WO2012105103A1 - ヒンダードアミン骨格を有する化合物及び樹脂組成物 - Google Patents
ヒンダードアミン骨格を有する化合物及び樹脂組成物 Download PDFInfo
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- WO2012105103A1 WO2012105103A1 PCT/JP2011/076276 JP2011076276W WO2012105103A1 WO 2012105103 A1 WO2012105103 A1 WO 2012105103A1 JP 2011076276 W JP2011076276 W JP 2011076276W WO 2012105103 A1 WO2012105103 A1 WO 2012105103A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/14—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to a novel compound having a hindered amine skeleton and a resin composition containing the compound.
- the compound of the present invention is useful as a stabilizer capable of imparting heat resistance to the resin, and the resin composition of the present invention is excellent in heat resistance.
- SiC (Silicon Carbide) power semiconductors have lower energy loss during energization, less heat generation, and higher heat resistance than currently widely used silicon power semiconductors, so they can handle higher power.
- the heat-resistant limit temperature of silicon power semiconductor devices is about 150 ° C.
- use of SiC power semiconductor devices at 200 to 300 ° C. has been studied.
- Resins used for SiC power semiconductors and used for the resins Even higher heat resistance is required for the additive.
- a resin used as a sealing material / insulating material for a silicon power semiconductor device has a problem that it deteriorates when used at a temperature exceeding 200 ° C. for a long period of time, resulting in a decrease in sealing properties and electrical insulating properties.
- HALS hindered amine light stabilizer
- HALS having a polysiloxane structure obtained by polymerizing a siloxane monomer having a hindered amine skeleton is also known as a high molecular weight HALS (see, for example, Patent Document 2).
- Conventionally known HALS having a siloxane structure is generally highly polar and poorly compatible with the resin, so that it tends to bleed when used for a long period of time and is difficult to use depending on the application.
- an object of the present invention is to provide a compound that is excellent in heat resistance and compatibility with a resin and can sufficiently improve the heat resistance of the resin.
- a compound in which a hindered amine skeleton is introduced at the terminal of polysiloxane is excellent in heat resistance and compatibility with the resin, and can improve the heat resistance of the resin. .
- the present invention has been made on the basis of the above knowledge, and 0.001 to 10 parts by mass of the compound is blended with 100 parts by mass of the compound represented by the following general formula (1) and the resin.
- the present invention provides a resin composition characterized by comprising:
- R 1 to R 4 represent a linear or branched alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.
- alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, amyl group, isoamyl group, hexyl group, heptyl group, Examples include isoheptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, dodecyl group and the like.
- aryl group examples include phenyl group, naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-vinylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, Examples include 4-butylphenyl group, 4-isobutylphenyl group, 4-tertiarybutylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group and the like.
- R 1 to R 4 are preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, more preferably a methyl group, an ethyl group, or a phenyl group, because they are particularly excellent in compatibility with the resin.
- a methyl group or a phenyl group is more preferable.
- R ⁇ 1 >, R ⁇ 2 >, R ⁇ 3 > and R ⁇ 4 > of General formula (1) may mutually be same or different.
- a plurality of R 1 in the general formula (1) may be the same or different from each other in the same molecule, and the same applies to R 2 , R 3 and R 4 .
- a plurality of monomers may be used as raw materials and polymerized.
- R 1 and R 2 are preferably all the same substituents in the same molecule.
- R 3 in the general formula (1) is preferably two or more substituents in the same molecule (where y is 2 or more), and a mixture of one or more aryl groups and one or more alkyl groups. More preferably.
- R 4 is the same as R 3 . Since the heat resistance of the compound is higher, the content of the aryl group is preferably 5 to 35 mol% in the total of the aryl group and alkyl group represented by R 1 to R 4 in the same molecule. It is more preferably 5 to 30 mol%, and further preferably 10 to 30 mol%.
- Y in the general formula (1) represents a number of 1 to 2000, preferably 20 to 1000.
- X 1 in the general formula (1) represents a group represented by the general formula (2) or the general formula (3), and the thermal stability of the compound represented by the general formula (1) is better.
- the group represented by the general formula (2) is preferable.
- R 5 represents a hydrogen atom, O., a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched alkoxy group having 1 to 12 carbon atoms
- L 1 represents a linear or branched carbon group. It represents an alkylene group having 1 to 6 hydrogen atoms or an arylene group having 6 to 12 carbon atoms.
- O. represents an oxy radical.
- Examples of the alkyl group include those exemplified as the alkyl group represented by R 1 to R 4 in the general formula (1).
- Examples of the alkoxy group include a methoxy group, a methoxymethoxy group, a methoxyethoxymethoxy group, a methylthiomethoxy group, an ethoxy group, a vinyloxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tertiary butoxy group, and a tertiary group.
- R 5 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
- An alkyl group having 1 or 2 or an alkoxy group having 1 to 12 carbon atoms is more preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is most preferable because synthesis is easy.
- L 1 in the general formula (2) represents a linear or branched alkylene group having 1 to 6 hydrocarbon atoms or an arylene group having 6 to 12 carbon atoms.
- the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.
- the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a substituted phenylene group (the substituent is an alkyl group having 1 to 6 carbon atoms or a phenyl group), Examples include 1,4-naphthylene group and biphenylene group.
- L 1 is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group or a propylene group, and even more preferably a propylene group.
- X 2 in the general formula (3) represents a group represented by the general formula (2) or a hydrogen atom, and at least one of s X 2 is a group represented by the general formula (2).
- the ratio of the group represented by the general formula (2) to the total amount of the hydrogen atom and the group represented by the general formula (2) is It is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 75 mol% or more.
- the heat resistance of the resin may be insufficient when used as a stabilizer.
- R 6 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms, such as those exemplified as the alkyl group represented by R 1 to R 4 in the general formula (1) Examples thereof include those having 1 to 4 carbon atoms and those exemplified as the aryl group having 6 to 12 carbon atoms represented by R 1 to R 4. Group, propyl group and phenyl group are preferred, and methyl group is more preferred.
- L 2 represents a straight or branched hydrocarbon having 1-6 alkylene group or an arylene group having 6 to 12 carbon atoms, for example, those illustrated are exemplified as L 1 in formula (1), L 2 Is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group or a propylene group, and still more preferably an ethylene group.
- S represents a number of 2 to 6, and the number of 2 to 5 is preferable, the number of 2 to 4 is more preferable, and 3 is still more preferable because industrial acquisition of the corresponding synthetic raw material is easy.
- R 1 and R 2 are the same as those in the general formula (1).
- Examples of the linear or branched alkyl group having 1 to 12 carbon atoms represented by R 7 and R 8 include those exemplified as the alkyl group represented by R 1 to R 4 in the general formula (1).
