TW555811B - Curable silicone composition - Google Patents

Abstract

The present invention relates to a curable silicone composition which contains an air-oxidation-curable unsaturated compound, and which is cured by means of a hydrosilylation rection and a condensation reaction. An example of such a curable silicone composition is a curable silicone composition which includes (A) a mixture of (a) an organopolysiloxane which contains at least two alkoxy groups bonded to silicon atoms in each molecule, and which does not contain any alkenyl groups bonded to silicon atoms, and an organopolysiloxane which contains at least two alkeyl groups bonded to silicon atoms in each molecule, and which does not contain any alkoxy groups bonded to silicon atoms, or (b) an organopolysi1oxane which respectively contains at least two alkoxy groups bonded to silicon atoms and two alkenyl groups bonded to silicon atoms in each molecule, (B) an organopolysi1oxane which contains at least two hydrogen atoms bonded to silicon atoms in each molecule, (C) a condensation reaction catalyst, (D) a platinum type catalyst, and (E) an air-oxidation-curable unsaturated compound.

Description

555811 V. Description of the invention (1) The present invention relates to an excellent matte property such as borrowing hydrogen, which can be borrowed or added for use. However, the hardened LED (light shape, hard vision recognition will therefore be used in this group to impart the obtained reason and add hydrogen silane to the hard hydrogen silane heat or by the motor, which has the characteristics of emitting dichemical products. No, the obtained compound is sufficient for this combination. The field of the invention is a well-characterized reaction product. The field of the invention is a hardenable mash I composition. More specifically, it relates to the results of the hardening of the silylation reaction and the condensation reaction. A hardenable crushed ketone composition capable of forming a hardened product. Background of the invention The hardenable crushed ketone composition hardened by air in a reaction and condensation reaction is hardened by water in the air. Therefore, this composition is suitable as a filler for electronic devices and the like. Or adhesive, such as the case of hardenable silicone compositions such as sealants, the surface gloss obtained by hardening, as a result, the hardened product is used as a waterproof filler or adhesive for display devices such as polar bodies. The reflection comes from The light from LEDs and the light from the outside makes the eyes good. The hardened product obtained by mixing the inorganic filler and the hardenable silicone composition was tried to remove gloss; however, it was impossible to impart sufficient matte properties. In addition, a large amount of filler must be used for the matte properties; however, if such a large amount of filler is used, the fluidity of the silicone composition is reduced, and the composition is degraded. In order to provide a hardenable silicone composition, which can be formed with excellent matte properties as a result of hardening by condensation reaction. DETAILED DESCRIPTION OF THE INVENTION

Page 6 555811 V. Description of the invention (2) The present invention relates to a hardenable silicone composition which is hardened by a hydrosilylation reaction and a condensation reaction, and is characterized in that the composition contains an air-oxidizable hardenable unsaturated compound. Facts. This unsaturated compound is an ingredient for imparting sufficient matte properties to a hardened product obtained by hardening the composition. This unsaturated compound is hardened by oxidizing an unsaturated bond in the molecule with oxygen contained in the air; a typical example of this unsaturated compound is an aliphatic compound having at least two unsaturated bonds per molecule. Examples of such compounds include unsaturated high-carbon fatty acids, such as hypolinoleic acid and linoleic acid; etc .; intentional lipids and oils, including unsaturated high-carbon fatty acids and glycerol, such as tung oil, linseed oil, and soybean oil; etc .; Esters of saturated high-carbon fatty acids and alcohols, such as ethyl linolenate and ethyl linoleate; unsaturated hydrocarbon compounds such as butadiene, pentadiene, and hexadiene; and polymers of such compounds . In particular, it is particularly desirable to be linolenic acid, linolenic acid vinegar, tung oil, linseed oil, 1,3-hexadiene and polybutadiene. In the present invention, it is desirable that the content of the above-mentioned air oxidation-hardenable unsaturated compound is in the range of 0.01 to 50 parts by weight per 100 parts by weight of the silicone component in the composition; even more desirably in the range of 0.1 to 20 parts by weight The content is particularly desirable in a range of 0.1 to 10 parts by weight. It should be noted that if the content of this unsaturated compound is below the lower limit of the above range, it tends to impart insufficient matte properties to the resulting hardened silicone product. On the other hand, if the content exceeds the upper limit of the above range, the mechanical characteristics of the resulting hardened silicone product tends to deteriorate. Hope that this kind of hardenable silicone hardened by hydrogen silylation reaction and condensation reaction

