WO2012133080A1 - 硬化性シリコーン樹脂組成物及びシリコーン樹脂硬化物 - Google Patents
硬化性シリコーン樹脂組成物及びシリコーン樹脂硬化物 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F30/00—Homopolymers and 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
- C08F30/04—Homopolymers and 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
- C08F30/08—Homopolymers and 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—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
- C08F230/04—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
- C08F230/08—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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
- C08L43/04—Homopolymers or copolymers of monomers containing silicon
Definitions
- the present invention relates to a curable silicone resin composition and a cured silicone resin. More specifically, the present invention relates to a curable silicone resin composition containing a cage silsesquioxane resin and a cured silicone resin obtained by curing the same.
- a glass plate is widely used as a transparent substrate such as a liquid crystal display device substrate, a color filter substrate, an organic EL display device substrate, an electronic paper substrate, a TFT substrate, or a solar cell substrate.
- a transparent plastic plate as an alternative has been studied because glass plates are easily broken, cannot be bent, have a large specific gravity, and are not suitable for weight reduction.
- silsesquioxane having a cage structure is attracting attention in various fields because it can exhibit a specific function by utilizing its characteristic structure.
- a cured product of a cage-type silsesquioxane resin is expected as a material for a transparent plastic plate that can be used as a substitute for a glass plate because it has excellent heat resistance, weather resistance, optical properties, dimensional stability, and the like.
- Patent Document 1 a cage silsesquioxane having a vinyl group as a curable functional group and a SiH group.
- cured material obtained by hydrosilylating the compound which has this, and the compound which has a vinyl group is disclosed.
- the cured product described in the same document although high heat resistance and transparency are achieved to some extent, when used as an alternative material for a glass plate, the linear expansion coefficient is large, and further in the hydrosilylation reaction. Commonly used platinum catalysts have the problem of being expensive and economically disadvantageous.
- Patent Document 2 a cage silsesquioxane resin represented by [RSiO 3/2 ] n and having a (meth) acryloyl group as a functional group, an unsaturated compound, and the like
- a silicone resin copolymer obtained by radical copolymerization of a silicone resin composition comprising:
- Patent Document 3 a cage type represented by [RSiO 3/2 ] n and having any one of (meth) acryloyl group, glycidyl group and vinyl group. Silsesquioxane resins are disclosed.
- Patent Document 4 International Publication No. 2008/099850 discloses a cage cleavage type silsesquioxane resin having a vinyl group or the like.
- the silicone resin copolymer described in Patent Document 2 is highly transparent and has a linear expansion coefficient that is small to some extent.
- the silicone resin copolymer described in Patent Document 2 has a cage like the silicone resin copolymer described in the same document.
- the cured resin having a (meth) acryloyl group which is a hydrophilic group on all silicon atoms in the type silsesquioxane skeleton has a problem of high water absorption and a large linear expansion coefficient. The inventors have found.
- This invention is made
- An object is to provide a curable silicone resin composition and a cured silicone resin obtained by curing the composition.
- the present inventors contain a cage silsesquioxane resin having a specific structure having a vinyl group and a (meth) acryloyl group in the silicone resin composition. It is found that by curing a curable silicone resin composition, a cured silicone resin having excellent transparency, moldability and low water absorption and a sufficiently small linear expansion coefficient can be obtained, and the present invention is completed. It came to.
- R 2 represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, and an allyl group
- h represents any integer selected from the group consisting of 8, 10, 12, and 14.
- R 1 and R 2 may be the same or different.
- the ratio of the number of vinyl groups to the number of (meth) acryloyl groups is preferably 1: 4 to 13: 1.
- the curable silicone resin composition of the present invention preferably further contains an unsaturated compound having a (meth) acryloyl group, and the content of the radical polymerization initiator is 0.01 to 10% by mass. It is preferable.
- the cured silicone resin of the present invention is obtained by radical polymerization of the curable silicone resin composition.
- the present inventors infer as follows. That is, in the curable silicone resin composition of the present invention, the combination of a vinyl group and a (meth) acryloyl group as a curable functional group surprisingly has excellent characteristics of both functional groups. The present inventors speculate that it is possible to obtain a cured silicone resin having a low water absorption and a sufficiently low linear expansion coefficient, as well as being exhibited without loss, excellent transparency and moldability. .
- the (meth) acryloyl group means a methacryloyl group and an acryloyl group.
- the curable silicone resin composition of the present invention since it contains two or more functional groups, it has excellent compatibility with other compounds, and even if other compounds are contained, it is a uniform resin. A composition can be obtained. Therefore, the present inventors speculate that the cured silicone resin obtained exhibits excellent transparency and moldability.
- a curable silicone resin composition having excellent transparency, moldability and low water absorption, and capable of obtaining a cured silicone resin having a sufficiently small linear expansion coefficient, and obtained by curing the same. It is possible to provide a cured silicone resin.
- 2 is a chromatogram showing the results of GPC of the resin mixture I obtained in Synthesis Example 1.
- 2 is a graph showing a 1 H-NMR spectrum of a resin mixture I obtained in Synthesis Example I. It is an enlarged view of FIG. 2A.
- 2 is a graph showing an ESI-MS spectrum of a resin mixture I obtained in Synthesis Example I. It is a chromatogram which shows the result of GPC of the resin mixture II obtained by the synthesis example II. It is a chromatogram which shows the result of GPC of the resin mixture III obtained by the synthesis example III. It is a chromatogram which shows the result of GPC of the resin mixture IV obtained by the synthesis example IV.
- 6 is a chromatogram showing a GPC result of a resin mixture V obtained in Synthesis Example V. It is a chromatogram which shows the result of GPC of the resin mixture VI obtained by the synthesis example VI.
- the curable silicone resin composition of the present invention contains a cage silsesquioxane resin and a radical polymerization initiator, and the content of the cage silsesquioxane resin is 10 to 80% by mass. .
- R 3 represents a hydrogen atom or a methyl group.
- R 3 is particularly preferably a methyl group from the viewpoint that water absorption can be further reduced due to the repulsive effect of the three-dimensional structure.
- R 4 represents any one selected from the group consisting of an alkylene group, an alkylidene group, and a phenylene group, and the alkylene group may be linear or branched.
- the number of carbon atoms is preferably 1 to 3, and the alkylidene group may be linear or branched, Examples include propane-2-ylidene, and the phenylene group includes, for example, 1,2-phenylene having a lower alkyl group in addition to the unsubstituted phenylene group.