- An alkyl group having 1 to 6 carbon atoms is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is still more preferable.
- Examples of the aryl group having 6 to 12 carbon atoms represented by R 9 and R 10 include those exemplified as the aryl group represented by R 1 to R 4 in the general formula (1).
- An aryl group having a number of 6 to 10 is preferred, and a phenyl group is more preferred.
- m + n corresponds to y in the general formula (1), and m and n each independently represent a number such that m + n is 1 to 2000.
- m is preferably a number from 15 to 800, and n is preferably a number from 10 to 500.
- the ratio of m and n is not particularly limited, it is preferably 95/5 to 65/35, more preferably 95/5 to 70/30, and more preferably 90/10 to 70/30 because of its particularly high heat resistance. Further preferred. If it is out of 95/5 to 65/35, the heat resistance may be lowered or the compatibility with the resin may be insufficient.
- the compound represented by the general formula (4) may be a random copolymer or a block copolymer, but the random copolymer is easier to produce.
- the compound represented by the general formula (1) of the present invention is not particularly limited as to its production method, and can be produced by applying a known reaction.
- the body Q may be synthesized and the two may be reacted.
- an intermediate R represented by the following general formula (7) is synthesized, the intermediate R is reacted with a commercially available intermediate S represented by the following general formula (8), and then the reaction product. May be reacted with intermediate P.
- the intermediate P can be obtained by etherifying a compound having an allyl halide and a 4-hydroxy-2,2,6,6-tetramethyl skeleton in a solvent in the presence of a base according to the following reaction formula 1.
- Solvents and bases are not particularly limited, and those used in general Williamson ether synthesis may be used. Further, when water is used as a solvent, a quaternary ammonium salt may be used as a phase transfer catalyst.
- L 1 in the general formula (2) is other than propyl group, the allyl halide may be replaced with the corresponding alkenyl halide.
- (q-1) a method in which a dihalosilane compound or a dialkoxysilane compound is decomposed and polycondensed by a sol-gelation reaction, and then SiH groups are introduced into both ends or (q- 2)
- a method for producing the intermediate Q for example, (q-1) a method in which a dihalosilane compound or a dialkoxysilane compound is decomposed and polycondensed by a sol-gelation reaction, and then SiH groups are introduced into both ends or (q- 2)
- a method in which a cyclic siloxane compound as a starting material is subjected to ring-opening polymerization and a SiH group is introduced at the terminal.
- the intermediate Q may be polymerized by random or block polymerization, but is preferably produced by random polymerization because of easy production.
- reaction between the intermediate P having an allyl group and the intermediate Q having two SiH groups may be performed by a conventionally known method as a hydrosilylation reaction.
- the hydrosilylation reaction between the SiH group and the allyl group is preferably performed using a catalyst.
- the hydrosilylation catalyst include a platinum-based catalyst, a palladium-based catalyst, and a rhodium-based catalyst.
- platinum catalysts include chloroplatinic acid, complexes of chloroplatinic acid and alcohols, aldehydes, ketones, etc., platinum-olefin complexes, platinum carbon complexes, platinum-carbonylvinylmethyl complexes (Ossko catalysts), platinum-divinyltetra Methyldisiloxane complex (KaRstedt catalyst), platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, platinum-phosphine complex (for example, Pt [P (C 6 H 5 ) 3 ] 4 , PtCl [P (C 6 H 5 ) 3 ] 3 , Pt [P (C 4 H 9 ) 3 ) 4 ], platinum-phosphite complex (eg Pt [P (OC 6 H 5 ) 3 ] 4 ), Pt [P (OC 4 H 9 3 ) 4 ), dicarbonyldichloroplatinum and the like.
- reaction conditions for hydrosilylation are not particularly limited, and may be carried out under the conditions known in the art using the above catalyst, but from the viewpoint of the reaction rate, it is preferably carried out at 25 ° C. to 130 ° C.
- toluene, hexane, Conventionally known solvents such as methyl isobutyl ketone, cyclopentanone, and propylene glycol monomethyl ether acetate may be used.
- reaction of Intermediate R and Intermediate S The reaction between the vinyl group of the intermediate R and the SiH group of the intermediate S may be performed by a conventionally known method as a hydrosilylation reaction.
- a catalyst and a solvent as exemplified in the reaction of the intermediate P and the intermediate Q are used. What is necessary is just to use, and the preferable catalyst, the usage-amount of a catalyst, and reaction temperature are the same.
- the mass average molecular weight means a mass average molecular weight in terms of polystyrene when GPC (Gel Permeation Chromatography, also called gel permeation chromatography) analysis is performed using tetrahydrofuran as a solvent.
- GPC Gel Permeation Chromatography, also called gel permeation chromatography
- the compound of the present invention is useful as a stability-imparting agent for resins.
- the compound of the present invention is particularly suitable as a heat resistance imparting agent for resins, and in addition to resins used for applications exposed outdoors, applications requiring weather resistance, applications requiring maintenance of physical properties, etc. , And can be used as a stabilizer for imparting necessary weather resistance, physical property stability, and the like.
- the resin composition of the present invention is obtained by blending 0.001 to 10 parts by mass of the compound of the present invention with respect to 100 parts by mass of the resin.
- the compounding amount of the compound of the present invention is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and most preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the resin. If it is less than 0.001 part by mass, the effect may be insufficient, and if it exceeds 10 parts by mass, the compatibility with the resin may deteriorate.
- the resin used in the resin composition of the present invention is not particularly limited as long as it is conventionally used as a resin.
- high-density polyethylene isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, Polybutene-1, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene / propylene block or random copolymer, ethylene-vinyl acetate copolymer, olefin -Polyolefin resins such as maleimide copolymers and copolymers of monomers giving these polymers; polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer , Vinyl chloride-ethylene copolymer, salt Halogen-containing resins such as vinyl-vinylidene
- polysiloxane, siloxane copolymer, phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin and the like can be mentioned.
- NR natural rubber
- IR polyisoprene rubber
- SBR styrene butadiene rubber
- BR polybutadiene rubber
- EPDM ethylene-propylene-diene rubber
- IIR ethylene-propylene-diene rubber
- chloroprene rubber acrylonitrile butadiene rubber
- NBR butyl rubber
- the polysiloxane is a polymer polymerized from a siloxane monomer and having a
- thermosetting resin such as a urethane resin, a phenol resin, a urea resin, a melamine resin, an epoxy resin, a polyaminobismaleimide resin, a polysiloxane, a siloxane copolymer, and an unsaturated polyester resin.
