WO2009119253A1 - Composé silsesquioxane de type cage, durcissable, contenant un groupe silanol, copolymère de silicone durcissable, contenant une structure en cage, leurs procédés de production, et composition de résine durcissable - Google Patents

Composé silsesquioxane de type cage, durcissable, contenant un groupe silanol, copolymère de silicone durcissable, contenant une structure en cage, leurs procédés de production, et composition de résine durcissable Download PDF

Info

Publication number
WO2009119253A1
WO2009119253A1 PCT/JP2009/053751 JP2009053751W WO2009119253A1 WO 2009119253 A1 WO2009119253 A1 WO 2009119253A1 JP 2009053751 W JP2009053751 W JP 2009053751W WO 2009119253 A1 WO2009119253 A1 WO 2009119253A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
general formula
meth
oxirane ring
vinyl
Prior art date
Application number
PCT/JP2009/053751
Other languages
English (en)
Japanese (ja)
Inventor
充洋 小池
憲 齋藤
Original Assignee
新日鐵化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 新日鐵化学株式会社 filed Critical 新日鐵化学株式会社
Priority to JP2010505478A priority Critical patent/JPWO2009119253A1/ja
Publication of WO2009119253A1 publication Critical patent/WO2009119253A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences

Definitions

  • the present invention relates to a novel curable cage-type silsesquioxane compound, a copolymer obtained using the curable cage-type silsesquioxane compound, a method for producing these, and a curable resin composition.
  • the present invention relates to a copolymer and a production method thereof, and further relates to a curable resin composition containing the cage-type structure-containing curable silicone copolymer.
  • Non-Patent Document 1 discloses a silsesquioxane having an incompletely condensed structure (a structure that is not a complete octahedral structure but is cleaved in at least one place and is not closed) with a siloxane bond.
  • a method for producing a linked copolymer is disclosed.
  • Non-Patent Document 2 discloses a method for producing a copolymer obtained by reacting a silanol group possessed by an incomplete cage-type silsesquioxane with aminosilane or the like.
  • Non-Patent Document 3 shows an example composed of a vinyl group-containing silsesquioxane and a hydrosilyl group-containing silsesquioxane. However, all of these resins are rigid and very brittle materials.
  • the conventional silsesquioxane copolymer has an unclear structure and lacks stability, and when graft-type silsesquioxane is graft-polymerized to the main chain, it becomes a crosslinking point and gels. It is difficult to obtain a structure satisfying the characteristics. Therefore, a copolymer having excellent moldability, in which a cage silsesquioxane having excellent heat resistance, weather resistance, optical properties and the like is used as the main chain and the position of the bond is clearly limited is desired.
  • Patent Documents 1 and 2 below have Si-ONa as a reactive group by hydrolyzing a silane compound having a trifunctional hydrolyzable group in an organic solvent in the presence of a monovalent alkali metal hydroxide. After synthesis of incomplete cage-type silsesquioxane, by reacting this incomplete cage-type silsesquioxane with a chlorosilane having a functional group according to the purpose, by copolymerization with various compounds A method for obtaining a copolymer has been reported. However, as far as the present inventor knows, no other examples have been reported, and the above method is limited in the side chain of the cage silsesquioxane skeleton and is not curable, so that it is heat resistant. There is concern about inferiority.
  • an optical material including a substrate for a liquid crystal display device, an optical lens, and a light emitting diode sealing material
  • a material having a low birefringence, a low photoelastic coefficient, and a high optical transparency is used.
  • the materials used in the manufacturing process must have high heat resistance.
  • glass or the like has been used as a material that satisfies these requirements.
  • optical lenses are used on curved surfaces, and substrates for liquid crystal display devices are required to be thin, and conventionally used glass has a property of being brittle in strength. The range of use has become limited.
  • a polymer material can be considered as a tough material, but in general, a polymer material has low heat resistance.
  • an acrylate resin may be colored by heat because of its low heat resistance. Therefore, the introduction of an aromatic skeleton as a means of developing high heat resistance has been studied, but on the other hand, since the birefringence increases and the photoelastic coefficient increases, high heat resistance and optical performance are achieved. It is difficult to achieve both.
  • an object of the present invention is to provide a curable cage-type silsesquioxane compound containing a silanol group and a copolymer incorporating the same in the main chain.
  • each of the curable cage-type silsesquioxane compound containing a silanol group, and the copolymer which incorporated this in the principal chain is provided. Furthermore, it is providing the curable resin composition which can obtain the molded object which was excellent in heat resistance, an optical characteristic, and dimensional stability, and also had toughness.
  • the present inventors have found that a curable cage-type silsesquioxane compound containing a silanol group under specific reaction conditions and a co-polymer incorporating this in the main chain.
  • the inventors found that a coalescence can be obtained, and further found that a curable resin composition containing such a copolymer gives a cured product having excellent heat resistance, optical properties, and dimensional stability, and completed the present invention. It came to do.
  • the present invention provides the following general formula (1) [R 1 SiO 3/2 ] n (1) (However, R 1 is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, which may be the same or different from each other, but are included in one molecule.
  • At least one of R 1 is a vinyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, and n represents a number of 6 to 14.)
  • the silsesquioxane compound is cleaved by one or more siloxane bonds in an organic solvent containing one or both of a nonpolar solvent and a polar solvent to cleave the counter cation derived from the basic compound.
  • the compound represented by the following general formula (2) is characterized in that it can be converted to a hydroxyl group by treating with an acid after binding to the moiety.
  • R 1 is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group, or an oxirane ring, and they may be the same or different from each other. At least one of R 1 contained is any one of a vinyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, n is a number of 6 to 14, and m is a number of 1 to 4.
  • a silanol group-containing curable caged silsesquioxane compound represented by:
  • R 1 is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, which may be the same or different from each other, but are included in one molecule.
  • At least one of R 1 is a vinyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, and n represents a number of 6 to 14.
  • R 1 is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, which may be the same or different from each other, but are included in one molecule. And at least one of R 1 is a vinyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, n is a number of 6 to 14, and m is a number of 1 to 4. .) Is a method for producing a silanol group-containing curable caged silsesquioxane compound.
  • R 1 is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, which may be the same or different from each other, but are included in one molecule.
  • At least one of R 1 is any one of a vinyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, n represents a number of 6 to 14, and l represents a number of 1 to 2000.
  • Z represents the following general formula (4)
  • R 2 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, which may be the same or different from each other
  • R 1 is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, which may be the same or different from each other, but are included in one molecule.
  • R 1 is a vinyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring
  • n is a number of 6 to 14
  • m is a number of 1 to 4.
  • R 3 is a group having hydrogen, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and may be the same or different from each other).
  • a monovalent group. The cocoon structure containing curable silicone copolymer characterized by having the structural unit represented by these.
  • the present invention provides the following general formula (2) [R 1 SiO 3/2 ] n [HO 1/2 ] m (2)
  • R 1 is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, which may be the same or different from each other, but are included in one molecule.
  • at least one of R 1 is a vinyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring
  • n is a number of 6 to 14
  • m is a number of 1 to 4.
  • R 2 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, which may be the same or different from each other, Is a hydrogen atom, a halogen atom or an alkoxyl group, which may be the same or different from each other, and b represents a number of 0 to 30), or a condensation reaction with a compound represented by The following general formula (8) (Wherein R 3 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, and may be the same or different from each other).
  • R 1 is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, which may be the same or different from each other, but are included in one molecule.
  • At least one of R 1 is any one of a vinyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, n represents a number of 6 to 14, and l represents a number of 1 to 2000.
  • Z represents the following general formula (4)
  • R 2 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, which may be the same or different from each other
  • R 1 is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, which may be the same or different from each other, but are included in one molecule.
  • R 1 is a vinyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring
  • n is a number of 6 to 14
  • m is a number of 1 to 4.
  • R 3 is a group having hydrogen, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, which may be the same or different from each other). It is a monovalent group.
  • a cocoon structure-containing curable silicone copolymer having a structural unit represented by the following formula:
  • the present invention provides the following general formula (3) Y- [Z- (R 1 SiO 3/2 ) n ] l -ZY (3) (The explanation in the formula is the same as described above)
  • a curable resin composition obtained by blending either or both of a hydrosilylatable compound having a hydrogen atom on at least one silicon atom and a compound having an unsaturated group in the molecule.
  • the present invention is a cured product (molded product) obtained by molding and curing the curable resin composition, and specifically obtained by hydrosilylation and radical polymerization of the curable resin composition. Cured product (molded product).
  • silanol group-containing curable caged silsesquioxane compound represented by the general formula (2) are shown in the following structural formulas (9) to (15), respectively.
  • the structural unit represented by the general formula (2) is not limited to those represented by the structural formulas (9) to (15).
  • R 1 is the same as in General Formula (2).
  • a curable cage-type silsesquioxane compound represented by the general formula (1) is polarized with a nonpolar solvent in the presence of a basic compound.
  • a curable cage-type silsesquioxane compound represented by the general formula (1) is polarized with a nonpolar solvent in the presence of a basic compound.
  • Examples of the basic compound used for synthesizing the silanol group-containing curable silsesquioxane compound represented by the general formula (2) include, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutyl hydroxide.
  • Examples thereof include ammonium hydroxide salts such as ammonium, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide, and monovalent alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide.
  • an ammonium hydroxide salt is preferable because it is effective in serving as a counter cation.
  • An example of a preferred ammonium hydroxide salt is tetramethylammonium hydroxide.
  • the amount of the basic compound used is preferably in the range of 0.5 to 3 mol, more preferably 1.5 to 2.5 mol, relative to 1 mol of the structural unit represented by the general formula (1). It is good to be. When the amount of the basic compound used is less than 0.5 mol during this reaction, the reaction does not proceed. On the other hand, when it exceeds 3 mol, the cleavage reaction of the cocoon structure is excessively promoted and decomposes.
  • the basic compound is usually used as an alcohol solution. Examples of the alcohol solution to be used include methanol, ethanol, propanol, and isopropanol. Among these, methanol is preferable.
  • the organic solvent used in the synthesis of the silanol group-containing curable silsesquioxane compound represented by the general formula (2) is a solvent obtained by combining one or both of a nonpolar solvent and a polar solvent.
  • nonpolar solvents include hydrocarbon solvents such as hexane, toluene, xylene, and benzene.
  • polar solvents include ether solvents such as diethyl ether and tetrahydrofuran, ester solvents such as ethyl acetate, alcohol solvents such as methanol, ethanol and isopropanol, and ketone solvents such as acetone and methyl ethyl ketone. it can.
  • a polar solvent is preferable from the viewpoint of structure control contribution due to the solvation effect, and tetrahydrofuran is more preferable among them.
  • the amount of the organic solvent used is preferably in the range of 0.01 to 10 M molar concentration (mol / l: M) relative to 1 mol of the structural unit represented by the general formula (1), more preferably 0.01 to 1M is preferable.
  • About the addition amount of the nonpolar solvent and / or polar solvent with respect to an organic solvent it is good for a nonpolar solvent to be small with respect to a polar solvent.
  • a preferable blending ratio is 1 for the nonpolar solvent with respect to the polar solvent 10 to 100, and more preferably 1 for the nonpolar solvent with respect to the polar solvent 50 to 100.
  • the reaction temperature is preferably 0 to 60 ° C, more preferably 20 to 40 ° C.
  • the reaction rate becomes slow and remains in the state of uncleaved completely caged silsesquioxane, resulting in a long reaction time.
  • the temperature is higher than 60 ° C., the reaction rate is too high, so that a complex condensation reaction proceeds, and as a result, a high molecular weight is promoted.
  • the reaction time varies depending on the substituent R 1 having the structure represented by the general formula (1), but is usually from several minutes to several hours, preferably from 1 to 3 hours.
  • water or water-containing reaction solvent is separated. Separation of the water or the water-containing reaction solvent can employ means such as washing the solution with a saline solution to sufficiently remove moisture and other impurities, and then drying with a drying agent such as anhydrous magnesium sulfate.
  • a polar solvent means such as evaporation under reduced pressure can be employed.
  • a nonpolar solvent is added to dissolve the polycondensate, followed by washing and drying in the same manner as described above.
  • the weakly acidic solution sulfuric acid diluted solution, hydrochloric acid diluted solution, citric acid diluted solution, acetic acid, ammonium chloride aqueous solution, malic acid solution, oxalic acid solution and the like are used. If the nonpolar solvent is separated by means such as evaporation, the reaction product can be recovered. However, if the nonpolar solvent can be used as the nonpolar solvent used in the next reaction, it is not necessary to separate it.
  • the silanol group-containing curable cage-type silsesquioxane compound obtained above can be represented by the following general formula (2). [R 1 SiO 3/2 ] n [HO 1/2 ] m (2) (However, R 1 is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group, or an oxirane ring, and they may be the same or different from each other.
  • At least one of R 1 contained has a curable functional group of any one of a vinyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, n is a number of 6 to 14, and m is 1 to 4 Indicates the number of
  • silanol group-containing curable caged silsesquioxane compound represented by the general formula (2) is not considered to have a partly silanol group at the terminal and does not form a completely closed space. It is a fully condensed silsesquioxane.
  • the silanol group-containing curable caged silsesquioxane compound represented by the general formula (2) and the following general formula (7) (Wherein R 2 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, and may be the same or different from each other.
  • R 1 is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, which may be the same or different from each other, but at least the general formula (3 ) -1 has one curable functional group of vinyl group, (meth) acryloyl group, allyl group or group having oxirane ring, and n is a number from 6 to 14.
  • And 1 represents a number of 1 to 2000.
  • a cocoon structure-containing curable silicone copolymer having a structural unit represented by the following formula can be obtained.
  • Z is the following general formula (4) (Wherein R 2 is hydrogen, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, and may be the same or different from each other.
  • a divalent group represented by the number of 30 is the following general formula (4) (Wherein R 2 is hydrogen, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, and may be the same or different from each other.
  • Y 1 represents the following general formula (5 ′) HO 1/2- (5 ') Or the following general formula (5) -[R 1 SiO 3/2 ] n [HO 1/2 ] m-1 (5)
  • R 1 is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, which may be the same or different from each other, but are included in one molecule.
  • at least one of R 1 is a vinyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring
  • n is a number of 6 to 14
  • m is a number of 1 to 4.
  • cocoon structure-containing curable silicone copolymer obtained by condensation reaction of silanol group-containing curable cage-type silsesquioxane compound represented by general formula (2) and compound represented by formula (7)
  • the production method varies depending on the type of the substituent X of the compound represented by the general formula (7).
  • R 2 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group, or a group having an oxirane ring, and may be the same or different from each other.
  • Silanol group-containing curable caged silsesquioxane compound is added to a mixed solution in which triethylamine is added or dissolved in an amine solvent as a solvent and base, and one or both of a nonpolar solvent and an ether solvent are used.
  • the solution dissolved in the combined solvent is dropped at room temperature under an inert gas atmosphere such as nitrogen, and then stirred at room temperature for 2 hours or more. Good. At this time, if the reaction time is short, the reaction may not be completed.
  • dichlorosilane in which b is 0 in the general formula (16) include allyldichlorosilane, allylhexyldichlorosilane, allylmethyldichlorosilane, allylphenyldichlorosilane, methyldichlorosilane, dimethyldichlorosilane, ethyldisilane.
  • Chlorosilane methylvinyldichlorosilane, ethylmethyldichlorosilane, ethoxymethyldichlorosilane, divinyldichlorosilane, diethyldichlorosilane, methylpropyldichlorosilane, diethoxydichlorosilane, butylmethyldichlorosilane, phenyldichlorosilane, diallyldichlorosilane, methylpentyl Dichlorosilane, methylphenyldichlorosilane, cyclohexylmethyldichlorosilane, hexylmethyldichlorosilane, phenylvinyldichlorosilane, 6- Methyldichlorosilyl-2-norbornene, 2-methyldichlorosilylnorbornene, 3-methacryloxypropyldichloromethylsilane, hept
  • ⁇ , ⁇ -dichlorosiloxane in which b is 1 to 30 are as follows: 1,1,3,3-tetramethyl-1,3-dichlorosiloxane, 1,1 , 3,3-tetracyclopentyl-1,3-dichlorosiloxane, 1,1,3,3, -tetraisopropyl-1,3-dichlorosiloxane, 1,1,3,3,5,5-hexamethyl-1, Examples include 5-dichlorotrisiloxane, 1,1,3,3,5,5,7,7-octamethyl-1,7-dichlorotetrasiloxane.