- an alkylene group having 1 to 3 carbon atoms is preferable.
- R 4 a propylene group is more preferable from the viewpoint that the raw materials are easily available, the distance between crosslinks is not increased, and the linear expansion coefficient is decreased.
- R 2 represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, and an allyl group.
- R 2 is more preferably a hydrogen atom, a methyl group, an ethyl group, a phenyl group, or an allyl group from the viewpoint that the linear expansion coefficient is sufficiently small.
- the cage silsesquioxane resin according to the present invention has one or more (meth) acryloyl groups by satisfying the condition represented by the above formula (ii), the transparent curing by radical polymerization.
- the compatibility is improved, so that a more transparent cured product can be obtained.
- the cage silsesquioxane resin according to the present invention has a cage structure which is almost completely condensed. Thus, it is possible to obtain a cured silicone resin having excellent transparency, moldability and low water absorption, and having a sufficiently small linear expansion coefficient.
- R 1 and R 2 may be the same or different.
- the ratio of n to m (n: m) is more preferably 1: 4 to 13: 1, and 1: 3 to 13: 1 is particularly preferred.
- the number of n is less than the lower limit, the crosslinking density of the resin tends to decrease and the linear expansion coefficient of the cured silicone resin tends to increase.
- the number exceeds the upper limit vinyl having low radical polymerizability is low.
- the curable silicone resin composition of the present invention by using such a cage-type silsesquioxane resin, a silicone having excellent transparency, moldability and low water absorption, and having a sufficiently small linear expansion coefficient. A cured resin can be obtained.
- k represents an integer of 1 to 3.
- n 6
- m 2
- j 0
- R 4 is (CH 2 ) k
- k represents an integer of 1 to 3.
- n 8
- m 2
- j 0
- R 4 is (CH 2 ) k
- k represents an integer of 1 to 3.
- n 6
- m 6
- j 2
- R 4 is (CH 2 ) k
- R 2 is CH 3 CH 2 —.
- formula (7) the following formula (7):
- n 6
- m 4
- j 4
- R 4 is (CH 2 )
- R 2 is CH 3 CH 2- Yes
- a compound represented by the following formula (14) may be mentioned.
- the cage silsesquioxane resin as the cage silsesquioxane resin, one kind may be used alone, or two or more kinds may be used in combination.
- the content of the cage silsesquioxane resin the total mass of the cage silsesquioxane resin needs to be 10 to 80% by mass with respect to the curable silicone resin composition of the present invention. is there.
- the content of the cage silsesquioxane resin is less than the lower limit, in the cured silicone resin, physical properties such as transparency, low thermal expansion, low water absorption, and compatibility are deteriorated.
- the viscosity of the curable silicone resin composition increases, making it difficult to produce a molded product.
- the content of the cage silsesquioxane resin is particularly preferably 15 to 80% by mass.
- the ratio of the number of vinyl groups to the number of all (meth) acryloyl groups in the entire cage silsesquioxane resin (total number of vinyl groups: total number of (meth) acryloyl groups). ) Is preferably 1: 4 to 13: 1.
- the vinyl group content is less than the lower limit, the crosslink density of the resin tends to decrease and the linear expansion coefficient of the cured silicone resin tends to increase. Since the ratio of low vinyl groups increases, many unreacted vinyl groups tend to remain in the cured silicone resin. Further, from the viewpoint of better low thermal expansion and low water absorption, the ratio (total number of vinyl groups: total number of (meth) acryloyl groups) is more preferably 1: 3 to 13: 1.
- the ratio between the number of vinyl groups and the total number of (meth) acryloyl groups in the cage silsesquioxane resin is 1 H-NMR (device name: JNM-ECA400, manufacturer name: JEOL, (Solvent: deuterated chloroform, temperature: 23 ° C., 400 MHz), which can be determined from the integration ratio of peaks of vinyl group and (meth) acryloyl group.
- R 2 has the same meaning as R 2 in formula (1), and Z is any one selected from the group consisting of an alkoxy group, an acetoxy group, a halogen atom and a hydroxy group.
- a hydrolyzable group is shown.
- a basic catalyst In the presence of a basic catalyst, and in the presence of a basic catalyst, it is hydrolyzed in a nonpolar solvent and / or polar solvent and partially condensed, and the resulting hydrolysis reaction product is Furthermore, a method of recondensing in the presence of a nonpolar solvent and a basic catalyst can be mentioned.
- Examples of the silicon compound (A) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, and the like. These may be used alone or in combination of two or more. Among these, vinyltrimethoxysilane is preferably used from the viewpoint of easy availability of raw materials.
- Examples of the silicon compound (B) include methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, Examples thereof include 3-acryloxypropyltriethoxysilane, and these may be used alone or in combination of two or more. Of these, 3-methacryloxypropyltrimethoxysilane is preferably used from the viewpoint of easy availability of raw materials.
- Examples of the silicon compound (C) include phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, and n-propyltriethoxy.
- a molar ratio of the silicon compound (A) and the silicon compound (B) (number of moles of A: B
- the molar ratio of the silicon compound (C) to the total of the silicon compound (A) and the silicon compound (B) (the number of moles of A + B: the number of moles of C) Is preferably mixed so that the ratio is 1: 0 to 5: 2.
- the basic catalyst used in the hydrolysis reaction includes alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, cesium hydroxide; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyl Examples thereof include ammonium hydroxide salts such as trimethylammonium hydroxide and benzyltriethylammonium hydroxide. Among these, it is preferable to use tetramethylammonium hydroxide from the viewpoint of high catalytic activity.
- the amount of such a basic catalyst is preferably 0.01 to 20% by mass with respect to the total mass of the silicon compounds (A) to (C).
- the basic catalyst is usually used as an aqueous solution.
- the presence of water is essential, but this can be supplied from an aqueous solution of the basic catalyst or added as water separately.
- the amount of water should be more than the mass sufficient to hydrolyze the hydrolyzable group, and the theoretical amount (mass) of the hydrolyzable group calculated from the mass of the silicon compounds (A) to (C).
- the amount is preferably 1.0 to 1.5 times.
- a nonpolar solvent and / or a polar solvent As such a solvent, if only a nonpolar solvent is used, the reaction system will not be uniform, and the hydrolysis reaction will not proceed sufficiently, and unreacted hydrolyzable groups tend to remain. It is preferable to use both a polar solvent and a polar solvent, or use only a polar solvent.