- a thermosetting resin such as a urethane resin, a phenol resin, a urea resin, a melamine resin, an epoxy resin, a polyaminobismaleimide resin, a polysiloxane, a siloxane copolymer, and an unsaturated polyester resin.
- an epoxy resin, a polyamino bismaleimide resin, a polysiloxane, and a siloxane copolymer are more preferable and compatible.
- Polysiloxanes and polysiloxane copolymers are more preferred, and polysiloxanes are most preferred because the improvement effect and the effect of improving thermal stability are particularly high.
- Examples of the alkylene group having 2 to 4 carbon atoms represented by L 3 in the general formula (X) include an ethylene group, a propylene group, a butylene group, and the like, and an ethylene group is preferable because of high heat resistance. Since K is easy to synthesize, 3 is preferable.
- Examples of the alkenyl group having 2 to 4 carbon atoms represented by Z include CH 2 ⁇ CH—, CH 2 ⁇ CH—CH 2 —, CH 2 ⁇ CH—CH 2 —CH 2 —, CH 2 ⁇ C (CH 3 )-, CH 2 ⁇ C (CH 3 ) —CH 2 —, CH 2 ⁇ CH—CH (CH 3 ) — and the like.
- Examples of the alkynyl group having 2 to 4 carbon atoms represented by Z include the following groups. Z is preferably a hydrogen atom.
- a preferred form of the polysiloxane represented by the general formula (X) is a polysiloxane represented by the following general formula (Xa).
- the method for synthesizing the polysiloxane represented by the general formula (X) is not particularly limited, and the polysiloxane can be obtained, for example, according to the reaction of the intermediate R and the intermediate S described above. What is obtained by this synthesis method is a polysiloxane represented by the following general formula (Xa) or a mixture of a plurality of polysiloxanes represented by the above general formula (X).
- the main component is polysiloxane represented by Xa).
- a polyfunctional cyclopolysiloxane represented by (R a SiHO) K was used as a compound for introducing a cyclopolysiloxane ring. Even in cases, production is negligible. This is because the formation of a compound in which an acyclic polysiloxane is bonded to two or more Si—H of cyclopolysiloxane via L 3 is greatly disadvantageous in terms of energy.
- R a to R g in the general formula (X) or the general formula (Xa) when the ratio of the linear or branched alkyl group having 1 to 12 carbon atoms is increased, the flexibility of the obtained cured product is increased. When the property is improved and the ratio of the aryl group having 6 to 12 carbon atoms is increased, the heat resistance and hardness of the obtained cured product are improved.
- the ratio of the alkyl group to the aryl group can be arbitrarily set depending on the physical properties required for the cured product.
- a preferable ratio (number) of the alkyl group: the aryl group is 100: 1 to 1: 2, and 20: 1 to 1: 1 is more preferable.
- the alkyl group having 1 to 12 carbon atoms is preferably a methyl group because of good heat resistance, and the aryl group having 6 to 12 carbon atoms is preferably a phenyl group because of good heat resistance.
- K in the general formula (X) and k in the general formula (Xa) are 2 to 7. When it is larger than 7, the flexibility required for the cured product obtained by having too many functional groups cannot be obtained. K and k are preferably 2 to 5, since they are easily available industrially and the number of functional groups is appropriate, and 3 is most preferred.
- the mass average molecular weight of the polysiloxane represented by the general formula (X) or (Xa) is 3000 to 1,000,000. If it is less than 3000, the resulting cured product has insufficient heat resistance, and if it is greater than 1 million, the viscosity increases and hinders handling.
- the mass average molecular weight is preferably from 5,000 to 500,000, and more preferably from 10,000 to 100,000.
- thermal stability improves further by using together the compound of this invention represented by General formula (1), and inorganic powder.
- the inorganic powder that can be used in the present invention is not particularly limited, and examples thereof include metals, inorganic salts, metal oxides, natural minerals, fillers, and more specifically, copper, silver, nickel, and the like.
- the particle diameter of the inorganic powder is preferably 1 nm to 100 ⁇ m from the viewpoints of dispersibility, mixing properties, viscosity, and the like.
- the resin composition of the present invention includes an antioxidant (phenolic, phosphorous, thioether, etc.) ordinarily used according to the type of resin used, an ultraviolet absorber (benzotriazole ultraviolet absorber, triazine ultraviolet absorber). And other additives such as hindered amine stabilizers, plasticizers and processing aids other than the compounds of the present invention.
- an antioxidant phenolic, phosphorous, thioether, etc.
- an ultraviolet absorber benzotriazole ultraviolet absorber, triazine ultraviolet absorber
- additives such as hindered amine stabilizers, plasticizers and processing aids other than the compounds of the present invention.
- the blending amount can be appropriately selected according to the purpose of use of each additive, but the viewpoint of not impairing the effects of the present invention. Therefore, the total amount of all additives is preferably 10 parts by mass or less with respect to 100 parts by mass of the resin.
- phenolic antioxidant examples include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4). -Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl) -M-cresol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 2,2′-ethylidenebis (4-secondarybutyl-6-tert-butylphenol)
- Examples of the phosphorus-based antioxidant include [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite.
- Octyl diphenyl phosphite di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol Diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, bis (2, 4-Dicumylphenyl) pentaerythritol diphosphite, tetra ( Ridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4′-n-butyliden
- benzotriazole ultraviolet absorber examples include 2- (2′-hydroxy- 5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl) -5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) ) Benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole, 2,2′-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol, etc. 2- (2′-hydroxyphenyl) benzotriazoles.
- benzophenone ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). And 2-hydroxybenzophenones.
- the blending amount of the ultraviolet absorber is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the resin.
- hindered amine stabilizer examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate.
- the blending amount of the hindered amine stabilizer is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the resin.
- the amount of the hindered amine stabilizer is preferably 10% by mass or less based on the amount of the compound of the present invention.
- polyester plasticizer examples include a chain polyester composed of an aliphatic dibasic acid and / or an aromatic dibasic acid and a diol compound, and a chain polyester of hydroxycarboxylic acid.
- aliphatic dibasic acid examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, 1,3 -Cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid, 2,5-norbornene dicarboxylic acid and the like.
- polyester plasticizers include trivalent or higher polyols and monocarboxylic acid polyesters.
- the trivalent or higher polyols include glycerin, trimethylolpropane, pentaerythritol, sorbitol, and their condensates such as dipentaerythritol and tripentaerythritol.
- polyether polyols obtained by adding alkylene oxides such as ethylene oxide to these polyols may be used.
- the resin composition of the present invention can be used for various molded products, adhesives, sealants, coating agents and the like depending on the type of resin. Since the resin composition of the present invention is excellent in heat resistance, weather resistance, and light stability, the resin composition is used in various molding methods (solution casting method, injection molding method, melt extrusion method, etc.), and is exposed outdoors. It is preferable to use it for applications where long-term heat resistance is required.
