 weight parts)
E: the organosilicon resin composition 3 (compound that makes in the synthesis example 1: 25 weight parts, glycerine dimethacrylate: 75 weight parts)
F: the organosilicon resin composition 4 (compound that makes in the synthesis example 1: 25 weight parts, pentaerythritol triacrylate: 55 weight parts, glycerine dimethacrylate: 20 weight parts)
G:1-hydroxycyclohexylphenylketone (polymerization starter)
Table 1
| A | B | C | D | E | F | G | |
| Embodiment 1 | 45 | 7.2 | 55 | - | - | - | 2.5 |
| 2 | 30 | 1.3 | 70 | - | - | - | 2.5 |
| 3 | 25 | 0.25 | 75 | - | - | - | 2.5 |
| 4 | 30 | 1.3 | - | 70 | - | - | 2.5 |
| 5 | 20 | 0.78 | - | 80 | - | - | 2.5 |
| 6 | 50 | 4.0 | - | - | 50 | - | 2.5 |
| 7 | 44 | 3.5 | - | - | - | 56 | 2.5 |
| Comparative example 1 | - | - | 100 | - | - | - | 2.5 |
| 2 | - | - | - | 100 | - | - | 2.5 |
| 3 | - | - | - | - | 100 | - | 2.5 |
| 4 | - | - | - | - | - | 100 | 2.5 |
Table 2
| Second-order transition temperature (℃) | Total light penetration (%) | Coefficient of linear expansion (ppm/K) | Viscosity (mPas) | Formability | |
| Embodiment 1 | ＞300 | 89 | 31 | ＞100000 | △ |
| 2 | ＞300 | 89 | 37 | ＞100000 | △ |
| 3 | ＞300 | 89 | 35 | ＞100000 | △ |
| 4 | ＞300 | 89 | 32 | ＞100000 | △ |
| 5 | ＞300 | 89 | 36 | ＞100000 | △ |
| 6 | ＞300 | 89 | 27 | 23000 | ○ |
| 7 | ＞300 | 89 | 31 | 87000 | ○ |
| Comparative example 1 | ＞300 | 89 | 46 | 5500 | ○ |
| 2 | ＞300 | 89 | 48 | 811 | ○ |
| 3 | ＞300 | 89 | 70 | 90 | △ |
| 4 | ＞300 | 89 | 53 | 393 | ○ |
1) second-order transition temperature: dynamic thermomechanical analysis, 5 ℃/minute of heat-up rates, spacing jig is from 10mm
2) total light penetration (with reference to specification JIS K 7361-1): test portion thickness 0.4mm
3) linear expansivity: thermomechanical analysis, 5 ℃/minute of heat-up rates, compression load 0.1N
4) viscosity: E type viscometer (23 ℃)
5) formability: curtain coating resin 30g, the thickness of the forming composition that applying load 40kg, 18 minutes after fixing make, less than set ± be designated as zero at 5% o'clock, less than being designated as △ at ± 10% o'clock, ± 10% be designated as when above *.
Can make high heat-resisting, high transparent according to the present invention, have the formed body of high-dimensional stability, can be used for the various uses such as window material of the optical applications of for example lens, CD, photoconductive fiber and flat display substrate etc., various conveying machinery, dwelling house etc.Formed body is a transparent component in light weight, high impact, and also wide as its range of application of glass equivalent material, the utility value on the industry is also high.
Claims (9)
1. contain the organosilicon resin composition of silicon-dioxide, it is characterized in that: will with shown in the general formula (1), the organic poly sesquisiloxane that has cagelike structure in the structural unit is to contain at least 1-R in the cage modle silicone resin of main component and the molecule
3-CR
4=CH
2Or-CR
4=CH
2(in the formula, R
3Expression alkylidene group, alkylidene or-the OCO-base, R
4The expression hydrogen or alkyl) unsaturated group shown in, can carry out in the organosilicon resin composition that free-radical polymerized unsaturated compound cooperates by 1: 99～99: 1 part by weight with aforementioned silicone resin, the silica particle that contains median size 1～100nm with the scope of 1～70 weight %
[RSiO
3/2]
n (1)
In the formula, R is the organo-functional group with (methyl) acryl, and n is 8,10 or 12.
2. the described organosilicon resin composition that contains silicon-dioxide of claim 1; wherein silicone resin is to make the reaction that is hydrolyzed of the silicon compound shown in the general formula (3) in the presence of polar solvent and basic catalyst; make the part condensation simultaneously; again with the hydrolysis resultant that obtains in the presence of non-polar solvent and basic catalyst again condensation make; Siliciumatom number in the molecule equates with (methyl) acryloyl radix; and has cagelike structure
RSiX
3 (3)
In the formula, R is the organo-functional group with (methyl) acryl, and X represents hydrolization group.
3. claim 1 or the 2 described organosilicon resin compositions that contain silicon-dioxide, wherein the unsaturated compound of free redical copolymerization comprises the unsaturated compound with hydroxyl shown in the following general formula (4),
In the formula, R is the organo-functional group with (methyl) acryl, and X is hydrogen or has the organo-functional group of (methyl) acryl that n is 0 or 1 integer.
4. the described organosilicon resin composition that contains silicon-dioxide of claim 1, wherein silica particle uses the silane compound of 0.1～80 weight % to handle.
5. the described organosilicon resin composition that contains silicon-dioxide of claim 4, wherein silane compound is by following general formula (5) expression,
R
mSiA
nX
4-m-n (5)
In the formula, R is the organo-functional group with (methyl) acryl, and A is an alkyl, and X is alkoxyl group or halogen atom, and it is 1～3 integer that m and n satisfy m+n, and m is 0 or 1, and n is 0～3 integer.
6. the silicone resin multipolymer that contains silicon-dioxide, it makes each described organosilicon resin composition that contains silicon-dioxide of claim 1～5 carry out free-radical polymerized making.
7. resin-formed body, it makes each described organosilicon resin composition that contains silicon-dioxide of claim 1～5 carry out free-radical polymerized making.
8. the described resin-formed body of claim 7, wherein the linear expansivity of resin-formed body is below the 40ppm/K, total light penetration is more than 85% and second-order transition temperature is more than 300 ℃.
9. the manufacture method of resin-formed body is characterized in that: each described organosilicon resin composition that contains silicon-dioxide of claim 1～5 is heated or irradiation energy ray and make it to carry out free-radical polymerized.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819677A (en) * | 2012-11-19 | 2014-05-28 | 新日铁住金化学株式会社 | Cage silsesquioxane compound, curable resin composition using the same and its cured resin |
| CN104011118A (en) * | 2011-12-22 | 2014-08-27 | 新日铁住金化学株式会社 | Glass fiber composite resin substrate |
| CN104203570A (en) * | 2012-08-03 | 2014-12-10 | 马自达汽车株式会社 | Transparent layered object and process for producing same |
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| CN112225534B (en) * | 2020-10-25 | 2022-05-03 | 湖南长重机器股份有限公司 | High-strength porous ceramsite and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5000303B2 (en) | 2012-08-15 |
| TWI388629B (en) | 2013-03-11 |
| KR100991025B1 (en) | 2010-10-29 |
| TW200615334A (en) | 2006-05-16 |
| KR20070058665A (en) | 2007-06-08 |
| JPWO2006035646A1 (en) | 2008-07-31 |
| CN100545184C (en) | 2009-09-30 |
| WO2006035646A1 (en) | 2006-04-06 |
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