Page 7 555811 5. Description of the invention (3) The composition is a composition including at least the following: (A) (a) each molecule contains at least two alkoxy groups bonded to a silicon atom, and it does not contain any bonds Organic polysiloxanes bonded to silicon alkenyl groups, and organic polysiloxanes containing at least two alkenyl groups bonded to silicon atoms in each molecule, and not containing any alkoxy groups bonded to silicon atoms Alkanes, and (b) a mixture of organopolysiloxanes containing at least two alkenyl groups bonded to a silicon atom in each molecule and not containing any alkoxy groups bonded to a silicon atom, or (a) and A combination of (b), (c) an organopolysiloxane containing at least two alkoxy groups bonded to a silicon atom and two alkenyl groups bonded to a silicon atom in each molecule, (B) in each molecule Organic polylithic oxygen institute containing at least two hydrogen atoms bonded to silicon atom, (C) condensation reaction catalyst, (D) platinum type catalyst, and (E) unsaturated compound which can be hardened by air oxidation. The component (A) is (a) an organic polysiloxane which contains at least two alkoxy groups bonded to a silicon atom in each molecule, and does not contain any alkenyl group bonded to a silicon atom, and contains At least two diluent radicals bonded to the Shixi atom, and which do not contain any alkoxy groups bonded to the silicon atom, and (b) each molecule containing at least two bonds to the silicon atom A mixture of alkenyl groups which do not contain any alkoxy group bonded to a silicon atom, or (c) each molecule containing at least two alkoxy groups bonded to a silicon atom and two Alkenyl organic polysiloxanes bonded to silicon atoms. Component (a) should have at least two alkoxy groups bonded to the silicon atom in each molecule; if the number of alkoxy groups bonded to the silicon atom is less than two per molecule, it is difficult to use a condensation reaction

Page 8 555811 V. Description of the invention (4) Full hardening of the resulting composition is obtained. The molecular structure of component (a) can be linear, linear with partial branching, or branching. In particular, a linear structure is particularly desirable. Examples of the alkoxy group which may constitute the alkoxy group bonded to the silicon atom in the component (a) include methoxy, ethoxy, propoxy, butoxy, methoxymethoxy, and methoxy Ethoxy. In particular, alkoxy is particularly desirable. The bonding position of these alkoxy groups may be on the terminal of the molecular chain, or on the side chain of the molecular bond; it is particularly desirable that the bonding is on the terminal of the molecular chain, because the reactivity at this bonding position is good. These alkoxy groups may be directly bonded to a silicon atom of the main chain, or may be bonded to a silicon atom sequentially bonded to a silicon atom of the main chain through an alkylene group. In addition, examples of the group other than the alkoxy group which can be bonded to the silicon atom in the component (a) include an alkyl group such as a fluorenyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. , Nonyl, decyl and octadecyl, etc .; cycloalkyl, such as cyclopentyl and cyclohexyl, etc .; aryl, such as phenyl, fluorenyl, xylyl and naphthyl, etc .; aralkyl, such as T Radicals, phenethyl and phenylpropyl, etc .; and alkylene radicals, such as 3-chloropropyl and 3,3,3-trifluoropropyl and the like. In particular, methyl and phenyl are particularly desirable. In addition, it is desirable that the viscosity of the component (a) is in the range of 20 to 2 0, 0 0 0 1 ^ 8.3 at 25 ° C, and particularly preferably in the range of 100 to 100,000 111 to 3.3. It should be noted that if the viscosity is lower than the lower limit of the above range at 25 ° C, the physical properties of the hardened product tend to deteriorate, such as softness and elongation; on the other hand, if the viscosity exceeds the upper limit of the above range, the composition Processing and processing characteristics tend to degrade. Examples of the organopolysiloxane which can be used as the component (a) include a polyfluorinated polysiloxane in which both ends of the molecular chain are closed with a trimethoxysiloxy group.