- polar solvent alcohols such as methanol, ethanol, 2-propanol, or other polar solvents can be used. Of these, lower alcohols having 1 to 6 carbon atoms that are soluble in water are preferred, and 2-propanol is more preferred.
- the amount of the nonpolar solvent and / or the polar solvent used is preferably in the range where the total molar concentration (mol / liter: M) of the silicon compounds (A) to (C) is 0.01 to 10M. .
- the reaction temperature is preferably 0 to 60 ° C., more preferably 20 to 40 ° C.
- the reaction rate becomes slow, so that the hydrolyzable group remains in an unreacted state, and the reaction time tends to be long.
- the reaction temperature exceeds the above upper limit, the reaction rate is too high, so that a complex condensation reaction proceeds, and as a result, high molecular weight of the hydrolysis reaction product tends to be promoted.
- the reaction time is preferably 2 hours or more. When the reaction time is less than the lower limit, the hydrolysis reaction does not proceed sufficiently and the hydrolyzable group tends to remain in an unreacted state.
- the reaction solution is made neutral or acidic using a weakly acidic solution, and then water or a water-containing reaction solvent is separated.
- a weakly acidic solution include sulfuric acid diluted solution, hydrochloric acid diluted solution, citric acid solution, acetic acid, ammonium chloride aqueous solution, malic acid solution, phosphoric acid solution, oxalic acid solution and the like.
- the reaction solution is washed with a saline solution or the like to sufficiently remove moisture and other impurities, and then dried with a drying agent such as anhydrous magnesium sulfate. Means can be employed.
- the hydrolysis reaction product As a method for recovering the hydrolysis reaction product when a polar solvent is used as the solvent, first, the polar solvent is removed by evaporation under reduced pressure, and then a nonpolar solvent is added to the hydrolysis reaction product. A method of washing and drying in the same manner as described above can be employed after dissolving the above.
- the hydrolysis reaction product when a nonpolar solvent is used as the solvent, the hydrolysis reaction product can be recovered by separating the nonpolar solvent by means such as evaporation. However, the nonpolar solvent is used in the next recondensation reaction. If it can be used as the nonpolar solvent to be used, it is not necessary to separate it.
- the hydrolysis reaction product contains a polycondensate produced by the condensation.
- a polycondensate varies depending on the reaction conditions, but has a number average molecular weight of 500 to 10,000 (or Oligomer) mixture, which is composed of siloxanes having a plurality of types of cage-type, incomplete cage-type, ladder-type, and random-type structures.
- the hydrolysis reaction product is further heated in the presence of a nonpolar solvent and a basic catalyst to condense the siloxane bond (referred to as recondensation).
- recondensation it is preferable to selectively produce a recondensate (a siloxane having a cage structure).
- the nonpolar solvent may be any solvent that is not or hardly soluble in water, but is preferably a hydrocarbon solvent.
- the hydrocarbon solvent include nonpolar solvents having a low boiling point such as toluene, benzene, xylene, etc. Among them, it is preferable to use toluene.
- the amount of the nonpolar solvent used is preferably an amount sufficient to dissolve the hydrolysis reaction product, and is 0.1 to 20 times the mass of the total mass of the hydrolysis reaction product. preferable.
- a basic catalyst used in the hydrolysis reaction can be used, and alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide; tetramerammonium hyhydroxide, tetraethylammonium Mention may be made of ammonium hydroxide salts such as hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide and benzyltriethylammonium hydroxide. Among these, a catalyst that is soluble in a nonpolar solvent such as tetraalkylammonium is preferable. The amount of such a basic catalyst is preferably 0.01 to 20% by mass of the hydrolysis reaction product.
- the reaction temperature is preferably 90 to 200 ° C, more preferably 100 to 140 ° C.
- the reaction temperature is lower than the lower limit, a sufficient driving force is not obtained to cause the recondensation reaction, and the reaction tends not to proceed.
- the reaction temperature exceeds the above upper limit, a reactive organic functional group such as a vinyl group or a (meth) acryloyl group may cause a self-polymerization reaction. Etc. tend to arise.
- the reaction conditions for the recondensation reaction are preferably 2 to 12 hours.
- the hydrolysis reaction product used for the recondensation is preferably washed and dried as described above, and further concentrated, but can be used even if these treatments are not performed.
- water may be present, but it is not necessary to add it positively, and it is preferable to keep the amount of water supplied from the basic catalyst solution.
- the reaction solution is washed to remove the catalyst, and concentrated in a rotary evaporator or the like.
- a mixture of a plurality of types of cage silsesquioxane resins according to the present invention represented by the above formulas (3) to (14) and the like can get.
- the content of the cage silsesquioxane resin according to the present invention is preferably 40% by mass or more of the entire recondensation product (resin mixture).
- the radical polymerization initiator according to the present invention includes a thermal polymerization initiator and a photopolymerization initiator.
- radical polymerization of the cage silsesquioxane resin is promoted by the radical polymerization initiator, and a cured silicone resin having excellent strength and rigidity can be obtained.
- the thermal polymerization initiator is used when the curable silicone resin composition of the present invention is thermally cured.
- a thermal polymerization initiator is preferably an organic peroxide, and examples of the organic peroxide include ketone peroxides, diacylalkyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, Examples thereof include alkyl peresters and percarbonates.
- dialkyl peroxide is preferable from the viewpoint of high catalytic activity.
- dialkyl peroxide examples include cyclohexanone peroxide, 1,1-bis (t-hexaperoxy) cyclohexanone, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, diisopropyl peroxide, di- Examples thereof include t-butyl peroxide, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexanoate and the like.
- the thermal polymerization initiator one of these may be used alone, or two or more may be used in combination.
- the photopolymerization initiator is used when the curable silicone resin composition of the present invention is photocured.
- a photopolymerization initiator it is preferable to use compounds such as acetophenones, benzoins, benzophenones, thioxanthones, and acylphosphine oxides.
- the photopolymerization initiator one of these may be used alone, or two or more may be used in combination.
- the thermal polymerization initiator or the photopolymerization initiator may be used alone, or both may be used in combination.
- the content of such radical polymerization initiator is preferably 0.01 to 10% by mass and more preferably 0.05 to 5% by mass in the curable silicone resin composition of the present invention.
- the content is less than the lower limit, the composition is insufficiently cured, and thus the strength and rigidity of the obtained molded product tend to be low.