  • the organic solvent used when X in the compound represented by the general formula (7) is chlorine can be arbitrarily selected as long as it is inert to dichlorosilane or ⁇ , ⁇ -dichlorosiloxane.
  • the nonpolar solvent include hydrocarbon solvents such as hexane, toluene, xylene, and benzene.
  • the ether solvent include diethyl ether and tetrahydrofuran. Among these, ether solvents are preferable from the viewpoint of contribution to structure control due to the solvation effect, and tetrahydrofuran is more preferable among them.
  • amine solvent examples include pyridine, triethylamine, aniline, N, N-diisopropylamine.
  • a base such as triethylamine is added.
  • a preferable amount of the solvent used is in the range of 0.01 to 10M with respect to 1 mol of the silanol group-containing curable caged silsesquioxane structural unit represented by the general formula (2), preferably 0.01 to 1M is preferable.
  • X of the compound represented by the general formula (7) is an alkoxyl group, that is, the following general formula (17) (However, R 2 is hydrogen, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group, an alkoxyl group, or a group having an oxirane ring, and may be the same or different from each other.
  • ⁇ 4 is a methyl group, an ethyl group, or a propyl group, which may be the same or different from each other (b represents a number of 0 to 30), and a silanol group represented by the general formula (2) Dialkoxysilane represented by the above general formula (17) in the range of 0.5 to 10 mol, preferably 0.5 to 3.0 mol, relative to 1 mol of the curable cage-type silsesquioxane compound, or By reacting ⁇ , ⁇ -dialkoxysiloxane in the presence of a catalyst in a solvent including one or both of a nonpolar solvent and an ether solvent, the structural unit represented by the general formula (3) -1 can be obtained. Containing curable silicone copolymer with cocoon structure It is possible to obtain.
  • silanol group-containing curable caged silsesquioxane compound represented by general formula (2) and dialkoxysilane or ⁇ , ⁇ -dialkoxysiloxane represented by general formula (17)
  • a silanol group-containing curable silsesquioxane compound represented by the general formula (2), dialkoxysilane, or ⁇ , ⁇ -dialkoxysiloxane and a catalyst selected from a nonpolar solvent and an ether solvent When dissolved in one or both solvents, the concentration is preferably 0.1 to 2.0 M with respect to the silanol group-containing curable caged silsesquioxane compound.
  • the reaction temperature is preferably 0 to 130 ° C, more preferably 80 to 110 ° C.
  • the reaction rate becomes slow, resulting in a long reaction time.
  • the temperature is higher than 130 ° C., a cleavage reaction of the cocoon structure occurs, and as a result of a complicated condensation reaction, a gel-like solid is formed.
  • the reaction time is preferably 2 hours or more. At this time, if the reaction time is short, the reaction may not be completed.
  • the reaction solution is made neutral or acidic, and then water or a water-containing reaction solvent is separated. Separation of the water or the water-containing reaction solvent can employ means such as washing the solution with a saline solution to sufficiently remove moisture and other impurities, and then drying with a drying agent such as anhydrous magnesium sulfate.
  • a drying agent such as anhydrous magnesium sulfate.
  • an ether solvent means such as evaporation under reduced pressure can be employed.
  • a nonpolar solvent is added to dissolve the polycondensate, and washing and drying are performed in the same manner as described above.
  • dialkoxysilane in which b is represented by 0 for general formula (17) include dimethoxydimethylsilane, diethoxymethylsilane, diethoxyvinylsilane, diethoxydiethylsilane, dimethyldipropoxysilane, dimethoxymethylphenylsilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, diethoxymethylphenylsilane, 3-methacryloxypropylmethyldiethoxysilane, dimethoxydiphenylsilane, Examples include diethoxydodecylmethylsilane.
  • ⁇ , ⁇ -dialkoxysiloxane in which b is represented by 1 to 30 in the general formula (17) include 1,3-dimethoxytetramethyldisiloxane, 1,3-diethoxytetramethyldisiloxane, 1 1,5-dimethoxyhexamethyltrisiloxane, 1,7-dimethoxyoctamethyltetrasiloxane, 1,5-diethoxyhexamethyltrisiloxane, 1,7-diethoxyoctamethyltetrasiloxane, and the like.
  • the organic solvent used when X of the compound represented by the general formula (7) is an alkoxyl group can be arbitrarily selected as long as it is inert with respect to alkoxysilane or ⁇ , ⁇ -dialkoxysiloxane, Of these, specific examples of nonpolar solvents include hydrocarbon solvents such as hexane, toluene, xylene, and benzene. Specific examples of the ether solvent include diethyl ether and tetrahydrofuran. Among these, it is preferable to use toluene as a solvent. Further, a mixed system of an ether solvent and a nonpolar solvent may be used. The amount of the organic solvent used is preferably in the range of 0.01 to 10M, preferably 0.1 to 1M, with respect to 1 mol of the structural unit represented by the general formula (2). .
  • the catalyst used when X of the compound represented by the general formula (7) is an alkoxyl group includes potassium hydroxide, sodium hydroxide, alkali metal hydroxides such as cesium hydroxide, tetramethylammonium hydroxide, and the like.
  • X of the compound represented by the general formula (7) is a hydrogen atom, that is, the following general formula (18) (However, R 2 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group, an alkoxyl group, or a group having an oxirane ring, and may be the same or different from each other.
  • b represents a number from 0 to 30)), 0.5 to 10 mol, preferably 0 to 1 mol of the silanol group-containing curable silsesquioxane compound represented by the general formula (2)
  • the cage structure containing curable silicone copolymer which has a structural unit represented by General formula (3) -1 can be obtained.
  • a silanol group-containing curable silsesquioxane compound represented by the general formula (2) and dihydrogensilane, or ⁇ , ⁇ -dihydrogensiloxane and a catalyst are mixed with a nonpolar solvent and an ether.
  • the concentration is 0.1 to 2 with respect to the silanol group-containing curable silsesquioxane compound represented by the general formula (2).
  • the reaction temperature is preferably 0-100 ° C, more preferably 20-80 ° C.
  • the reaction time is preferably 2 hours or more. At this time, if the reaction time is short, the reaction may not be completed.
  • the reaction solution is made neutral or acidic, and then water or a water-containing reaction solvent is separated.
  • those whose terminal groups are not silanol groups are converted into silanol groups by hydrolysis.
  • Separation of the water or the water-containing reaction solvent can employ means such as washing the solution with a saline solution to sufficiently remove moisture and other impurities, and then drying with a drying agent such as anhydrous magnesium sulfate.
  • a drying agent such as anhydrous magnesium sulfate.
  • an ether solvent means such as evaporation under reduced pressure can be employed.
  • a nonpolar solvent is added to dissolve the polycondensate, and washing and drying are performed in the same manner as described above.
  • dihydrogensilane in which b is 0 are diethylsilane, diphenylsilane and the like.
  • ⁇ , ⁇ -dihydrogensiloxane in which b is represented by 1 to 30 in the general formula (18) are 1,1,3,3-tetramethyldisiloxane, 1,1,3, 3-tetracyclopentyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5,7 , 7-octamethyltetrasiloxane and the like.
  • the organic solvent used when X of the compound represented by the general formula (7) is a hydrogen atom is arbitrary as long as it is inert to dihydrogensilane or ⁇ , ⁇ -dihydrogensiloxane.
  • hydrocarbon solvents such as hexane, toluene, xylene, and benzene can be mentioned as specific examples of nonpolar solvents.
  • Specific examples of the ether solvent include diethyl ether and tetrahydrofuran. Among these, it is preferable to use toluene as a solvent.
  • a mixed system of a polar solvent and an ether solvent may be used.
  • the amount of the organic solvent used is preferably in the range of 0.01 to 10M, preferably 0.1 to 1M, with respect to 1 mol of the structural unit represented by the general formula (2). .
  • X in the compound represented by the general formula (7) is a hydrogen atom, tetraethoxytitanium, tetrabutoxytitanium, hydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine
  • examples thereof include hydroxylamine compounds such as N-ethylhydroxylamine, N, N-diethylhydroxylamine and the like. Among these, it is preferable to use N, N-diethylhydroxylamine.
  • cocoon structure-containing curable silicone copolymer represented by the general formula (3) -1 is converted into the following general formula (8): (However, R 3 is a group having hydrogen, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and may be the same or different from each other).
  • R 1 is a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group, or an oxirane ring, and they may be the same or different from each other.
  • At least one of R 1 contained is any one of a vinyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, n represents a number of 6 to 14, and l represents a number of 1 to 2000.
  • Z represents the following general formula (4) (However, R 2 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, which may be the same or different from each other, and a is 0 Y 2 is a divalent group represented by the following general formula (5 ′): HO 1/2- (5 ') Or the following general formula (6) (Wherein R 3 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, and may be the same or different from each other). Is a monovalent group. ) -Containing curable silicone copolymer having a structural unit represented by:
  • the chlorosilane represented by the general formula (8) in the range of 2 to 100 moles per mole of the cocoon structure-containing curable silicone copolymer having the structural unit represented by the general formula (3) -1 Is reacted in a solvent that combines one or both of a nonpolar solvent and a polar solvent under basic conditions, and has a cocoon structure-containing curable silicone having a structural unit represented by general formula (3) -2 A copolymer can be obtained.