Page 9 555811 V. Description of the invention (5) Siloxane, in which the two molecular ends of the molecular chain are closed with trimethoxysiloxy, a difluorenylsiloxane-methylphenylsiloxane copolymer, in which the molecule Dimethylpolysiloxane blocked with triethoxysiloxy at both ends of the chain, and dimethylpolysiloxane blocked with tripropoxysiloxy at both ends of the molecular chain, Dimethyl polysiloxane blocked with methyldimethoxysiloxy at both ends, in which difluorenyl polysiloxane blocked with fluorenyldimethoxysiloxy at both ends of the molecular chain, in which the molecule Dimethicone with methyldiethoxysiloxy at both ends of the chain Diphenyl siloxane copolymer, in which both ends of the molecular chain are blocked with trimethoxysilylethyldifluorenylsiloxy, and the two ends of the molecular chain are triethoxylated. Disilyl ethyl dimethyl siloxy blocked difluorenyl polysiloxane, where both ends of the molecular chain are blocked with trimethoxy silyl propyl difluorenyl siloxy Dimethylpolysiloxane, in which both ends of the molecular chain are closed with trimethoxysilylethyldifluorenylsiloxy, a difluorenylsiloxane-fluorenylphenylsiloxane copolymer, in which the molecular chain Dioxopolysiloxane blocked with methyldimethoxysilylethyldimethylsilyl at both ends, with methyldimethoxysilylethyldifluorenyl at both ends of the molecular chain Siloxane-blocked dimethylsiloxane-methylphenylsiloxane copolymer, in which both ends of the molecular chain are blocked with trimethoxysiloxanyl-dimethylsiloxane (trioxane Silylethyl) siloxane copolymer, in which both ends of the molecular chain are closed with trimethoxysiloxy, and the difluorenylsiloxane-fluorenyl (triethoxysilylethyl) siloxane A copolymer in which a difluorenylsiloxane-fluorenyl (trimethylsilylethyl) siloxane copolymer in which both ends of the molecular chain are closed with trimethoxysilylethyldifluorenylsiloxy, and

Page 10 555811 V. Description of the invention (6) Includes a mixture of two or more of these organic polysiloxanes. In addition, the component (b) should contain at least two alkenyl groups bonded to the stone atom in each molecule; its atom is that if the number of alkenyl groups bonded to the silicon atom is less than two per molecule, it is difficult to borrow hydrogen The silylation reaction results in sufficient hardening of the resulting composition. The molecular structure of component (b) may be linear, with some branched linear, branched, circular or resin forms. The alkenyl group bonded to the silicon atom in the component (b) may be vinyl, allyl, butenyl, pentenyl or hexenyl and the like. In particular, ethylene is particularly desirable. The bonding position of these dilute radicals may be on the terminal of the molecular chain or on the side chain of the molecular chain; it is particularly desirable that the bonding is on the terminal of the molecular chain because the reactivity at this bonding position is good. In addition, examples of the group other than the alkenyl group which can be bonded to the silicon atom in the component (b) include an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, Nonyl, decyl, and octadecyl; cycloalkyl, such as cyclopentyl and cyclohexyl; aryl, such as phenyl, fluorenyl, diphenyl, and naphthyl; aryl, such as T Groups, such as phenethyl and phenylpropyl; and iS alkyl groups, such as 3-chloropropyl and 3, 3, 3-trifluoropropyl. In particular, methyl and phenyl are particularly desirable. In addition, it is desirable that the viscosity of the component (b) is in the range of 20 to 2 0 0, 0 0 0 m P a · s at 25 ° C, and particularly desirable is 1 0 to 1 0 0, 0 0 0 m P a · The range of s. It should be noted that if the viscosity is lower than the lower limit of the above range at 25 ° C, the physical properties of the hardened product tend to deteriorate, such as softness and elongation; on the other hand, if the viscosity exceeds the upper limit of the above range, the composition Processing and processing characteristics tend to degrade. Examples of the organopolysiloxane which can be used as the component (b) include polyfluorenylsiloxane in which both ends of the molecular chain are closed with trimethylsiloxy