- the resin composition of the present invention is particularly excellent in heat resistance, and when used in an environment exposed to conditions exceeding 200 ° C. for a long time, the effect of the present invention is maximized and is particularly useful.
- the intermediate P is synthesized, in the following production examples 2 and 3, the intermediate Q is synthesized, and in the following production example 4, the intermediate R is synthesized, and then the intermediate R and the intermediate are synthesized.
- a reaction product was obtained by reacting with S.
- the reaction product (intermediate 2-3) obtained in Production Example 4 corresponds to the polysiloxane represented by the general formula (Xa).
- the intermediate body used as resin (polysiloxane) was synthesize
- the compounds of the present invention were synthesized using the intermediates obtained in Production Examples 1 to 4.
- resin compositions were prepared using the compounds of the present invention obtained in Examples 1-1 to 1-3, and in Comparative Examples 1-1 to 1-8 below. A resin composition was prepared using the comparative compound.
- pyridine (18 g, 0.23 mol) and dimethylvinylchlorosilane (18.5 g, 0.15 mol) were added and stirred at 70 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to 40 ° C., and 670 g of toluene was added. Water (850 g) was added for oil-water separation, and after stirring at 40 ° C. for 30 minutes, the aqueous layer was removed. Similarly, oil (water) separation was performed 3 times using water (850 g). The solvent and low molecular components were distilled off from the remaining organic layer under reduced pressure.
- Example 1-1 Compound No. 1 Synthesis of 1 Intermediate 500-1 (100 g, SiH group 23.8 mmol), Intermediate 1 (10.5 g, 71.4 mmol), 0.25 were added to a 500 mL four-necked flask equipped with a stirrer, a thermometer, and an argon inlet tube. % Ossko catalyst toluene solution (2.0 g), hydroquinone (1.02 g, 9.26 mmol) and toluene (50.0 g) were added, and the mixture was stirred at 100 to 110 ° C. for 2 hours under an argon stream.
- Test Compound ⁇ Component A Compound of the Present Invention and Comparative Compound>
- A-3 Compound No.
- B-1 Fumed titanium dioxide (manufactured by Nippon Aerosil Co., Ltd., product name: AEROXIDE TiO 2 T805)
- B-2 Fumed titanium dioxide (manufactured by Nippon Aerosil Co., Ltd., product name: AEROXIDE TiO 2 P25)
- B-3 Anatase type titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd., product name: MS-50)
- B-4 Rutile type titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd., product name: TTO-SS (A))
- B-5 Bulkite type titanium dioxide (manufactured by High Purity Chemical Laboratory Co., Ltd.)
- B-6 Zinc oxide (Ishihara Sangyo Co., Ltd., product name: FZO-50)
- B-7 Fumed aluminum oxide (manufactured by Nippon Aerosil Co., Ltd., product name: AEROXIDE
- ⁇ X component resin>
- the cured product of the resin composition was stored in an oven at 250 ° C. under air. After 100 hours and 200 hours from the start of the storage test, the mass of the cured product of each resin composition is measured and compared with the mass before the start of the test, and the residual ratio ⁇ calculation formula: 100-[(mass before test ⁇ 100 Time or mass after elapse of 200 hours) ⁇ mass before test ⁇ 100]>.
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Abstract