  • the preferred amount of chlorosilane to be used is 2 to 30 moles per mole of the cocoon structure-containing curable silicone copolymer having the structural unit represented by the general formula (3) -1.
  • chlorosilane is nonpolar.
  • a silanol group is dissolved in a solvent in which one or both of a solvent and a polar solvent are combined and one equivalent or more of triethylamine is added to chlorosilane, or a solvent in which chlorosilane is dissolved in pyridine as a base.
  • a solution prepared by dissolving the curable cocoon-type silsesquioxane compound in a solvent containing one or both of a nonpolar solvent and a polar solvent is added dropwise at room temperature under an inert gas atmosphere such as nitrogen, and then at room temperature. Stirring should be performed for 2 hours or more. At this time, if the reaction time is short, the reaction may not be completed. After completion of the reaction, toluene and water are added, and the soot structure-containing curable silicone copolymer having the structural unit represented by the general formula (3) -2 is dissolved in toluene, and excess chlorosilanes, by-product hydrochloric acid, And the hydrochloride is dissolved and removed in the aqueous layer.
  • the organic layer was dried using a desiccant such as magnesium sulfate, the used base and solvent were removed by concentration under reduced pressure, and a cocoon structure-containing curable silicone copolymer represented by the general formula (3) -2 was obtained. obtain.
  • the chlorosilane represented by the general formula (8) is used as a nonpolar solvent. Dissolve in one or both of polar solvents and mix with 1 or more equivalents of triethylamine to chlorosilane, or chlorosilane represented by general formula (7) as solvent and base into pyridine Use a dissolved mixture.
  • dichlorosilane is added dropwise to the silanol group-containing curable cage-type silsesquioxane compound and stirred for 2 hours or more, then the chlorosilane solution prepared above is added dropwise, and again stirred at room temperature for 2 hours or more. At this time, if the reaction time is short, the reaction may not be completed.
  • toluene and water are added, and the cocoon structure-containing curable silicone copolymer having the structural unit represented by the general formula (3) -2 is dissolved in toluene, and excess chlorosilanes, by-product hydrochloric acid, And the hydrochloride is dissolved and removed in the aqueous layer.
  • the organic layer is dried using a desiccant such as magnesium sulfate, and the base and solvent used are removed by concentration under reduced pressure to obtain a cocoon structure-containing curable silicone copolymer represented by the general formula (3) -2.
  • chlorosilane represented by the general formula (8) include trimethylchlorosilane, allyldimethylchlorosilane, dimethylpropylchlorosilane, dimethylisopropylchlorosilane, t-butyldimethylchlorosilane, triethylchlorosilane, dimethylphenylchlorosilane, benzyldimethylchlorosilane, Examples include propylchlorosilane, tributylchlorosilane, diphenylvinylchlorosilane, and triphenylchlorosilane.
  • the cage structure-containing curable silicone copolymer having the structural unit represented by the general formula (3) is blended with either or both of a hydrosilylation catalyst and a radical initiator,
  • a curable resin composition is obtained by blending either or both of a hydrosilylatable compound having a hydrogen atom on at least one silicon atom and a compound having an unsaturated group in the molecule. Also good.
  • cured material can be obtained by thermosetting or photocuring this curable resin composition and carrying out hydrosilylation or radical polymerization.
  • a curable resin composition is obtained by blending a photopolymerization initiator, a photoinitiator assistant, a sensitizer and the like.
  • the compound having a hydrogen atom on the silicon atom used together with the cocoon structure-containing curable silicone copolymer represented by the general formula (3) can be hydrosilylated in at least one molecule.
  • Oligomers and monomers having hydrogen atoms on silicon atoms include polyhydrogensiloxanes, polydimethylhydroxysiloxanes and copolymers thereof, and siloxanes whose ends are modified with dimethylhydrosiloxy. .
  • Examples of monomers having a hydrogen atom on a silicon atom include cyclic siloxanes such as tetramethylcyclotetrasiloxane and pentamethylcyclopenta, dihydrodisiloxanes, trihydromonosilanes, dihydromonosilanes, and monohydromonosilanes. And dimethylsiloxysiloxanes, and two or more of these may be mixed.
  • the compound having an unsaturated group used together with the cocoon structure-containing curable silicone copolymer represented by the general formula (3) is a heavy polymer having a repeating unit of about 2 to 20 structural units. It is roughly divided into a reactive oligomer that is a coalescence and a low-molecular-weight and low-viscosity reactive monomer. Moreover, it divides roughly into the monofunctional unsaturated compound which has one unsaturated group, and the polyfunctional unsaturated compound which has two or more.
  • reactive oligomers include polyvinylsiloxanes, polydimethylvinylsiloxysiloxanes and copolymers thereof, siloxanes modified with dimethylvinylsiloxy at the ends, epoxy acrylates, epoxidized oil acrylates, urethane acrylates, Examples thereof include saturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, polybutadiene, and polystyrylethyl methacrylate. These include monofunctional unsaturated compounds and polyfunctional unsaturated compounds.
  • reactive monofunctional monomers examples include vinyl-substituted silicon compounds such as triethylvinylsilane and triphenylvinylsilane, cyclic olefins such as cyclohexene, styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n- Examples include hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate, and the like.
  • vinyl-substituted silicon compounds such as triethylvinylsilane and triphenylvinylsilane
  • cyclic olefins such as cyclohexene, styrene,
  • reactive polyfunctional monomers examples include vinyl-substituted silicon compounds such as tetravinylsilane and divinyltetramethyldisiloxane, vinyl-substituted cyclic silicon compounds such as tetramethyltetravinylcyclotetrasiloxane and pentamethylpentavinylcyclopentasiloxane, and bis (trimethylsilyl).
  • Acetylene derivatives such as acetylene and diphenylacetylene, cyclic polyenes such as norbornadiene, dicyclopentadiene and cyclooctadiene, vinyl-substituted cyclic olefins such as vinylcyclohexene, divinylbenzenes, diethynylbenzenes, trimethylolpropane diallyl ether, penta Erythritol triallyl ether, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate hydroxypivalate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate,
  • the compound having a hydrogen atom on the silicon atom and the compound having an unsaturated group in the molecule used in the present invention may be used alone or in combination of two or more.
  • the curable resin composition of the present invention contains a hydrosilylation catalyst, a radical initiator, or a hydrogen atom on a silicon atom and a silyl structure-containing curable silicone copolymer represented by the general formula (3). And a compound having an unsaturated group.
  • the cured product (molded product) of the present invention is obtained by molding and curing this curable resin composition. That is, a cured product (molded article) can be obtained by hydrosilylation curing and radical polymerization of the curable resin composition.
  • the addition amount is in the range of 1 to 1000 ppm, more preferably 20 to 500 ppm as a metal atom with respect to the weight of the soot structure-containing curable silicone copolymer represented by the general formula (3). It is good. Further, when a photopolymerization initiator or a thermal polymerization initiator is blended as a radical initiator, the amount added is 0.1 to 100 parts by weight with respect to 100 parts by weight of the cocoon structure-containing curable silicone copolymer represented by the general formula (3). The range is preferably 10 parts by weight, and more preferably 0.1 to 5 parts by weight.
  • this addition amount is less than 0.1 parts by weight, curing will be insufficient, and the strength and rigidity of the resulting molded product will be reduced. On the other hand, when it exceeds 10 parts by weight, there is a possibility that problems such as coloring of the molded product may occur. Further, the hydrosilylation catalyst and the radical initiator may be used alone or in combination of two or more.
  • Hydrosilylation catalysts include platinum chloride, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone complexes, chloroplatinic acid and olefin complexes, platinum and vinylsiloxane complexes, and dicarbonyldichloroplatinum.
  • platinum group metal catalysts such as palladium catalysts and rhodium catalysts.
  • chloroplatinic acid, a complex of chloroplatinic acid and olefins, and a complex of platinum and vinylsiloxane are preferable. Moreover, these may be used independently and may be used together 2 or more types.
  • the photopolymerization initiator used when the curable resin composition is a photocurable resin composition
  • a compound such as an acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, or acylphosphine oxide-based compound is preferably used. Can do.
  • the photoinitiator adjuvant and sensitizer which show an effect in combination with a photoinitiator can also be used together.
  • thermal polymerization initiators used for the above purpose various types such as ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, etc.
  • the organic peroxide can be suitably used. Specifically, cyclohexanone peroxide, 1,1-bis (t-hexaperoxy) cyclohexanone, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, diisopropyl peroxide, t-butyl peroxide-2-ethyl Although hexanoate etc. can be illustrated, it is not restrict
  • These thermal polymerization initiators may be used alone or in combination of two or more.