Page 11 555811 V. Description of the invention (7) Alkyl-methylvinylsiloxane copolymer, in which both ends of the molecular chain are closed with trimethylsilylfluorenylpolysiloxane, in which the molecular chain Dimethyllithium oxalate-methylphenyl oxalate-fluorenyl phenylsilyl copolymer closed with trimethyl crushed oxygen at both ends, with dimethylethylene at both ends of the molecular chain Dimethylsiloxy-blocked dimethylpolysiloxane, in which both ends of the molecular chain are blocked with dimethylvinylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymer, in which the molecule Dioxoyl oxynitride blocked with diethyl vinylsiloxy at both ends of the chain " methyl ethyl ketone xyloxy-pyridyl phenyl oxidene copolymer, including formula (CH2 = CH) ( CH3) 2Si01 / 2 is the unit of siloxane and organic polyoxygen sintered by the unit of oxidized oxidized by Si 04/2, including the unit of siloxane represented by the formula (CH3) 3Si01 / 2. = CH) (CH3) 2Si01 / 2 The organopolysiloxane represented by the siloxane unit represented by the formula Si 04/2 and the organopolysiloxane represented by the formula Si 04/2, including the siloxane represented by the formula (CH3) 3Si01 / 2 Position, Shixian unit of oxygen expressed by formula (CH2 = CH) (CH3) 2Si01 / 2, Shixoxane unit expressed by formula (CH3) 2Si 02/2 and Siloxane unit expressed by formula Si 04/2 Organopolysiloxanes, and mixtures comprising two or more of these organopolysiloxanes. It is desirable that the content of the component (a) in the component (A) is in the range of 5 to 95% by weight, and the content of the component (b) constitutes the remaining components (A) (% by weight). It should be noted that if the content of the component (a) in the component (A) is lower than the lower limit of the above range, it tends to be difficult to obtain sufficient hardening of the resulting composition by a condensation reaction; on the other hand, if the content exceeds the above range, The upper limit is that it tends to be difficult to obtain sufficient hardening of the resulting composition by a hydrosilylation reaction. In addition, component (c) is an organopolysiloxane containing at least two alkoxy groups bonded to a silicon atom and two alkenyl groups bonded to a silicon atom in each molecule. to make

Page 12 555811 V. Description of the invention (8) Part (C) contains at least two alkoxy groups bonded to silicon atom in each molecule; if the number of alkoxy groups bonded to silicon atom is less than two per molecule It is difficult to obtain sufficient hardening of the resulting composition by a condensation reaction. In addition, the component (C) contains at least two alkenyl groups bonded to the silicon atom in each molecule; if the number of alkenyl groups bonded to the silicon atom is less than two per molecule, it is difficult to obtain it by hydrogen silanization. The composition is sufficiently hardened. The molecular structure of component (C) can be linear, linear with some branches, or branches. In particular, a linear structure is particularly desirable. Examples of the alkoxy group which can be bonded to the silicon atom in the component (C) include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like. In particular, ethoxy and ethoxy are particularly desirable. Further, examples of the alkenyl group which can be bonded to the silicon atom in the component (C) include vinyl, allyl, butenyl, pentenyl, hexenyl and heptenyl. In particular, vinyl is particularly desirable. The bonding position of these alkenyl groups may be on the terminal of the molecular chain, or on the molecular side chain. In addition, examples of the group other than the alkoxy group and the alkenyl group which may be bonded to the silicon atom in the component (C) include an alkyl group such as a fluorenyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. , Octyl, nonyl, decyl and octadecyl, etc .; cycloalkyl, such as cyclopentyl and cyclohexyl, etc .; aryl, such as phenyl, tolyl, difluorenyl and naphthyl, etc .; aralkyl , Such as benzyl, phenethyl and phenylpropyl, etc .; and halogenated alkyl, such as 3-p-propyl and 3,3,3-trifluoropropyl, etc. In addition, the viscosity of the component (c) is desirably in the range of 20 to 200,000 mPa · s at 25 ° C, and particularly in the range of 100 to 100, 000 m Pa · s. The reason is as follows: In particular, if the viscosity is lower than the lower limit of the above range at 25 ° C, the physical properties of the hardened product tend to be degraded; on the other hand, if the viscosity exceeds the upper limit of the above range, the treatment and processing of the resulting composition Features tend to degenerate.