- the content exceeds the upper limit, the molded product is colored. Tend to cause problems.
- the curable silicone resin composition of the present invention preferably further contains an unsaturated compound having a (meth) acryloyl group.
- an unsaturated compound having a (meth) acryloyl group By containing such an unsaturated compound, it becomes possible to obtain a cured product having desired physical properties such as viscosity, resin rigidity, and strength of the silicone resin composition.
- the unsaturated compound is not particularly limited as long as it has a (meth) acryloyl group capable of radical copolymerization with the cage silsesquioxane resin, and when the viscosity of the curable silicone resin composition is increased.
- a reactive oligomer, a low-molecular-weight and / or low-viscosity reactive monomer, or the like which is a polymer having about 2 to 20 structural units is preferable.
- Examples of the reactive oligomer include epoxy acrylate, epoxidized acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, and polystyrylethyl methacrylate.
- Examples of the reactive monomer include butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate.
- Monofunctional monomers such as dicyclopentanyl diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol acrylate, dimethylol tricyclodecane diacrylate, bisphenol A diglycidyl ether di Acrylate, tetraethylene glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, trimethylo Le propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, include polyfunctional monomers such as dipentaerythritol hexaacrylate. As the unsaturated compound, one of these may be used alone, or two or more may be used in combination.
- the content of the unsaturated compound is 10:90 to 80:20 in a mass ratio with respect to the cage silsesquioxane resin (cage silsesquioxane resin: unsaturated compound). Is preferable. If the content is less than the lower limit, the viscosity of the silicone resin composition tends to increase, making it difficult to produce a molded product. On the other hand, if the content exceeds the upper limit, the cured silicone resin is transparent. Properties, low thermal expansion, low water absorption, compatibility and the like tend to be reduced.
- the curable silicone resin composition of the present invention can further contain other resins as long as the effects of the present invention are not impaired.
- the other resins include ladder-type siloxanes and random-type siloxanes produced as by-products in the production of the cage silsesquioxane resin.
- the content is a sum of the contents (mass) of the cage silsesquioxane resin according to the present invention
- b is the content (mass) of the unsaturated compound
- the following formula 10/90 ⁇ a / (b + c) ⁇ 80/20
- the condition represented by When the content of the cage silsesquioxane resin is less than the lower limit, physical properties such as transparency, low thermal expansion, low water absorption, and compatibility of the cured silicone resin tend to be lowered.
- the said upper limit physical properties such as transparency, low thermal expansion, low water absorption, and compatibility of the cured silicone resin tend to be lowered.
- the curable silicone resin composition of the present invention in order to further improve the physical properties of the cured silicone resin and / or to promote radical polymerization, as long as the effects of the present invention are not impaired, A thermal polymerization accelerator, a photoinitiator aid, a sharpener, and the like can be contained.
- the curable silicone resin composition of the present invention includes an organic / inorganic filler, an inorganic filler, a plasticizer, a flame retardant, a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, and an antistatic agent.
- various additives such as a mold release agent, a foaming agent, a colorant, a crosslinking agent, a dispersion aid, and a resin component may be contained.
- the cured silicone resin of the present invention is obtained by radical polymerization of the curable silicone resin composition.
- the radical polymerization method include a method of thermosetting by heating and a method of photocuring by light irradiation.
- any one of the thermosetting and photocuring methods may be used alone, or both methods may be used in combination.
- the reaction temperature is room temperature (about 25 ° C.) to about 200 ° C.
- the reaction time is 0.5 to 10 hours.
- a wide range of degrees can be selected.
- it can be set as the molded object of a desired shape by carrying out the polymerization hardening of the said curable silicone resin composition in a metal mold
- all of general molding methods such as injection molding, extrusion molding, compression molding, transfer molding, calendar molding, and cast (casting) molding can be applied.
- Examples of the photocuring method include a method of irradiating the curable silicone resin composition with ultraviolet rays having a wavelength of 10 to 400 nm or visible rays having a wavelength of 400 to 700 nm for about 1 to 1200 seconds.
- the wavelength is not particularly limited, but near ultraviolet light having a wavelength of 200 to 400 nm is preferable.
- Examples of the lamp used as the ultraviolet ray generation source include a low-pressure mercury lamp (output: 0.4 to 4 W / cm), a high-pressure mercury lamp (40 to 160 W / cm), and an ultrahigh-pressure mercury lamp (173 to 435 W / cm).
- the curable silicone resin composition is poured into a mold made of a transparent material such as quartz glass, cured by radical polymerization, and then removed from the mold to obtain a desired shape.
- a molded body having a desired shape can be obtained by a method of manufacturing a molded body, a method of curing on the steel belt, or the like.
- Electrospray ionization mass spectrometry (ESI-MS) apparatus device name: LC apparatus; Separation module 2690 (manufactured by Waters), MS apparatus; ZMD4000 (manufactured by Micromass), measurement conditions: electrospray ionization method, capillary voltage: 3. 5 kV, cone voltage: +30 V).
- reaction solution in the reaction vessel after stirring is adjusted to neutral (pH 7) with a citric acid aqueous solution, and then pure water is added to separate the organic phase and the aqueous phase, and anhydrous magnesium sulfate is added to the organic phase. 10 g was added and dehydrated. The anhydrous magnesium sulfate was filtered off and concentrated by a rotary evaporator to obtain 48.49 g of a hydrolysis reaction product (silsesquioxane). This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents.
- reaction solution in the reaction vessel after stirring is adjusted to neutral (pH 7) with a citric acid aqueous solution, and then pure water is added to separate the organic phase and the aqueous phase, and anhydrous magnesium sulfate is added to the organic phase. 10 g was added and dehydrated. The anhydrous magnesium sulfate was filtered off and concentrated by a rotary evaporator to obtain 39.15 g of a resin mixture I. The obtained resin mixture I was a colorless viscous liquid soluble in various organic solvents.
- FIGS. 2A to 2B graphs showing 1 H-NMR spectra of the obtained resin mixture I are shown in FIGS. 2A to 2B. From these results, a vinyl group peak was detected at 6.1 to 5.7 ppm, and a methacryloyl group peak was detected at 5.5 ppm.