Description
シリコンパワー半導体装置の封止材料・絶縁材料として使用される樹脂は、200℃を超える温度で長期間使用すると劣化が生じ、封止性や電気絶縁性が低下するという問題があった。
てなることを特徴とする樹脂組成物を提供するものである。
R1~R4は炭素原子数1~12の直鎖若しくは分岐のアルキル基又は炭素原子数6~12のアリール基を表す。
上記アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、セカンダリーブチル基、ターシャリーブチル基、ペンチル基、アミル基、イソアミル基、ヘキシル基、ヘプチル基、イソヘプチル基、オクチル基、イソオクチル基、2-エチルヘキシル基、ノニル基、イソノニル基、デシル基、ドデシル基等が挙げられる。
上記アリール基としては、例えば、フェニル基、ナフチル基、2-メチルフェニル基、3-メチルフェニル基、4-メチルフェニル基、4-ビニルフェニル基、3-イソプロピルフェニル基、4-イソプロピルフェニル基、4-ブチルフェニル基、4-イソブチルフェニル基、4-ターシャリーブチルフェニル基、4-ヘキシルフェニル基、4-シクロヘキシルフェニル基等が挙げられる。
一般式(1)中のR3は、同一分子中で2種以上の置換基であること(但しyは2以上)が好ましく、1種以上のアリール基と1種以上のアルキル基との混合であることがさらに好ましい。R4についてもR3と同様である。
化合物の耐熱性がより高いため、同一の分子中では、R1~R4で表されるアリール基とアルキル基の合計のうち、アリール基の含有量が5~35モル%であることが好ましく、5~30モル%であることがより好ましく、10~30モル%であることが更に好ましい。
一般式(1)中のX1は、上記一般式(2)又は一般式(3)で表される基を表し、一般式(1)で表される化合物の熱安定性がより良好なため、一般式(2)で表される基が好ましい。
R5は水素原子、O・、炭素原子数1~12の直鎖若しくは分岐のアルキル基又は炭素原子数1~12の直鎖若しくは分岐のアルコキシ基を表し、L1は直鎖又は分岐の炭化水素数1~6のアルキレン基又は炭素原子数6~12のアリーレン基を表す。なお、O・はオキシラジカルを表す。
数6~12のアリーレン基を表す。
上記アルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基等が挙げられる。
上記アリーレン基としては、例えば、1,2-フェニレン基、1,3-フェニレン基、1,4-フェニレン基、置換フェニレン基(置換基は、炭素数1~6のアルキル基又はフェニル基)、1,4-ナフチレン基、ビフェニレン基等が挙げられる。
本発明の化合物の熱安定性がより良好なことから、L1は炭素原子数2~4のアルキレン基が好ましく、エチレン基、プロピレン基がより好ましく、プロピレン基が更に好ましい。
一般式(3)のX2は、一般式(2)で表される基又は水素原子を表し、s個のX2のうち少なくとも一つは一般式(2)で表される基である。本発明の化合物を添加した樹脂の耐熱性がより向上するため、水素原子と一般式(2)で表される基の合計量に対して、一般式(2)で表される基の割合が50モル%以上であることが好ましく、70モル%以上がより好ましく、75モル%以上が更に好ましい。一般式(2)で表される基が50モル%未満の場合は、安定剤として使用した場合に樹脂の耐熱性が不十分になる場合がある。
また、一般式(4)で表される化合物は、ランダム共重合体でもブロック共重合体でもよいが、ランダム共重合体の方が製造が容易である。
同様にX1=一般式(3)で表される基、L1=プロピレン基、L2=エチレン基である化合物は、公知の反応を応用して製造することができる。例えば、下記の一般式(7)で表される中間体Rを合成し、該中間体Rと下記一般式(8)で表される市販の中間体Sを反応させた後、その反応生成物を中間体Pと反応させればよい。
中間体Pは、下記反応式1に従い、アリルハロゲン化物と4-ヒドロキシ-2,2,6,6-テトラメチル骨格を有する化合物を塩基存在下、溶媒中でエーテル化することで得ることが出来る。溶媒及び塩基は特に限定されず、一般的なWilliamsonのエーテル合成で使用されているものを用いればよい。また、溶媒に水を使う時は相間移動触媒として4級アンモニウム塩を使用してもよい。尚、一般式(2)のL1がプロピル基以外の場合は、上記アリルハロゲン化物を、対応するアルケニルハロゲン化物に置き換えればよい。
中間体Qの製造方法としては、例えば、(q-1)ジハロシラン化合物又はジアルコキシシラン化合物をゾルゲル化反応により分解-縮重合して、次に両末端にSiH基を導入する方法又は(q-2)出発物質としての環状シロキサン化合物を開環重合させ、末端にSiH基を導入する方法がある。中間体Qの重合方法はランダム又はブロック重合でもよいが、製造が容易なためランダム重合による製造が好ましい。
アリル基を有する中間体PとSiH基を2つ有する中間体Qとの反応は、ヒドロシリル化反応として従来公知の方法によればよい。SiH基とアリル基とのヒドロシリル化反応では、触媒を用いて行うことが好ましく、ヒドロシリル化触媒としては、例えば、白金系触媒、パラジウム系触媒、ロジウム系触媒等が挙げられる。白金系触媒としては、例えば、塩化白金酸、塩化白金酸とアルコール、アルデヒド、ケトン等との錯体、白金-オレフィン錯体、白金炭素錯体、白金-カルボニルビニルメチル錯体(Ossko触媒)、白金-ジビニルテトラメチルジシロキサン錯体(KaRstedt触媒)、白金-シクロビニルメチルシロキサン錯体、白金-オクチルアルデヒド錯体、白金-ホスフィン錯体(例えば、Pt[P(C6H5)3]4、PtCl[P(C6H5)3]3、Pt[P(C4H9)3)4]、白金-ホスファイト錯体(例えば、Pt[P(OC6H5)3]4)、Pt[P(OC4H9)3]4)、ジカルボニルジクロロ白金等が挙げられる。パラジウム系触媒又はロジウム系触媒としては、例えば、上記白金系触媒の白金原子の代わりにパラジウム原子又はロジウム原子を含有する化合物が挙げられる。これらは1種で用いてもよく、2種以上を併用してもよい。ヒドロシリル化触媒としては、反応性の点から、白金系触媒が好ましく、白金-ジビニルテトラメチルジシロキサン錯体及び白金-カルボニルビニルメチル錯体が更に好ましく、白金-カルボニルビニルメチル錯体が最も好ましい。また、触媒の使用量は反応性の点から、各原料の合計量の5質量%以下が好ましく、0.0001~1.0質量%が更に好ましく、0.001~0.1質量%が最も好ましい。ヒドロシリル化の反応条件は特に限定されず、上記触媒を使用して従来公知の条件で行なえばよいが、反応速度の点から、25℃~130℃で行なうのが好ましく、反応時にトルエン、ヘキサン、メチルイソブチルケトン、シクロペンタノン、プロピレングリコールモノメチルエーテルアセテート等の従来公知の溶媒を使用してもよい。
中間体Rの製造方法としては、例えば、一般式(3)のL2がエチレン基である場合、(r-1)ジハロシラン化合物又はジアルコキシシラン化合物をゾルゲル化反応により分解-縮重合して、次に両末端にビニル基を導入する方法、(r-2)出発物質としての環状シロキサン化合物を開環重合させ、末端にビニル基を導入する方法、(r-3)両端にビニル基を有するシロキサン化合物に環状シロキサン化合物を挿入-平衡化重合する方法が挙げられる。中間体Rの重合方法はランダム又はブロック重合でもよいが、製造が容易なためランダム重合による製造が好ましい。
中間体Rのビニル基と中間体SのSiH基との反応は、ヒドロシリル化反応として従来公知の方法によればよく、中間体P及び中間体Qの反応時で例示したような触媒、溶媒を使用すればよく、好ましい触媒、触媒の使用量、反応温度は同じである。