  • additives can be added to the curable resin composition without departing from the object of the present invention.
  • Various additives include organic / inorganic fillers, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, UV absorbers, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, colorants, Crosslinking agents, dispersion aids, resin components and the like can be exemplified.
  • the molded body composed of a cocoon structure-containing curable silicone copolymer represented by the general formula (3) of the present invention is obtained by heating a curable resin composition containing either a hydrosilylation catalyst or a radical polymerization initiator, or both of them. Or it can manufacture by making it harden
  • the molding temperature can be selected from a wide range from room temperature to around 200 ° C., depending on the selection of the thermal polymerization initiator and the accelerator.
  • a cured product (molded product) having a desired shape can be obtained by polymerization and curing in a mold or on a steel belt. More specifically, all of general molding methods such as injection molding, extrusion molding, compression molding, transfer molding, calendar molding, and cast (casting) molding are applicable.
  • a molded product in the case of producing a cured product (molded product) by light irradiation, a molded product can be obtained by irradiating ultraviolet rays having a wavelength of 100 to 400 nm or visible light having a wavelength of 400 to 700 nm.
  • the wavelength of light to be used is not particularly limited, but near ultraviolet light having a wavelength of 200 to 400 nm is particularly preferably used.
  • the lamps used as ultraviolet light sources are low-pressure mercury lamps (output: 0.4 to 4 W / cm), high-pressure mercury lamps (40 to 160 W / cm), ultra-high pressure mercury lamps (173 to 435 W / cm), metal halide lamps (80 ⁇ 160 W / cm), pulse xenon lamp (80 to 120 W / cm), electrodeless discharge lamp (80 to 120 W / cm), and the like.
  • Each of these ultraviolet lamps is characterized by its spectral distribution, and is therefore selected according to the type of photoinitiator used.
  • a method of obtaining a cured product (molded body) by light irradiation for example, it is injected into a mold having an arbitrary cavity shape and made of a transparent material such as quartz glass, and irradiated with ultraviolet rays by the above-described ultraviolet lamp.
  • the present invention has been made in order to develop the opposite physical properties of low thermal expansion and high toughness, and has a reactive functional group on the side chain of a siloxane skeleton having a strong polyhedral structure (a cage structure) in the molecular structure. It is possible to provide a copolymer obtained by incorporating a curable resin having the above formula into a silicone main chain and to provide a production method thereof. That is, by using the cage-containing curable silicone copolymer represented by the general formula (3) of the present invention, in addition to the characteristics of silicone excellent in heat resistance and transparency, there is a conflict between low thermal expansion and high toughness. It becomes possible to create a molded body having both physical properties. For this reason, it is possible to obtain an optically transparent material having heat resistance and high dimensional stability that are impossible with plastic properties that are mainly composed of hydrocarbons and imparting toughness that is difficult to achieve with glass.
  • a cured product having excellent heat resistance, optical properties, and dimensional stability can be obtained.
  • the obtained cured product can be used for various applications such as window materials for various transport machines and houses, including optical applications such as touch panel substrates, flat panel display substrates, lenses, optical disks, and optical fibers. It can also be used as a light-weight transparent member, and its application range is wide as an alternative material for glass that has been used so far, and its industrial utility value is extremely high.
  • the above characteristics can be obtained by using a silanol group-containing cage-type silsesquioxane compound represented by the general formula (2) having a highly reactive silanol group as a starting material.
  • a silanol group-containing cage-type silsesquioxane compound represented by the general formula (2) having a highly reactive silanol group as a starting material.
  • FIG. 1 is a GPC chart of silanol group-containing cage-type silsesquioxane compound [R 1 SiO 3/2 ] n [HO 1/2 ] m obtained in Example 1.
  • 2 is an NMR chart of the silanol group-containing cage silsesquioxane compound [R 1 SiO 3/2 ] n [HO 1/2 ] m obtained in Example 1.
  • FIG. 3, obtained in Example 5 curable cage-type silicone copolymer Y 1 - [Z- (R 1 SiO 3/2) n] l -Z-Y 1 of the GPC chart
  • FIG. 4 shows an NMR chart of the cocoon structure-containing curable silicone copolymer Y 2- [Z— (R 1 SiO 3/2 ) n ] l —ZY 2 obtained in Example 5.
  • TMAH methanol tetramethylammonium hydroxide
  • the structure of the colorless viscous liquid obtained was determined to be a silanol group-containing curable silsesquioxane compound (R 1 is a vinyl group) represented by the general formula (2).
  • Example 5 A reaction vessel equipped with a stirrer and a dropping funnel was charged with 1.99 g of dimethyldichlorosilane and 15.38 ml of pyridine, and the atmosphere was replaced with nitrogen.
  • n of the compound having the soot structure represented by the general formula (2) estimated above is 8, the ratio of dimethylsiloxane corresponding thereto is 1.48.
  • Mw 451,620 obtained by GPC by a molecular structure of 757.5 where n is 8 cage structure and dimethylsiloxane 1.48 is 1 unit. It is suggested.
  • the structure of the colorless viscous solid obtained has the following general formula (3) -1 Y 1- [Z- (R 1 SiO 3/2 ) n ] l -ZY 1 (3) -1 ⁇ structure-containing curable silicone copolymer having a structural unit represented by the following formula: [R 1 is vinyl group, n is 8, l is 596, and Z is the following general formula (4) (R 2 is a methyl group, a is 0.48), and Y 1 is the following general formula (5 ′) HO 1/2- (5 ') It is. It was judged.
  • Example 6 A reaction vessel equipped with a stirrer and a dropping funnel was charged with 1.19 g of dimethyldichlorosilane, 2.14 ml of triethylamine, and 9.3 ml of tetrahydrofuran, and purged with nitrogen.
  • the structure of the colorless viscous liquid obtained was a cocoon structure-containing curable silicone copolymer having a structural unit represented by the general formula (3) -1 [R 1 is Vinyl group, n is 8, l is 5, Z is the above general formula (4) (R 2 is methyl group, a is 0.4), Y 1 is the following general formula (5 ′) HO 1/2- (5 ') It is. It was judged.
  • reaction solution was returned to room temperature and neutralized by adding 30 ml of 10% aqueous citric acid solution. After extraction of the organic layer, this was washed 3 times with distilled water and twice with saturated brine, and dehydrated over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 5.03 g of colorless viscous liquid (recovery rate: 91%).
  • Example 9 In a reaction vessel equipped with a stirrer and a cooling tube, 5.0 g of cocoon structure-containing curable silicone copolymer having a structural unit represented by the general formula (3) -1 obtained in Example 7 and 30 ml of pyridine was replaced with nitrogen. To the dropping funnel, 5.0 g of trimethylchlorosilane and 20 ml of pyridine were added dropwise over 30 minutes at room temperature and stirred for 2 hours. After stirring for 2 hours, 30 mL of toluene and 30 mL of distilled water were added, and the organic layer and the aqueous layer were separated.
  • the structure of the colorless viscous liquid obtained has the following general formula (3) -2 Y 2- [Z- (R 1 SiO 3/2 ) n ] l -ZY 2 (3) -2 ⁇ structure-containing curable silicone copolymer having a structural unit represented by the following formula: [R 1 is vinyl group, n is 8, l is 16, Z is the above general formula (4) (R 2 is methyl group, a is 0.64), and Y 2 is the following general formula (6) (R 3 is a methyl group). It was judged.
  • Example 10 A reaction vessel equipped with a stirrer and a dropping funnel was charged with 1.99 g of dimethyldichlorosilane and 15.38 ml of pyridine, and the atmosphere was replaced with nitrogen.
  • Curable silicone copolymer [R 1 is vinyl group, n is 8, l is 165, Z is the above general formula (4) (R 2 is methyl group, a is 0.76), Y 2 is The above general formula (6) (R 3 is a methyl group). It was judged.
  • Example 11 A reaction vessel equipped with a stirrer and a dropping funnel was charged with 0.94 g of 1,1,3,3-tetramethyl-1,3-dichlorosiloxane and 9.23 ml of pyridine and purged with nitrogen.
  • the structure of the colorless viscous liquid obtained was a cocoon structure-containing curable silicone copolymer having a structural unit represented by the general formula (3) -1 [R 1 is Vinyl group, n is 8, l is 104, Z is the above general formula (4) (R 2 is methyl group, a is 1.32), Y 1 is the following general formula (5 ′) HO 1/2- (5 ') It is. It was judged.
  • 3.0 g, 0.9 g of 1,3-dimethoxydimethyldisiloxane, 0.084 g of TMAH solution and 46.2 ml of toluene were weighed in and stirred at 90 ° C.
  • reaction solution was returned to room temperature and neutralized by adding 20 ml of 10% aqueous citric acid solution. After extraction of the organic layer, this was washed 3 times with distilled water and twice with saturated brine, and dehydrated over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 3.1 g of colorless viscous liquid (recovery rate: 84%).
  • the structure of the colorless viscous liquid obtained was a cocoon structure-containing curable silicone copolymer having a structural unit represented by the general formula (3) -1 [R 1 is Vinyl group, n is 8, l is 18, Z is the above general formula (4) (R 2 is methyl group, a is 1.4), Y 1 is the following general formula (5 ′) HO 1/2- (5 ') It is. It was judged.
  • the structure of the colorless viscous liquid obtained was a cocoon structure-containing curable silicone copolymer having a structural unit represented by the general formula (3) -1 [R 1 is Vinyl group, n is 8, l is 20, Z is the above general formula (4) (R 2 is methyl group, a is 1.12), Y 1 is the following general formula (5 ′) HO 1/2- (5 ') It is. It was judged.