- the peak integration ratio of the vinyl group was 2. It was confirmed that the ratio of the number of vinyl groups to the number of methacryloyl groups in the resulting cage-type silsesquioxane resin (total number of vinyl groups: total number of methacryloyl groups) was 2.96: 1. It was done. In addition, this ratio shows that the condensate which has a functional group of the same ratio as the molar ratio of the vinyl group at the time of preparation and a methacryloyl group is obtained.
- FIG. 1 shows the detected main peaks (m / z) and the corresponding numerical values of n and m in the above formula (I).
- the detected peak (m / z) has the above formula (I) (where n is 1 to 12, m is 6 to 14, and the sum of n and m is 8 to 14).
- a resin mixture VI was obtained in the same manner as in Synthesis Example I except that 42.0 g of the hydrolysis reaction product obtained above was used and toluene was changed to 260 ml.
- the obtained resin mixture VI was a colorless viscous liquid soluble in various organic solvents.
- Example 1 First, with respect to 100 parts by mass of resin mixture I (cage-type silsesquioxane resin content: 45% by mass) containing a cage-type silsesquioxane resin having a vinyl group and a methacryloyl group obtained in Synthesis Example I , 1.0 part by mass of 1-hydroxycyclohexyl phenyl ketone (Irg184, manufactured by Ciba Japan Co., Ltd.) and 1.0 part by mass of dicumyl peroxide (Park Mill D, manufactured by NOF Corporation) as a polymerization initiator were mixed, A curable silicone resin composition was obtained.
- resin mixture I carrier-type silsesquioxane resin content: 45% by mass
- Example 2 70 parts by mass of a resin mixture I containing a cage silsesquioxane resin having a vinyl group and a methacryloyl group obtained in Synthesis Example I, and dicyclopentanyl diacrylate (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.)
- DCP-A dicyclopentanyl diacrylate
- 1.0 part by mass of 1-hydroxycyclohexyl phenyl ketone (Irg184, manufactured by Ciba Japan Co., Ltd.) and dicumyl peroxide (Park Mill D, Japan) 1.0 parts by mass of Ogyu Co., Ltd.
- a cured silicone resin was obtained in the same manner as in Example 1 using the obtained curable silicone resin composition.
- Example 3 A curable silicone resin composition as in Example 1 except that the resin mixture II obtained in Synthesis Example II (cage-type silsesquioxane resin content: 50% by mass) was used instead of the resin mixture I. And the cured silicone resin was obtained.
- Example 4 A curable silicone resin composition and a cured silicone resin were obtained in the same manner as in Example 2 except that the resin mixture II obtained in Synthesis Example II was used in place of the resin mixture I.
- Example 5 A curable silicone resin composition as in Example 1 except that the resin mixture III obtained in Synthesis Example III (cage-type silsesquioxane resin content: 75% by mass) was used instead of the resin mixture I. And the cured silicone resin was obtained.
- Example 6 A curable silicone resin composition and a cured silicone resin were obtained in the same manner as in Example 2 except that the resin mixture III obtained in Synthesis Example III was used in place of the resin mixture I.
- Example 7 A curable silicone resin composition as in Example 1 except that the resin mixture IV (cage-type silsesquioxane resin content: 45% by mass) obtained in Synthesis Example IV was used in place of the resin mixture I. And the cured silicone resin was obtained.
- Example 8 A curable silicone resin composition and a cured silicone resin were obtained in the same manner as in Example 2 except that the resin mixture IV obtained in Synthesis Example IV was used in place of the resin mixture I.
- the silicone resin cured products obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were evaluated for film formability, water absorption, linear expansion coefficient, and total light transmittance by the following methods. It was.
- Evaluation of film formability Visually check for cracks in the cured silicone resin: Evaluation A: No cracks or breaks are observed in the film. Evaluation B: Evaluation is made as a mesh-like crack or break is observed in the film. The obtained results are shown in Table 2.
- thermomechanical analysis method was performed using a device name: TMA4000SA (manufactured by BRUKER). Measurement was performed based on the temperature rise rate (5 ° C./min, compression load: 0.1 N, temperature range: 50 to 150 ° C.).
- the coefficient of linear expansion is: The coefficient of linear expansion (ppm / K) was calculated from the displacement per 1 m of the test piece / temperature displacement. The obtained results are shown in Table 2.
- the cured silicone resins obtained in Examples 1 to 8 all have excellent transparency, moldability and low water absorption, and have a sufficient linear expansion coefficient. It was confirmed to be small.
- the cured silicone resins obtained in Comparative Examples 1 and 2 were confirmed to have a high water absorption rate and a high linear expansion coefficient, and the cured silicone resins obtained in Comparative Examples 3 to 4 It was confirmed to be inferior.
- a curable silicone resin composition capable of obtaining a cured silicone resin having excellent transparency, moldability and low water absorption, and having a sufficiently small linear expansion coefficient, and It becomes possible to provide a cured silicone resin obtained by curing this.
- Such silicone resin cured products include liquid crystal display element substrates, color filter substrates, organic EL display element substrates, electronic paper substrates, TFT substrates, solar cell substrates, and other transparent substrates, touch panels, and transparent electrodes.
- liquid crystal display element substrates color filter substrates, organic EL display element substrates, electronic paper substrates, TFT substrates, solar cell substrates, and other transparent substrates, touch panels, and transparent electrodes.
- optical film application for films, light guide plates, protective films, polarizing films, retardation films, lens sheets, etc. as a glass substitute material for various transport machinery, housing window materials, etc., its range of use has become wide and its industrial utility value Is extremely high.