生成した合成物は、例えばL1=プロピレン基の場合は中間体Pと反応させることで、所望の化合物とすることができる。
尚、上記ポリシロキサンは、シロキサンモノマーから重合され、構造中にシロキサン結合の繰り返し単位を持つポリマーである。また、上記シロキサン共重合体は、ポリアミド、ポリイミド及びエポキシ等から選択される樹脂と、上記ポリシロキサンとの共重合体である。
Zで表される炭素原子数2~4のアルケニル基としては、CH2=CH-、CH2=CH-CH2-、CH2=CH-CH2-CH2-、CH2=C(CH3)-、CH2=C(CH3)-CH2-、CH2=CH-CH(CH3)-等が挙げられる。Zで表される炭素原子数2~4のアルキニル基としては、例えば下記の基が挙げられる。Zは水素原子が好ましい。
上記一般式(X)で表されるポリシロキサンの合成方法は特に限定されず、該ポリシロキサンは例えば前述の中間体R及び中間体Sの反応に準じて得ることが出来るが、このような通常の合成手法により得られるものは、下記一般式(X-a)で表されるポリシロキサンか、上記一般式(X)で表されるポリシロキサンの複数種の混合物であって、下記一般式(X-a)で表れるポリシロキサンを主な成分とするものである。例えば、上記一般式(X)のK-Tが1より大きい数である化合物は、シクロポリシロキサン環を導入する化合物として多官能の(RaSiHO)Kで表されるシクロポリシロキサンを用いた場合であっても、生成はわずかである。これは、シクロポリシロキサンの2つ以上のSi-Hに非環状のポリシロキサンがL3を介して結合した化合物の生成は、エネルギー的に大きく不利であるためである。
5'-メチルフェニル)ベンゾトリアゾール、2-(2'-ヒドロキシ-3',5'-ジ第三ブチルフェニル)-5-クロロベンゾトリアゾール、2-(2'-ヒドロキシ-3'-第三ブチル-5'-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2'-ヒドロキシ-5'-第三オクチルフェニル)ベンゾトリアゾール、2-(2'-ヒドロキシ-3',5'-ジクミルフェニル)ベンゾトリアゾール、2-(2'-ヒドロキシ-3'-第三ブチル-5'-カルボキシフェニル)ベンゾトリアゾール、2,2'-メチレンビス(4-第三オクチル-6-ベンゾトリアゾリル)フェノール等の2-(2'-ヒドロキシフェニル)ベンゾトリアゾール類が挙げられる。
の2-ヒドロキシベンゾフェノン類が挙げられる。
上記ヒドロキシカルボン酸としては、例えば、4-ヒドロキシルメチルシクロヘキサンカルボン酸、ヒドロキシトリメチル酢酸、6-ヒドロキシカプロン酸、グリコール酸、乳酸等が挙げられる。
尚、本発明の樹脂組成物において樹脂として熱硬化性のポリシロキサンを用いた場合は、本発明の樹脂組成物は公知の方法によって硬化させることができる。例えば、必要に応じて触媒を使用し、25~250℃に0.1~10時間加熱して重合させることにより、硬化させることができる。
また、下記製造例5及び6においては、樹脂(ポリシロキサン)として用いられる中間体を合成した。これらの中間体は、加熱によりさらに(共)重合して高分子化するものである。
下記実施例1-1~1-3では、製造例1~4において得られた中間体を用いて本発明の化合物を合成した。下記実施例2-1~2-15では、実施例1-1~1-3で得られた本発明の化合物を用いて樹脂組成物を調製し、下記比較例1-1~1-8では、比較化合物を用いて樹脂組成物を調製した。
攪拌機、温度計及び滴下漏斗を備えた1000ml4つ口フラスコに1,2,2,6,6-ペンタメチルピペリジン-4-オール(100g、0.58mmol)、テトラブチルアンモニウム硫酸水素塩(10g、0.03mmol)及び塩化アリル(202g、2.69mmol)を加えた。25℃で撹拌し、12.5mol/l水酸化ナトリウム水溶液(200ml)を30分かけて滴下し、滴下終了後50℃で6時間攪拌した。反応終了後25℃まで冷却し、トルエン150gを加えた。油水分離のために水250gを加え、25℃で30分間攪拌後、水層を除去した。同様の油水分離操作を8回行った。残った有機層から減圧下で溶媒及び未反応物を留去し、中間体1を119.7g(収率90%)を得た。
攪拌機、温度計、窒素封入管及び冷却管を備えた3000mlの4つ口フラスコにオクタフェニルシクロテトラシロキサン(361g、0.46mol)、カリウムメトキサイド(28.6g、0.41mol)及びオクタメチルシクロテトラシロキサン(540g、1.82mol)を加え、窒素気流下150℃で1.5時間攪拌した。反応終了後50℃まで冷却し、トルエン(600g)及び6N塩酸(1.50kg)を加え、窒素気流下90℃で14時間還流した。50℃まで冷却し水層を除去した後に、油水分離のため、0.1%ピリジン水溶液(1.50kg)を加え、50℃で30分間攪拌後、水層を除去した。同様に0.1%ピリジン水溶液を使用し油水分離操作を1回、水(1.50kg)を使用し油水分離を1回行った。さらに40℃まで冷却し、30-60mmHgで2時間還流した。その後、ピリジン(164g、2.07mol)及びジメチルクロロシラン(131g、1.38mol)を加え、40℃で1時間攪拌した。反応終了後、油水分離のため、水(1.5kg)を加え、40℃で30分間攪拌後、水層を除去した。同様に水(1.5kg)を使用し油水分離を3回行った。残った有機層から減圧下で溶媒及び低分子成分を留去し、中間体2-1(614g、収率65%)を得た。
上記中間体2-1の合成において、オクタフェニルシクロテトラシロキサンを590g(0.744mol)使用し、オクタメチルシクロテトラシロキサンを410g(1.382mol)使用した以外は中間体2-1と同様の製法で、中間体2-2を合成した。
攪拌機、温度計、窒素封入管及び冷却管を備えた3000mlの4つ口フラスコにオクタフェニルシクロテトラシロキサン(590g、0.74mol)、1,3-ジビニル1,1,3,3-テトラメチルジシロキサン(23.7g、0.13mol)、水酸化カリウム(216mg、3.85mmol)、N-メチルピロリドン(129g)及びオクタメチルシクロテトラシロキサン(410g、1.38mol)を加え、窒素気流下70℃で3時間攪拌した。その後、ピリジン(18g、0.23mol)及びジメチルビニルクロロシラン(18.5g、0.15mol)を加え、70℃で1時間攪拌した。反応終了後40℃まで冷却し、トルエン670gを加えた。油水分離のため、水(850g)を加え、40℃で30分間攪拌後、水層を除去した。同様に水(850g)を使用し油水分離を3回行った。残った有機層から減圧下で溶媒及び低分子成分を留去した。その後、1,3,5,7-テトラメチルシクロテトラシロキサン(191g、0.80mol)、0.40%Ossko触媒トルエン溶液(7.30g)及びトルエン(560g)を加え、アルゴン気流下3時間還流した。反応終了後25℃まで冷却し、減圧下で溶媒留去した。その後、分離操作を行うために生成物にアセトニトリル560gを加え、25℃で30分間攪拌した。生成物とアセトニトリルは2層に分離するので、アセトニトリル層を除去した。同様の分離操作を2回行った。残った有機層から減圧下で溶媒及び未反応物を留去し、中間体2-3(560g、収率52%)を得た。