  • Example 14 The same operation as in Example 9 was performed on 3.0 g of the cocoon structure-containing curable silicone copolymer having the structural unit represented by the general formula (3) -1 obtained in Example 12, and 3.0 g of trimethylchlorosilane was obtained. The reaction was performed to obtain 2.89 g of colorless viscous liquid (recovery rate 96%).
  • Curable silicone copolymer [R 1 is vinyl group, n is 8, l is 18, Z is the above general formula (4) (R 2 is methyl group, a is 1.4), Y 2 is The above general formula (6) (R 3 is a methyl group). It was judged.
  • Example 15 A similar experiment was conducted by changing 1.99 g of dimethyldichlorosilane used in Example 10 to 1.57 g of 1,1,3,3-tetramethyl-1,3-dichlorosiloxane. 12 g (recovery rate 85%) was obtained.
  • Curable silicone copolymer [R 1 is vinyl group, n is 8, l is 142, Z is the above general formula (4) (R 2 is methyl group, a is 1.36), Y 2 is The above general formula (6) (R 3 is a methyl group). It was judged.
  • Example 16 A reaction vessel equipped with a stirrer and a dropping funnel was charged with 0.89 g of dimethyldichlorosilane and 15.38 ml of pyridine and purged with nitrogen.
  • Example 17 Into a reaction vessel equipped with a stirrer and a cooling tube, 5.0 g of the cocoon structure-containing curable silicone copolymer represented by the general formula (3) -1 obtained in Example 5 and 30 ml of pyridine are weighed. Replaced with nitrogen. To the dropping funnel, 5.0 g of trimethylchlorosilane and 20 ml of pyridine were added dropwise over 30 minutes at room temperature and stirred for 2 hours. After stirring for 2 hours, 30 mL of toluene and 30 mL of distilled water were added, and the organic layer and the aqueous layer were separated.
  • Example 18 100 parts by weight of cocoon structure-containing curable silicone copolymer represented by the general formula (3) -1 obtained by the same synthesis method as in Example 5 above, 1,3,5,7-tetramethyl-1, A transparent curable resin composition comprising 30 parts by weight of 3,5,7-tetravinylcyclotetrasiloxane and 5 parts by weight of di-t-butyl peroxide (Perbutyl D manufactured by NOF Corporation) as a thermal polymerization initiator.
  • Perbutyl D di-t-butyl peroxide
  • Example 18 having a predetermined thickness, a thermosetting program was executed by heating, further increasing the temperature from 160 ° C. to 200 ° C. at 1 ° C./min, and then decreasing the temperature to 50 ° C. at 1.5 ° C./min. Such a cage structure-containing curable silicone resin molding was obtained.
  • Example 19 100 parts by weight of a cocoon structure-containing curable silicone copolymer represented by the general formula (3) -2 obtained by the same synthesis method as in Example 16 above, 1,3,5,7-tetramethyl-1, A transparent curable resin composition comprising 30 parts by weight of 3,5,7-tetravinylcyclotetrasiloxane and 5 parts by weight of di-t-butyl peroxide (Perbutyl D manufactured by NOF Corporation) as a thermal polymerization initiator.
  • Perbutyl D di-t-butyl peroxide
  • Example 19 having a predetermined thickness, a thermosetting program was executed by heating, further increasing the temperature from 160 ° C. to 200 ° C. at 1 ° C./min, and then decreasing the temperature to 50 ° C. at 1.5 ° C./min. Such a cage structure-containing curable silicone resin molding was obtained.
  • Example 20 100 parts by weight of a cocoon structure-containing curable silicone copolymer represented by the general formula (3) -3 obtained by the same synthesis method as in Example 17, 1,3,5,7-tetramethyl-1, A transparent curable resin composition comprising 30 parts by weight of 3,5,7-tetravinylcyclotetrasiloxane and 5 parts by weight of di-t-butyl peroxide (Perbutyl D manufactured by NOF Corporation) as a thermal polymerization initiator.
  • Perbutyl D di-t-butyl peroxide
  • Example 20 having a predetermined thickness, a thermosetting program was executed by heating, further increasing the temperature from 160 ° C. to 200 ° C. at 1 ° C./min, and then decreasing the temperature to 50 ° C. at 1.5 ° C./min.
  • a cage structure-containing curable silicone resin molding was obtained.
  • Example 21 100 parts by weight of a cocoon structure-containing curable silicone copolymer represented by the general formula (3) -3 obtained by the same synthesis method as in Example 17, 1,3,5,7-tetramethyl-1, 30 parts by weight of 3,5,7-tetravinylcyclotetrasiloxane, 2.5 parts by weight of di-t-butyl peroxide (Perbutyl D manufactured by NOF Corporation) as a thermal polymerization initiator, and 2-hydroxy- as a photoinitiator 2.5 parts by weight of 2-methyl-1-phenyl-propan-1-one (Darocur 1173 manufactured by Ciba Specialty Chemicals Co., Ltd.) was mixed to obtain a transparent curable resin composition.
  • a cocoon structure-containing curable silicone copolymer represented by the general formula (3) -3 obtained by the same synthesis method as in Example 17, 1,3,5,7-tetramethyl-1, 30 parts by weight of 3,5,7-tetravinylcyclotetrasiloxane, 2.5 parts by weight of
  • the curable resin composition obtained above was cast (flow cast) to a thickness of 0.5 mm, and using a 30 W / cm high-pressure mercury lamp, 2000 mJ / cm 2. Then, the temperature is increased from 100 ° C. to 160 ° C. at a rate of 0.5 ° C./min, and further increased from 160 ° C. to 200 ° C. at a rate of 1 ° C./min.
  • a thermosetting program for lowering the temperature to 0 ° C. was executed to obtain a ridge structure-containing curable silicone resin molding according to Example 21 having a predetermined thickness.
  • Example 22 100 parts by weight of a cocoon structure-containing curable silicone copolymer represented by the general formula (3) -3 obtained by the same synthesis method as in Example 17, 1,3,5,7-tetramethyl-1, A transparent curable resin composition was obtained by mixing 30 parts by weight of 3,5,7-tetravinylcyclotetrasiloxane and 0.5 parts by weight of a platinum-vinylsiloxane complex (SIP6830.3, manufactured by Azumax Co., Ltd.).
  • SIP6830.3, manufactured by Azumax Co., Ltd. platinum-vinylsiloxane complex
  • the curable resin composition obtained above was cast (flow cast) so as to have a thickness of 0.5 mm, and was 100 ° C. for 1 hour, 140 ° C. for 1 hour, and 180 ° Each of them was heated at 0 ° C. for 1 hour to obtain a ridge structure-containing curable silicone resin molding according to Example 22 having a predetermined thickness.
  • the curable resin composition obtained above was cast (flow cast) to a thickness of 0.5 mm, and the temperature was increased from 100 ° C. to 160 ° C. at 0.5 ° C./min.
  • a thermosetting program was executed by heating, further increasing the temperature from 160 ° C. to 200 ° C. at 1 ° C./min, and then decreasing the temperature to 50 ° C. at 1.5 ° C./min. Such a cage structure-containing curable silicone resin molding was obtained.
  • the curable resin composition obtained above was cast (cast) to a thickness of 0.5 mm using a roll coater, and 2000 mJ / cm 2 using a 30 W / cm high-pressure mercury lamp.
  • the sheet-like molded body according to Comparative Example 2 having a predetermined thickness was cured with the accumulated exposure amount.
  • the physical properties of the molded body were evaluated by the following methods.
  • (1) Heat resistance test (a) Linear expansion coefficient: Measured based on a thermomechanical analysis method at a heating rate of 5 ° C / min.
  • (2) Formability test After making a 10 cm square test piece having a thickness of 0.5 mm, it was determined that there was no crack after being produced, and that there was no x.
  • the cocoon-containing curable silicone copolymer of the present invention it is possible to obtain a cured product having both low thermal expansion properties and high toughness, in addition to the properties of silicone excellent in heat resistance and transparency.
  • a transparent material that has heat resistance and high dimensional stability that cannot be achieved with conventional plastics mainly composed of hydrocarbons and that has been provided with toughness that is difficult to achieve with glass. Therefore, the obtained cured product can be used for various applications such as optical materials such as touch panel substrates, flat panel display substrates, lenses, optical disks, and optical fibers, as well as various transport machines and window materials for houses, etc. Since it can also be used as a lightweight transparent member, it can be used as an alternative material for glass that has been used so far.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L’invention concerne un composé silsesquioxane de type cage, durcissable, contenant un groupe silanol ; un copolymère contenant le composé introduit dans la chaîne principale ; des procédés de production du composé et du copolymère ; et une composition de résine durcissable contenant le copolymère. Le composé durcissable est un composé représenté par la formule générale [R1SiO3/2]n[HO1/2]m, qui est obtenu par clivage d’une ou de plusieurs des liaisons siloxane d’un composé silsesquioxane de type cage, durcissable, représenté par la formule générale [R1SiO3/2]n en présence d’un composé basique dans un solvant organique comprenant un solvant non polaire et/ou un solvant polaire, liaison d’un contre-cation dérivé du composé basique à chaque partie clivée, puis traitement du composé résultant avec un acide pour convertir la partie clivée en un radical hydroxyle. Ce composé est condensé avec un composé représenté par la formule générale (7) pour obtenir un copolymère. La composition de résine durcissable contient ce copolymère.
PCT/JP2009/053751 2008-03-28 2009-02-27 Composé silsesquioxane de type cage, durcissable, contenant un groupe silanol, copolymère de silicone durcissable, contenant une structure en cage, leurs procédés de production, et composition de résine durcissable WO2009119253A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010505478A JPWO2009119253A1 (ja) 2008-03-28 2009-02-27 シラノール基含有硬化性籠型シルセスキオキサン化合物、籠型構造含有硬化性シリコーン共重合体、及びこれらの製造方法、並びに硬化性樹脂組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-086681 2008-03-28
JP2008086681 2008-03-28