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Abstract
Description
下記一般式(1):
[CH2=CHSiO3/2]n[R1SiO3/2]m[R2SiO3/2]j ・・・(1)
{式(1)中、R1は、下記一般式(2):
CH2=CR3-CO-O-R4- ・・・(2)
[式(2)中、R3は、水素原子又はメチル基を示し、R4は、アルキレン基、アルキリデン基及びフェニレン基からなる群より選択されるいずれか一種を示す。]
で表わされる(メタ)アクリロイル基を有する基を示し、R2は、水素原子、炭素数1~6のアルキル基、フェニル基及びアリル基からなる群より選択されるいずれか一種を示し、n、m及びjは下記式(i)~(iv):
n≧1 ・・・(i)、
m≧1 ・・・(ii)、
j≧0 ・・・(iii)、
n+m+j=h ・・・(iv)
[式(iv)中、hは8、10、12及び14からなる群より選択されるいずれかの整数を示す。]
で表わされる条件を満たす整数を示し、m及びjがそれぞれ2以上の場合にはR1及びR2はそれぞれ同一でも異なっていてもよい。}
で表わされるかご型シルセスキオキサン樹脂と、ラジカル重合開始剤とを含有しており、
前記かご型シルセスキオキサン樹脂の含有量が10~80質量%であるものである。
[CH2=CHSiO3/2]n[R1SiO3/2]m[R2SiO3/2]j ・・・(1)
で表わされる。
CH2=CR3-CO-O-R4- ・・・(2)
で表わされる(メタ)アクリロイル基を有する基を示す。前記式(2)中、R3は、水素原子又はメチル基を示す。R3としては、立体構造の反発効果により、吸水性をより低減できるという観点から、メチル基が特に好ましい。また、前記式(2)中、R4は、アルキレン基、アルキリデン基及びフェニレン基からなる群より選択されるいずれか一種を示し、前記アルキレン基としては、直鎖状であっても分岐鎖状であってもよく、線膨張係数が小さくなるという観点から、炭素数が1~3であることが好ましく、前記アルキリデン基としては、直鎖状であっても分岐鎖状であってもよく、例えば、プロパン-2-イリデン等が挙げられ、前記フェニレン基としては、例えば、無置換フェニレン基に加えて、低級アルキル基を有する1,2-フェニレン等が挙げられ、中でも、原料の入手が容易であるという観点から、炭素数が1~3のアルキレン基が好ましい。これらの中でも、R4としては、原料の入手が容易であり、架橋間距離が大きくならず、また、線膨張係数が小さくなるという観点から、プロピレン基がより好ましい。
n≧1 ・・・(i)、
m≧1 ・・・(ii)、
j≧0 ・・・(iii)、
n+m+j=h ・・・(iv)
[式(iv)中、hは8、10、12及び14からなる群より選択されるいずれかの整数を示す。]
で表わされる条件を満たす整数を示す。前記nが前記式(i)で表わされる条件を満たすことにより、本発明に係るかご型シルセスキオキサン樹脂は1つ以上のビニル基を有するため、ラジカル重合による架橋間距離が短くなり線膨張係数が十分に小さい硬化物を得ることが可能となる。また、前記mが前記式(ii)で表わされる条件を満たすことにより、本発明に係るかご型シルセスキオキサン樹脂は1つ以上の(メタ)アクリロイル基を有するため、ラジカル重合により透明な硬化物を得ることが可能となり、特に(メタ)アクリロイル基を有する不飽和化合物と共重合せしめる場合には相溶性が向上するためより透明な硬化物を得ることが可能となる。さらに、前記n、m及びjが前記式(i)~(iv)で表わされる条件を満たすことにより、本発明に係るかご型シルセスキオキサン樹脂はほぼ完全に縮合したかご型構造となるため、優れた透明性、成形性及び低吸水性を有し、線膨張係数が十分に小さいシリコーン樹脂硬化物を得ることが可能となる。なお、m及びjがそれぞれ2以上の場合にはR1及びR2はそれぞれ同一でも異なっていてもよい。
(n+m)/j≧1 ・・・(v)
で表わされる条件を満たすことがより好ましい。
で表わされる化合物、上記一般式(1)中、nが6であり、mが2であり、jが0であり、R4が(CH2)kであり、下記式(4):
で表わされる化合物、上記一般式(1)中、nが4であり、mが4であり、jが0であり、R4が(CH2)kであり、下記式(5):
で表わされる化合物、上記一般式(1)中、nが8であり、mが2であり、jが0であり、R4が(CH2)kであり、下記式(6):
で表わされる化合物、上記一般式(1)中、nが6であり、mが2であり、jが2であり、R4が(CH2)kであり、R2がCH3CH2-であり、下記式(7):
で表わされる化合物、上記一般式(1)中、nが7であり、mが3であり、jが0であり、R4が(CH2)kであり、下記式(8):
で表わされる化合物、上記一般式(1)中、nが6であり、mが4であり、jが0であり、R4が(CH2)kであり、下記式(9):
で表わされる化合物、上記一般式(1)中、nが11であり、mが1であり、jが0であり、R4が(CH2)kであり、下記式(10):
で表わされる化合物、上記一般式(1)中、nが10であり、mが2であり、jが0であり、R4が(CH2)kであり、下記式(11):
で表わされる化合物、上記一般式(1)中、nが8であり、mが4であり、jが0であり、R4が(CH2)kであり、下記式(12):
で表わされる化合物、上記一般式(1)中、nが10であり、mが4であり、jが0であり、R4が(CH2)であり、下記式(13):
CH2=CHSiX3 ・・・(15)
[式(15)中、Xはアルコキシ基、アセトキシ基、ハロゲン原子及びヒドロキシ基からなる群より選択されるいずれか一種の加水分解性基を示す。]
で表されるケイ素化合物(A)と、下記一般式(16):
R1SiY3 ・・・(16)
[式(16)中、R1は、上記式(1)中のR1と同義であり、Yはアルコキシ基、アセトキシ基、ハロゲン原子及びヒドロキシ基からなる群より選択されるいずれか一種の加水分解性基を示す。]
で表されるケイ素化合物(B)と、下記一般式(17):
R2SiZ3 ・・・(17)
[式(17)中、R2は、上記式(1)中のR2と同義であり、Zは、アルコキシ基、アセトキシ基、ハロゲン原子及びヒドロキシ基からなる群より選択されるいずれか一種の加水分解性基を示す。]
で表されるケイ素化合物(C)とを混合し、塩基性触媒存在下において、非極性溶媒及び/又は極性溶媒中で加水分解反応せしめると共に一部縮合させ、得られた加水分解反応生成物を更に非極性溶媒及び塩基性触媒の存在下で再縮合せしめる方法が挙げられる。