Page 13 555811 V. Description of the invention (9) Examples of organopolysiloxanes that can be used as component (c) include polydimethylsiloxanes in which both ends of the molecular chain are closed with trimethoxysiloxy groups Siloxane-methylvinylsiloxane copolymer, in which both ends of the molecular chain are closed with trimethoxysiloxy, difluorenylsiloxane-methylvinylsiloxane-methylphenylsiloxane Alkane copolymer, in which both ends of the molecular chain are blocked by triethoxysiloxy, and the two ends of the molecular chain are tripropyloxysilane Bis-fluorenylsiloxane-fluorenylvinylsiloxane copolymers in which the two ends of the molecular chain are blocked by fluorenyldimethoxysiloxy Oxyalkane copolymer, in which both ends of the molecular chain are blocked with methyldiethoxysiloxy, and dimethylsiloxane-methylvinylsiloxane copolymer, in which both ends of the molecular chain are terminated with methyldisiloxane Methoxysiloxy-blocked difluorenylsiloxane-fluorenylvinylsiloxane-fluorenylphenylsiloxane copolymer, in which both ends of the molecular chain Dimethoxyxyloxanyl-methylethoxyzyloxanyl-trioxo (trimethoxyxyloxanylethyl) xyloxane copolymer blocked with trimethoxyxanthoxy, wherein both ends of the molecular chain Dioxenyl oxalate-methylethoxyxyloxane-methyl (triethoxysilylethyl) siloxane copolymer blocked with trioxoethoxy, wherein both ends of the molecular chain A difluorenylsiloxane-fluorenylvinylsiloxane-fluorenyl (trimethylsilylethyl) siloxane copolymer blocked with trimethoxysilylethyldifluorenylsiloxy, and Includes a mixture of two or more such organic polysiloxanes. In addition, the organopolysiloxane of the component (B) is used for the hydrosilylation reaction between the alkenyl group bonded to the silicon atom in the component (A) and the hydrogen bonded to the silicon atom in the component. Ingredient for hardening the composition of the present invention. Ingredient (B) in

Page 14 555811 V. Description of the invention (ίο) Each molecule contains at least two hydrogen atoms bonded to silicon atoms; the reason is that if the number of hydrogen atoms bonded to silicon atoms is less than two per molecule, it becomes It is difficult to obtain sufficient hardening of the resulting composition by the hydrosilylation reaction; in addition, the molecular structure of the component (B) may be linear, with some branched linear, branched, ring, or resin forms. The bonding position of the hydrogen atom bonded to the silicon atom may be at the terminal end of the molecular chain, or on the molecular side chain. Further, examples of the group other than the hydrogen atom which can be bonded to the silicon atom in the component (B) include an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, Nonyl, decyl, and octadecyl, etc .; cycloalkyl, such as cyclopentyl and cyclohexyl, etc .; aryl, such as phenyl, fluorenyl, difluorenyl, and naphthyl; aralkyl, such as fluorene Groups such as phenethyl and phenylpropyl; halogenated alkyl groups such as 3-chloropropyl and 3, 3, 3-trifluoropropyl; and alkoxy groups such as methoxy and ethoxy. Particularly preferred are fluorenyl and phenyl. In addition, it is desirable that the viscosity of the component (B) is in the range of 2 to 20,000 mPa · s at 25 ° C. The reasons are as follows: In particular, if the viscosity is lower than the lower limit of the above range at 25 ° C, the organopolysiloxane tends to volatilize, causing the composition of the composition to be unstable. On the other hand, if the viscosity exceeds the upper limit of this range, The processing and processing characteristics of the resulting composition tend to degrade. Examples of the organopolysiloxane which may be used as the organopolysiloxane of this component (B) include a fluorenyl hydrogenated polysiloxane in which both ends of the molecular chain are closed with trimethylsiloxy, in which two of the molecular chain Dimethylsiloxane-fluorenyl hydrosiloxane copolymer blocked with trimethylsiloxy at the end, in which the two molecular ends of the molecular chain are difluorenylpolysiloxane blocked with difluorinated hydrogensiloxane, Dioxosiloxane-methyl hydrogen