Publications (1)

Publication Number Publication Date
WO2009119253A1 true WO2009119253A1 (fr) 2009-10-01

Family

ID=41113459

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/053751 WO2009119253A1 (fr) 2008-03-28 2009-02-27 Composé silsesquioxane de type cage, durcissable, contenant un groupe silanol, copolymère de silicone durcissable, contenant une structure en cage, leurs procédés de production, et composition de résine durcissable

Country Status (3)

Country Link
JP (1) JPWO2009119253A1 (fr)
TW (1) TW201000491A (fr)
WO (1) WO2009119253A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010204586A (ja) * 2009-03-05 2010-09-16 Nippon Steel Chem Co Ltd 位相差フィルム及びその製造方法
WO2010140635A1 (fr) * 2009-06-02 2010-12-09 チッソ株式会社 Composé organopolysiloxane, composition thermodurcissable contenant ledit composé organopolysiloxane et matériau d'étanchéité pour semi-conducteur optique
WO2011145638A1 (fr) * 2010-05-18 2011-11-24 Jnc株式会社 Nouveau composé organique du silicium et composition de résine thermodurcissable, résine durcie et matériau d'étanchéité pour semi-conducteur contenant ledit composé organique du silicium
CN102516542A (zh) * 2011-11-18 2012-06-27 西南科技大学 苯并环丁烯聚硅氧烷聚合单体或树脂及其制备方法
WO2012133080A1 (fr) * 2011-03-31 2012-10-04 新日鐵化学株式会社 Composition de résine silicone durcissable et résine silicone durcie
WO2012133079A1 (fr) * 2011-03-31 2012-10-04 新日鐵化学株式会社 Résine silsesquioxane de type panier, copolymère de silsesquioxane de type panier et leur procédé de production
JP2012214565A (ja) * 2011-03-31 2012-11-08 Nippon Steel Chem Co Ltd かご型シルセスキオキサン共重合体及びその製造方法
JP2012214564A (ja) * 2011-03-31 2012-11-08 Nippon Steel Chem Co Ltd かご型シルセスキオキサン樹脂及びその製造方法
CN110408034A (zh) * 2019-08-16 2019-11-05 湖北兴瑞硅材料有限公司 一种苯基嵌段硅树脂的合成方法
JP2019203039A (ja) * 2018-05-21 2019-11-28 株式会社ダイセル シルセスキオキサン組成物
JP2021050196A (ja) * 2020-07-22 2021-04-01 フマキラー株式会社 除菌剤
CN117487490A (zh) * 2023-11-08 2024-02-02 福建旭丰新材料科技有限公司 一种隔水耐候型电子环氧灌封胶及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI507497B (zh) * 2012-10-25 2015-11-11 Central Glass Co Ltd Followed by the following method, followed by the subsequent peeling method
JP6021605B2 (ja) * 2012-11-19 2016-11-09 新日鉄住金化学株式会社 かご型シルセスキオキサン化合物、それを用いた硬化性樹脂組成物及び樹脂硬化物