10/90 ≦ a/(b+c) ≦ 80/20
で表わされる条件を満たすことが好ましく、下記式:
20/80 ≦ a/(b+c) ≦ 75/25
で表わされる条件を満たすことがより好ましい。前記かご型シルセスキオキサン樹脂の含有量が前記下限未満である場合にはシリコーン樹脂硬化物の透明性、低熱膨張性、低吸水性、相溶性等の物性が低下する傾向にある。他方、前記上限を超える場合には、シリコーン樹脂組成物の粘度が増大して成形物の製造が困難となる傾向にある。
ゲルパーミエーションクロマトグラフィ(GPC)(装置名:HLC-8320GPC(東ソー社製)、溶媒:THF、カラム:超高速セミミクロSECカラム SuperH
シリーズ、温度:40℃、速度:0.6ml/min)を用いて行った。数平均分子量及び分子量分布(重量平均分子量/数平均分子量(Mw/Mn))は標準ポリスチレン(商品名:TSK-GEL、東ソー社製)による換算値として求めた。
1H-NMR測定器(装置名:JNM-ECA400(JEOL社製)、溶媒:重クロロホルム、温度:23℃、400MHz)を用いて測定した。得られた各構成単位のピークの積分値を求め、これらの比からビニル基の数と(メタ)アクリロイル基の数とのモル比を決定した。
エレクトロスプレーイオン化質量分析(ESI-MS)装置(装置名:LC装置;Separation module 2690(Waters社製)、MS装置;ZMD4000(Micromass社製)、測定条件:エレクトロスプレーイオン化法、キャピラリ電圧:3.5kV、コーン電圧:+30V)を用いて測定した。
先ず、撹拌機、滴下漏斗、温度計を備えた反応容器に、溶媒として2-プロパノール(IPA)120ml、トルエン150ml、塩基性触媒として5%テトラメチルアンモニウムヒドロキシド水溶液(TMAH水溶液)30.0mlを入れた。次いで、ビニルトリメトキシシラン(KBM-1003、信越化学工業株式会社製)53.36g(0.36mol)及び3-メタクリロキシプロピルトリメトキシシラン(SZ-6300、東レ・ダウコーニング・シリコーン株式会社製)29.80g(0.12mol)を混合して滴下漏斗に入れ、前記反応容器内に、撹拌しながら室温(約25℃)で30分かけて滴下した。滴下終了後、加熱することなく2時間撹拌した。攪拌後の反応容器内の溶液(反応溶液)をクエン酸水溶液で中性(pH7)に調整した後、純水を添加して有機相と水相とに分液し、有機相に無水硫酸マグネシウム10gを添加して脱水した。前記無水硫酸マグネシウムを濾別し、ロータリーエバポレーターにより濃縮することで加水分解反応生成物(シルセスキオキサン)を48.49g得た。この加水分解反応生成物は種々の有機溶剤に可溶な無色の粘性液体であった。
[CH2=CHSiO3/2]n[CH2=C(CH3)COOC3H6SiO3/2]m・・・(I)
で表わされるかご型シルセスキオキサン樹脂を含む樹脂混合物であることが確認された。
2-プロパノール(IPA)を110ml、トルエンを230mlとし、ビニルトリメトキシシランを70.76g(0.48mol)、3-メタクリロキシプロピルトリメトキシシランを16.94g(0.07mol)としたこと以外は合成例Iと同様にして加水分解反応生成物(シルセスキオキサン)を47.60g得た。この加水分解反応生成物は種々の有機溶剤に可溶な無色の粘性液体であった。
2-プロパノール(IPA)を80ml、トルエンを160mlとし、ビニルトリメトキシシランを28.68g(0.19mol)、3-メタクリロキシプロピルトリメトキシシランを48.06g(0.19mol)としたこと以外は合成例Iと同様にして加水分解反応生成物(シルセスキオキサン)を48.68g得た。この加水分解反応生成物は種々の有機溶剤に可溶な無色の粘性液体であった。次いで、上記で得られた加水分解反応生成物を45.0g用いたこと以外は合成例Iと同様にして樹脂混合物IIIを38.33g得た。得られた樹脂混合物IIIは種々の有機溶剤に可溶な無色の粘性液体であった。
2-プロパノール(IPA)を100ml、トルエンを200mlとし、ビニルトリメトキシシランを44.36g(0.30mol)、3-メタクリロキシプロピルトリメトキシシランを29.73g(0.12mol)とし、更にエチルトリメトキシシラン(LS-890、信越化学工業株式会社製)8.99g(0.06mol)を混合して滴下漏斗に入れたこと以外は合成例Iと同様にして加水分解反応生成物(シルセスキオキサン)を47.09g得た。この加水分解反応生成物は種々の有機溶剤に可溶な無色の粘性液体であった。
[CH2=CHSiO3/2]n[CH2=C(CH3)COOC3H6SiO3/2]m[CH3CH2SiO3/2]j・・・(IV)
で表わされるかご型シルセスキオキサン樹脂を含む樹脂混合物であることが確認された。また、得られた樹脂混合物IVの1H-NMRスペクトルから求めたかご型シルセスキオキサン樹脂中の全ビニル基数:全メタアクリロイル基数は4.96:2であった。
2-プロパノール(IPA)を60ml、トルエンを120mlとし、3-メタクリロキシプロピルトリメトキシシランを69.27g(0.28mol)とし、ビニルトリメトキシシランを用いなかったこと以外は合成例Iと同様にして加水分解反応生成物(シルセスキオキサン)を48.36g得た。この加水分解反応生成物は種々の有機溶剤に可溶な無色の粘性液体であった。
[CH2=C(CH3)COOC3H6SiO3/2]m・・・(V)
で表わされるかご型シルセスキオキサン樹脂を含む樹脂混合物であることが確認された。
2-プロパノール(IPA)を130ml、トルエンを260mlとし、ビニルトリメトキシシランを93.65g(0.632mol)とし、3-メタクリロキシプロピルトリメトキシシランを用いなかったこと以外は合成例Iと同様にして加水分解反応生成物(シルセスキオキサン)を44.03g得た。この加水分解反応生成物は種々の有機溶剤に可溶な無色の粘性液体であった。
[CH2=CHSiO3/2]n・・・(VI)
で表わされるかご型シルセスキオキサン樹脂を含む樹脂混合物であることが確認された。
先ず、合成例Iで得られたビニル基とメタアクリロイル基とを有するかご型シルセスキオキサン樹脂を含む樹脂混合物I(かご型シルセスキオキサン樹脂含有量:45質量%)100質量部に対し、重合開始剤として1-ヒドロキシシクロヘキシルフェニルケトン(Irg184、チバ・ジャパン株式会社製)1.0質量部及びジクミルパーオキサイド(パークミルD、日本油脂株式会社製)1.0質量部を混合し、硬化性シリコーン樹脂組成物を得た。