攪拌機、温度計、窒素封入管及び冷却管を備えた4つ口フラスコにオクタフェニルシクロテトラシロキサン(590g、0.74mol)、1,3-ジビニル1,1,3,3-テトラメチルジシロキサン(23.7g、0.13mol)、水酸化カリウム(216mg、3.85mmol)、N-メチルピロリドン(129g)及びオクタメチルシクロテトラシロキサン(880g、2.97mol)を加え、窒素気流下70℃で3時間攪拌した。その後、ピリジン(18g、0.23mol)及びジメチルビニルクロロシラン(18.5g、0.15mol)を加え、70℃で1時間攪拌した。反応終了後40℃まで冷却し、トルエン670gを加えた。油水分離のため、水(850g)を加え、40℃で30分間攪拌後、水層を除去した。同様に水(850g)を使用し油水分離を3回行った。残った有機層から減圧下で溶媒及び低分子成分を留去し、中間体3-1(550g、収率53%)を得た。
上記中間体3-1の合成において、オクタフェニルシクロテトラシロキサンを590g(0.744mol)使用し、オクタメチルシクロテトラシロキサンを410g(1.382mol)使用した以外は中間体3-1と同様の製法で、中間体3-2を合成した。
攪拌機、温度計及びアルゴン導入管を備えた500mL4つ口フラスコに中間体2-1(100g、SiH基23.8mmol)、中間体1(10.5g、71.4mmol)、0.25%Ossko触媒トルエン溶液(2.0g)、ヒドロキノン(1.02g、9.26mmol)、トルエン(50.0g)を加え、アルゴン気流下100~110℃で2時間攪拌した。反応終了後25℃まで冷却し、油水分離のため、1%炭酸水素ナトリウム水溶液(100g)を加え、25℃で30分間攪拌後、水層を除去した。同様に1%炭酸水素ナトリウム水溶液を使用し油水分離操作を6回、水(100g)を使用し油水分離を3回行った。残った有機層から減圧下で溶媒及び未反応物を留去し、化合物No.1(37.9g、収率72%)を得た。
-0.35-0.51(m:6mH),0.94(d:6H),1.09(s:6H),1.23-1.32(m:2H),1.52(brs:2H),1.77(brs:2H),2.17(s:3H),3.08-3.52(m:3H),6.89-7.74(m:10nH)
また、1H-NMR分析より、一般式(4)のm及びnは、比率m/nが8/2であった。
攪拌機、温度計及びアルゴン導入管を備えた500ml4つ口フラスコに中間体2-2(50.0g、SIH基15.5mmol)、中間体1(10.5g、46.8mmol)、0.25%Ossko触媒トルエン溶液(1.00g)、ヒドロキノン(528mg、4.80mmol)、トルエン(24.0g)を加え、アルゴン気流下100~110℃で2時間攪拌した。反応終了後、減圧下で溶媒留去した。25℃まで冷却し、分離操作を行うために生成物にアセトニトリル50gを加え、25℃で30分間攪拌した。生成物とアセトニトリルは2層に分離するので、アセトニトリル層を除去した。同様の分離操作を3回行った。残った有機層から減圧下で溶媒及び未反応物を留去し、化合物No.2(39.6g、収率74%)を得た。
-0.44-0.55(m:6mH),0.97(d:6H),1.12(d:6H),1.26-1.35(m:2H),1.51(brs:2H),1.76-1.82(m:2H),2.20(s:3H),3.12-3.53(m:3H),6.86-7.61(m:10nH)
また、1H-NMR分析より、一般式(4)のm及びnは、比率m/nが7/3であった。
攪拌機、温度計及びアルゴン導入管を備えた500ml4つ口フラスコに中間体2-3(10.0g、SIH基15.5mmol)、中間体1(10.3g、46.6mmol)、ヒドロキノン(100mg、0.90mmol)、トルエン(5.0g)を加え、アルゴン気流下100-110℃で11時間攪拌した。反応終了後、減圧下で溶媒留去した。25℃まで冷却し、分離操作を行うために生成物にアセトニトリル50gを加え、25℃で30分間攪拌した。生成物とアセトニトリルは2層に分離するので、アセトニトリル層を除去した。同様の分離操作を3回行った。残った有機層から減圧下で溶媒及び未反応物を留去し、化合物No.3(10.5g、収率78%)を得た。
-0.35-0.51(m:6mH+18H),0.99(s:6H),1.13(s:6H),1.29-1.35(t:2H),1.56(brs:2H),1.81-1.84(m:2H),2.20(s:3H),3.35-3.47(m:3H),6.87-7.61(m:10nH)
また、1H-NMR分析より、一般式(4)のm及びnは、比率m/nが7/3であった。
下記の条件でGPCにより質量平均分子量(Mw)、数平均分子量(Mn)を分析した。
装置:東ソー社製 HLC-8320 GPC
カラム:東ソー社製 TSKgel SuperMultiporeHZ-M×2、TSKguardcolumn SuperMP(HZ)-M
移動相:テトラヒドロフラン
標準物質:ポリスチレン
温度:40℃
流速:0.35mL/min
検出:示差屈折率検出器
東機産業株式会社製TV-22型粘度計にて、25℃における粘度(mPa・s)を測定した。
また、中間体3-1及び中間体3-2について、1H-NMR分析を行い、各中間体に含まれる-[SiCH3CH3-O]-で表される繰り返し単位の数m’、及び-[SiC6H5C6H5-O]-で表される繰り返し単位の数n’の比率m’/n’を求めた。
これらの結果を表2に示す。
以下の試験化合物を用い、下記表3、表4記載の配合により樹脂組成物を調製した。樹脂組成物を合計3.7gになるようにるつぼ(容量10mL、外径32mm、高さ24mm)にはかりとり、2時間、150℃で加熱した。尚、この加熱により、樹脂としての下記X-1、X-2及びX-3に含まれるポリシロキサン化合物の重合が進行して、樹脂組成物が硬化する。
<A成分:本発明の化合物及び比較化合物>
A-1:化合物No.1(一般式(4)において、R1、R2、R7及びR8=メチル基、R9及びR10=フェニル基、X1=一般式(2)、L1=プロピレン基、R5=メチル基、m/n=8/2)
A-2:化合物No.2(一般式(4)において、R1、R2、R7及びR8=メチル基、R9及びR10=フェニル基、X1=一般式(2)、L1=プロピレン基、R5=メチル基、m/n=7/3)
A-3:化合物No.3(一般式(4)において、R1、R2、R7及びR8=メチル基、R9及びR10=フェニル基、X1=一般式(3)、X2=一般式(2)/水素原子=8/2(モル比)の混合物、L1=プロピレン基、L2=エチレン基、s=3、R5及びR6=メチル基、m/n=7/3)
a-1:1,2,3,4-ブタンテトラカルボン酸と1,2,2,6,6-ペンタメチル-4-ピペリジノール及び3,9-ビス(2-ヒドロキシ-1,1-ジメチルエチル)-2,4,8,10-テトラオキサスピロ[5.5]ウンデカンとの混合エステル化物(ADEKA社製、製品名:アデカスタブLA-63P)
a-2:1,2,3,4-ブタンテトラカルボン酸と2,2,6,6-テトラメチル-4-ピペリジノール及び3,9-ビス(2-ヒドロキシ-1,1-ジメチルエチル)-2,4,8,10-テトラオキサスピロ[5.5]ウンデカンとの混合エステル化物(ADEKA社製、製品名:アデカスタブLA-68)
a-3:(テトラメチルピペリジニル)オキシプロピルメチルシロキサン-ジメチルシロキサンコポリマー(Gelest社製、製品名:UBS-0822)
B-1:フュームド二酸化チタン(日本アエロジル社製、製品名:AEROXIDE TiO2 T805)
B-2:フュームド二酸化チタン(日本アエロジル社製、製品名:AEROXIDE TiO2 P25)
B-3:アナターゼ型二酸化チタン(石原産業社製、製品名:MS-50)
B-4:ルチル型二酸化チタン(石原産業社製、製品名:TTO-SS(A))
B-5:ブルカイト型二酸化チタン(高純度化学研究所社製)
B-6:酸化亜鉛(石原産業社製、製品名:FZO-50)
B-7:フュームド酸化アルミニウム(日本アエロジル社製、製品名:AEROXIDE Alu C805)