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002363414A (ja) * 2001-06-12 2002-12-18 Asahi Kasei Corp 籠状シルセスキオキサン含有組成物
JP2003510337A (ja) * 1999-08-04 2003-03-18 ハイブリッド・プラスチックス 多面体オリゴマーシルセスキオキサンの形成方法
JP2004123936A (ja) * 2002-10-03 2004-04-22 Nippon Steel Chem Co Ltd シリコーン樹脂組成物及びシリコーン樹脂成形体
JP2004143449A (ja) * 2002-09-30 2004-05-20 Nippon Steel Chem Co Ltd 官能基を有するかご型シルセスキオキサン樹脂とその製造方法
JP2005290352A (ja) * 2004-03-12 2005-10-20 Asahi Kasei Corp カゴ状シルセスキオキサン構造を有する化合物
WO2007119627A1 (fr) * 2006-04-10 2007-10-25 Ube Industries, Ltd. Formule durcissable, silsesquioxanes durcis, et leurs procédés de production
JP2008266301A (ja) * 2007-03-26 2008-11-06 Nippon Steel Chem Co Ltd 新規シリコーン化合物及びその原料並びに新規シリコーン化合物の製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003510337A (ja) * 1999-08-04 2003-03-18 ハイブリッド・プラスチックス 多面体オリゴマーシルセスキオキサンの形成方法
JP2002363414A (ja) * 2001-06-12 2002-12-18 Asahi Kasei Corp 籠状シルセスキオキサン含有組成物
JP2004143449A (ja) * 2002-09-30 2004-05-20 Nippon Steel Chem Co Ltd 官能基を有するかご型シルセスキオキサン樹脂とその製造方法
JP2004123936A (ja) * 2002-10-03 2004-04-22 Nippon Steel Chem Co Ltd シリコーン樹脂組成物及びシリコーン樹脂成形体
JP2005290352A (ja) * 2004-03-12 2005-10-20 Asahi Kasei Corp カゴ状シルセスキオキサン構造を有する化合物
WO2007119627A1 (fr) * 2006-04-10 2007-10-25 Ube Industries, Ltd. Formule durcissable, silsesquioxanes durcis, et leurs procédés de production
JP2008266301A (ja) * 2007-03-26 2008-11-06 Nippon Steel Chem Co Ltd 新規シリコーン化合物及びその原料並びに新規シリコーン化合物の製造方法

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010204586A (ja) * 2009-03-05 2010-09-16 Nippon Steel Chem Co Ltd 位相差フィルム及びその製造方法
WO2010140635A1 (fr) * 2009-06-02 2010-12-09 チッソ株式会社 Composé organopolysiloxane, composition thermodurcissable contenant ledit composé organopolysiloxane et matériau d'étanchéité pour semi-conducteur optique
JP2010280766A (ja) * 2009-06-02 2010-12-16 Chisso Corp 有機ケイ素化合物、該有機ケイ素化合物を含む熱硬化性組成物、および光半導体用封止材料
WO2011145638A1 (fr) * 2010-05-18 2011-11-24 Jnc株式会社 Nouveau composé organique du silicium et composition de résine thermodurcissable, résine durcie et matériau d'étanchéité pour semi-conducteur contenant ledit composé organique du silicium
CN103459447A (zh) * 2011-03-31 2013-12-18 新日铁住金化学株式会社 固化性硅树脂组合物及硅树脂固化物
KR101831600B1 (ko) 2011-03-31 2018-02-23 신닛테츠 수미킨 가가쿠 가부시키가이샤 바구니형 실세스퀴옥산 수지 및 바구니형 실세스퀴옥산 공중합체, 그리고 그들의 제조방법
WO2012133079A1 (fr) * 2011-03-31 2012-10-04 新日鐵化学株式会社 Résine silsesquioxane de type panier, copolymère de silsesquioxane de type panier et leur procédé de production
JP2012214565A (ja) * 2011-03-31 2012-11-08 Nippon Steel Chem Co Ltd かご型シルセスキオキサン共重合体及びその製造方法
JP2012214564A (ja) * 2011-03-31 2012-11-08 Nippon Steel Chem Co Ltd かご型シルセスキオキサン樹脂及びその製造方法
WO2012133080A1 (fr) * 2011-03-31 2012-10-04 新日鐵化学株式会社 Composition de résine silicone durcissable et résine silicone durcie
KR101861774B1 (ko) 2011-03-31 2018-05-28 신닛테츠 수미킨 가가쿠 가부시키가이샤 경화성 실리콘 수지 조성물 및 실리콘 수지 경화물
JPWO2012133080A1 (ja) * 2011-03-31 2014-07-28 新日鉄住金化学株式会社 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
JP5844796B2 (ja) * 2011-03-31 2016-01-20 新日鉄住金化学株式会社 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
CN102516542B (zh) * 2011-11-18 2013-10-16 西南科技大学 苯并环丁烯聚硅氧烷聚合单体或树脂及其制备方法
CN102516542A (zh) * 2011-11-18 2012-06-27 西南科技大学 苯并环丁烯聚硅氧烷聚合单体或树脂及其制备方法
JP2019203039A (ja) * 2018-05-21 2019-11-28 株式会社ダイセル シルセスキオキサン組成物
JP7094141B2 (ja) 2018-05-21 2022-07-01 株式会社ダイセル シルセスキオキサン組成物
CN110408034A (zh) * 2019-08-16 2019-11-05 湖北兴瑞硅材料有限公司 一种苯基嵌段硅树脂的合成方法
CN110408034B (zh) * 2019-08-16 2021-07-13 湖北兴瑞硅材料有限公司 一种苯基嵌段硅树脂的合成方法
JP2021050196A (ja) * 2020-07-22 2021-04-01 フマキラー株式会社 除菌剤
CN117487490A (zh) * 2023-11-08 2024-02-02 福建旭丰新材料科技有限公司 一种隔水耐候型电子环氧灌封胶及其制备方法
CN117487490B (zh) * 2023-11-08 2024-05-31 福建旭丰新材料科技有限公司 一种隔水耐候型电子环氧灌封胶及其制备方法

Also Published As

Publication number Publication date
TW201000491A (en) 2010-01-01
JPWO2009119253A1 (ja) 2011-07-21

Similar Documents

Publication Publication Date Title
WO2009119253A1 (fr) Composé silsesquioxane de type cage, durcissable, contenant un groupe silanol, copolymère de silicone durcissable, contenant une structure en cage, leurs procédés de production, et composition de résine durcissable
JP4381636B2 (ja) シリコーン樹脂組成物及びシリコーン樹脂成形体
JP5342795B2 (ja) 籠構造含有硬化性シリコーン共重合体及びその製造方法並びに籠構造含有硬化性シリコーン共重合体を用いた硬化性樹脂組成物及びその硬化物
TWI476232B (zh) The silicone resin and the production method thereof are the same as those of the hardened resin composition containing the silicone resin
JP4142385B2 (ja) シリコーン樹脂組成物及びシリコーン樹脂成形体
TWI577691B (zh) 籠型倍半矽氧烷化合物、使用該化合物之硬化性樹脂組成物及樹脂硬化物
JPWO2007119627A1 (ja) 硬化性組成物、シルセスキオキサン硬化物、及びこれらの製造方法
KR20160127719A (ko) 반응성 실세스퀴옥산 화합물을 포함하는 중합성 조성물
JP2009079163A (ja) 硬化性組成物、シルセスキオキサン硬化物、及びシルセスキオキサン硬化物の製造法
KR101504308B1 (ko) 케이지구조 함유 경화성 실리콘 공중합체 및 그 제조방법 그리고 케이지구조 함유 경화성 실리콘 공중합체를 사용한 경화성 수지 조성물 및 그 경화물
JP2009167325A (ja) シラノール基含有硬化性籠型シルセスキオキサン化合物およびこれを用いた共重合体並びにそれらの製造方法
JP5073738B2 (ja) レンズ
JP5073450B2 (ja) 耐熱性複合型レンズの製造方法
TWI529202B (zh) A hardened silicone resin composition and a silicone resin cured product
JP2012162666A (ja) 多面体構造ポリシロキサン系組成物
JP2010242043A (ja) シリコーン系重合体粒子を含有するシリコーン系硬化性組成物
TWI470004B (zh) 硬化性樹脂組成物及硬化物
JP5336399B2 (ja) 耐熱性複合型レンズ
JP2011099035A (ja) 透明性に優れた硬化物の製造方法および硬化物
JP2012082303A (ja) 硬化性組成物
JP5620086B2 (ja) 多面体構造ポリシロキサン変性体、及び該変性体を含有する組成物
JP5813357B2 (ja) 硬化性組成物
JP2009242558A (ja) シロキサンプレポリマー、シリコーン樹脂及びその製造方法
JP5877028B2 (ja) 多面体構造ポリシロキサン変性体、及び該変性体を含有する組成物
TW202406993A (zh) 倍半矽氧烷衍生物及其製造方法、硬化性組成物、硬塗劑、硬化物、硬塗層、以及基材

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09724241

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2010505478

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09724241

Country of ref document: EP

Kind code of ref document: A1