合成例Iで得られたビニル基とメタアクリロイル基とを有するかご型シルセスキオキサン樹脂を含む樹脂混合物I 70質量部、及びジシクロペンタニルジアクリレート(DCP-A、共栄社化学株式会社製) 30質量部を混合した合計100質量部の混合物に対し、重合開始剤として1-ヒドロキシシクロヘキシルフェニルケトン(Irg184、チバ・ジャパン株式会社製)1.0質量部及びジクミルパーオキサイド(パークミルD、日本油脂株式会社製)1.0質量部を混合し、硬化性シリコーン樹脂組成物を得た。また、得られた硬化性シリコーン樹脂組成物を用い、実施例1と同様にしてシリコーン樹脂硬化物を得た。
樹脂混合物Iに代えて合成例IIで得られた樹脂混合物II(かご型シルセスキオキサン樹脂含有量:50質量%)を用いたこと以外は実施例1と同様にして硬化性シリコーン樹脂組成物及びシリコーン樹脂硬化物を得た。
樹脂混合物Iに代えて合成例IIで得られた樹脂混合物IIを用いたこと以外は実施例2と同様にして硬化性シリコーン樹脂組成物及びシリコーン樹脂硬化物を得た。
樹脂混合物Iに代えて合成例IIIで得られた樹脂混合物III(かご型シルセスキオキサン樹脂含有量:75質量%)を用いたこと以外は実施例1と同様にして硬化性シリコーン樹脂組成物及びシリコーン樹脂硬化物を得た。
樹脂混合物Iに代えて合成例IIIで得られた樹脂混合物IIIを用いたこと以外は実施例2と同様にして硬化性シリコーン樹脂組成物及びシリコーン樹脂硬化物を得た。
樹脂混合物Iに代えて合成例IVで得られた樹脂混合物IV(かご型シルセスキオキサン樹脂含有量:45質量%)を用いたこと以外は実施例1と同様にして硬化性シリコーン樹脂組成物及びシリコーン樹脂硬化物を得た。
樹脂混合物Iに代えて合成例IVで得られた樹脂混合物IVを用いたこと以外は実施例2と同様にして硬化性シリコーン樹脂組成物及びシリコーン樹脂硬化物を得た。
樹脂混合物Iに代えて合成例Vで得られた樹脂混合物Vを用いたこと以外は実施例1と同様にして硬化性シリコーン樹脂組成物及びシリコーン樹脂硬化物を得た。
樹脂混合物Iに代えて合成例Vで得られた樹脂混合物Vを用いたこと以外は実施例2と同様にして硬化性シリコーン樹脂組成物及びシリコーン樹脂硬化物を得た。
樹脂混合物Iに代えて合成例VIで得られた樹脂混合物VIを用いたこと以外は実施例1と同様にして硬化性シリコーン樹脂組成物及びシリコーン樹脂硬化物を得た。
樹脂混合物Iに代えて合成例VIで得られた樹脂混合物VIを用いたこと以外は実施例2と同様にして硬化性シリコーン樹脂組成物及びシリコーン樹脂硬化物を得た。
シリコーン樹脂硬化物の割れを目視により以下の基準:
評価A:フィルムに割れ、破断は観察されない
評価B:フィルムに網目状の割れまたは、破断が観察される
に従って評価した。得られた結果を表2に示す。
先ず、得られたシリコーン樹脂硬化物を24時間、50℃において保持し、予備乾燥を行った。次いで、プラスチック―吸水率の求め方(JISK7209)に基づいて吸水率の測定を行った。得られた結果を表2に示す。
得られたシリコーン樹脂硬化物(5mm×5mm×厚さ1mm(厚さ0.2mmの試験片を5枚重ねたもの)について、機器名:TMA4000SA(BRUKER社製)を用いて熱機械分析法に基づき測定を行った(昇温速度:5℃/min、圧縮荷重:0.1N、温度範囲:50~150℃)。
線膨張係数は、次式:
線膨張係数(ppm/K)=試験片1m当たりの変位量/温度変位量
により算出した。得られた結果を表2に示す。
得られたシリコーン樹脂硬化物(厚さ0.2mm)について、NDH2000(日本電色社製)を用いて全光の透過率を測定した。
透過率は、次式:
全光透過率(%)=透過光強度/入射光強度
により算出した。得られた結果を表2に示す。
Claims (5)
- 下記一般式(1):
[CH2=CHSiO3/2]n[R1SiO3/2]m[R2SiO3/2]j ・・・(1)
{式(1)中、R1は、下記一般式(2):
CH2=CR3-CO-O-R4- ・・・(2)
[式(2)中、R3は、水素原子又はメチル基を示し、R4は、アルキレン基、アルキリデン基及びフェニレン基からなる群より選択されるいずれか一種を示す。]
で表わされる(メタ)アクリロイル基を有する基を示し、R2は、水素原子、炭素数1~6のアルキル基、フェニル基及びアリル基からなる群より選択されるいずれか一種を示し、n、m及びjは下記式(i)~(iv):
n≧1 ・・・(i)、
m≧1 ・・・(ii)、
j≧0 ・・・(iii)、
n+m+j=h ・・・(iv)
[式(iv)中、hは8、10、12及び14からなる群より選択されるいずれかの整数を示す。]
で表わされる条件を満たす整数を示し、前記m及び前記jがそれぞれ2以上の場合にはR1及びR2はそれぞれ同一でも異なっていてもよい。}
で表わされるかご型シルセスキオキサン樹脂と、ラジカル重合開始剤とを含有しており、
前記かご型シルセスキオキサン樹脂の含有量が10~80質量%である硬化性シリコーン樹脂組成物。 - 前記かご型シルセスキオキサン樹脂において、ビニル基の数と(メタ)アクリロイル基の数との比(全ビニル基数:全(メタ)アクリロイル基数)が1:4~13:1である請求項1に記載の硬化性シリコーン樹脂組成物。
- (メタ)アクリロイル基を有する不飽和化合物を更に含有する請求項1又は2に記載の硬化性シリコーン樹脂組成物。
- 前記ラジカル重合開始剤の含有量が0.01~10質量%である請求項1~3のうちのいずれか一項に記載の硬化性シリコーン樹脂組成物。
- 請求項1~4のうちのいずれか一項に記載の硬化性シリコーン樹脂組成物をラジカル重合させて得られたものであるシリコーン樹脂硬化物。
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EP3511304A1 (de) * | 2018-01-11 | 2019-07-17 | Evonik Degussa GmbH | Spezielle zusammensetzung organofunktioneller alkoxysilane und deren verwendung |
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