X-1:フラスコに中間体3-1、中間体2-1、テトラメチルシクロテトラシロキサンをそれぞれ中間体3-1/中間体2-1/テトラメチルシクロテトラシロキサン=46.3/53.6/0.1(質量比)の比率で合計10gになるようにとり、Ossko触媒を80ppmとり25℃で均一となるように攪拌した。
X-2:フラスコに中間体3-2、中間体2-2、テトラメチルシクロテトラシロキサンをそれぞれ中間体3-2/中間体2-2/テトラメチルシクロテトラシロキサン=60.0/39.5/0.5(質量比)の比率で合計10gになるようにとり、Ossko触媒を80ppmとり25℃で均一になるように攪拌した。
X-3:中間体2-3(尚、中間体2-3は、一般式(X-a)で表されるポリシロキサンであり、一般式(X-a)において、Ra=Rb=Rc=Rd=メチル基、Re=Rf=Rg=フェニル基、Z=水素原子、L3=エチレン基、k=3、r:q=3:7、p=2、質量平均分子量Mw=15000、数平均分子量Mn=7900であった。)
得られた各樹脂組成物の硬化物について、以下の方法により残存率及びちょう度を測定した。これらの結果を表3、表4に示す。
樹脂組成物の硬化物を空気下、250℃オーブンに入れて保存した。保存試験開始から100時間及び200時間経過後それぞれの樹脂組成物の硬化物の質量を測定し、試験開始前の質量と比較し、残存率〈計算式:100-[(試験前の質量-100時間又は200時間経過後の質量)÷試験前の質量×100]〉を求めた。
樹脂組成物の硬化物を空気下、250℃オーブンに入れて保存した。保存試験開始前、並びに保存試験開始から100時間及び200時間経過後それぞれに、樹脂組成物の硬化物について下記の測定条件でちょう度を測定した。
・測定条件
JIS K2220-2003の試験方法に準拠して、ちょう度測定用1/4円すい(株式会社離合社:型式874)及び自動ちょう度計(株式会社離合社製、RPM-101)を使用して、ちょう度を測定した。尚、樹脂組成物は、酸化により劣化するにつれてちょう度が減少する。
尚、比較例3-3及び3-4おいて、化合物a-1及びa-2は、0.2質量部以上添加すると樹脂と均一に相溶しないため、上記表4記載の配合で試験を行った。
Claims (10)
- 樹脂100質量部に対して請求項1又は2記載の化合物を0.001~10質量部配合してなることを特徴とする樹脂組成物。
- 上記樹脂100質量部に対して無機粉体を0.001~20質量部配合してなる請求項3記載の樹脂組成物。
- 上記無機粉体が二酸化チタン、酸化亜鉛又は酸化アルミニウムである請求項4記載の樹脂組成物。
- 上記樹脂がポリシロキサンである請求項3~5のいずれか1項記載の樹脂組成物。
- 上記請求項3~7のいずれか1項記載の樹脂組成物を硬化させて得られる硬化物。
- 半導体装置の封止剤又は半導体装置の接着剤の用途に使用する請求項3~7のいずれか1項記載の樹脂組成物。
- 上記請求項8記載の樹脂組成物を硬化させて得られる硬化物を用いた半導体装置。
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US20040231815A1 (en) * | 2003-04-25 | 2004-11-25 | Rhodia Chimie | Novel water-resistant, repulpable and hydrophilic paper having a soft feel |
JP5248033B2 (ja) * | 2007-04-23 | 2013-07-31 | 株式会社Adeka | ケイ素含有化合物、硬化性組成物及び硬化物 |
TWI433875B (zh) * | 2008-01-28 | 2014-04-11 | Shinetsu Chemical Co | 二縮水甘油基異氰尿酸基改性有機聚矽氧烷以及含有該有機聚矽氧烷的組成物 |
JP5305452B2 (ja) * | 2009-06-12 | 2013-10-02 | 信越化学工業株式会社 | 光半導体素子封止用樹脂組成物 |
JP5801208B2 (ja) | 2010-07-27 | 2015-10-28 | 株式会社Adeka | 半導体封止用硬化性組成物 |
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- 2011-11-15 CN CN201180004920.5A patent/CN102958979B/zh not_active Expired - Fee Related
- 2011-11-15 JP JP2012524988A patent/JP5781511B2/ja not_active Expired - Fee Related
- 2011-11-15 KR KR1020127014985A patent/KR20130140535A/ko not_active Application Discontinuation
- 2011-11-15 WO PCT/JP2011/076276 patent/WO2012105103A1/ja active Application Filing
- 2011-11-15 US US13/518,170 patent/US8937122B2/en not_active Expired - Fee Related
- 2011-11-15 EP EP11847881.7A patent/EP2671905A4/en not_active Withdrawn
- 2011-11-23 TW TW100142977A patent/TW201237071A/zh unknown
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101855637B1 (ko) | 2015-03-05 | 2018-05-04 | 가부시키가이샤 엔유씨 | 가교성 수지 조성물 및 전선·케이블 |
JP2017160387A (ja) * | 2016-03-11 | 2017-09-14 | 信越化学工業株式会社 | 防曇剤 |
JP2018104576A (ja) * | 2016-12-27 | 2018-07-05 | 信越化学工業株式会社 | シリコーン樹脂組成物及び光半導体装置 |
JP2018118462A (ja) * | 2017-01-26 | 2018-08-02 | 日本特殊陶業株式会社 | 複合部材及び接着剤組成物 |
JP2018154745A (ja) * | 2017-03-17 | 2018-10-04 | 旭化成株式会社 | 硬化性組成物 |
Also Published As
Publication number | Publication date |
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US20130018132A1 (en) | 2013-01-17 |
JP5781511B2 (ja) | 2015-09-24 |
TW201237071A (en) | 2012-09-16 |
EP2671905A4 (en) | 2014-11-12 |
US8937122B2 (en) | 2015-01-20 |
KR20130140535A (ko) | 2013-12-24 |
CN102958979A (zh) | 2013-03-06 |
CN102958979B (zh) | 2015-06-03 |
EP2671905A1 (en) | 2013-12-11 |
JPWO2012105103A1 (ja) | 2014-07-03 |
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