Page 15 555811 V. Description of the invention (π) Siloxane copolymer, including the siloxane unit represented by the formula (CH3) 2HSi01 / 2 and the organopolysiloxane containing the siloxane unit represented by the formula Si 04/2 , Including the Shixian oxygen burning unit represented by the formula (CH3) 3Si01 / 2, the Shixoxane unit represented by the formula (CH3) 2HSi01 / 2, and the organopolysiloxane containing the siloxane unit represented by the formula Si 04/2 , Including the Shixian oxygen burning unit represented by the formula (CH3) 3Si01 / 2, the siloxane unit represented by the formula (CH3) 2HSi01 / 2 and the siloxane unit represented by the formula (CH3) 2Si02 / 2 or the formula Si04 / 2 Organopolysiloxanes, and mixtures of two or more such organopolysiloxanes. In the above composition, it is desirable that the content of the component (B) is such that the molar ratio of the hydrogen atom bonded to the silicon atom to the alkenyl group bonded to the silicon atom in the component (A) is 0.3. The amount is in the range of 20 to 20, and it is particularly desirable that the content of this mole ratio is in the range of 0.5 to 50. It should be noted that if the mole ratio of the hydrogen atom bonded to the silicon atom to the silicon atom in the component (A) is lower than the lower limit of the above range, it tends to become difficult to borrow hydrogen silane The chemical reaction results in sufficient hardening of the resulting composition; on the other hand, if the molar ratio exceeds the upper limit of the above range, the physical characteristics of the resulting product tend to deteriorate. In addition, the condensation reaction catalyst of the component (C) is a catalyst for accelerating the condensation reaction of the alkoxy group bonded to the silicon atom in the component (A). The catalysts that can be used as the condensation reaction catalyst of the component (C) include organic titanium type condensation reaction catalysts, organic fluorene type condensation reaction catalysts, and organic aluminum type condensation reaction catalysts. Examples of this organic titanium-type condensation reaction catalyst include organic titanates such as tetrabutyl titanate, tetraisopropyl titanate, and the like, and organic titanium clamping compounds such as diisopropoxyfluorene (ethylamidoethyl) ) Titanium and Titanium Diisopropoxide (Ethyl Acetate Acetate)

Page 16 555811 V. Description of Invention (12) and so on. Examples of the above-mentioned organic fluorene-type condensation reaction catalysts include organic zirconium esters, such as tetrapropionate and tetrabutyric acid, and the like, and organic misclamp compounds, such as osmium diacetate, tetrakis (ethylacetoacetonate), Zirconium acetoacetate, Zirconium acetoacetate, Zirconium acetoacetate, Zirconium acetoacetate, Zirconium acetoacetate and Ethyl acetoacetate ) Dibutoxine and so on. In addition, examples of the above-mentioned organoaluminum type condensation reaction catalysts include organoaluminum esters, such as aluminum triacetate, aluminum triisopropionate, aluminum tris (second butyrate) and aluminum diisopropylate (second butoxy), and the like. And organoaluminum clamping compounds, such as (ethyl acetoacetic acid) aluminum diisopropoxide, ginseng (ethyl acetoacetic acid) aluminum, osmium (ethyl acetoacetic acid) aluminum monoethyl acetoacetate and Ginseng (ethyl acetoacetate) aluminum. The above catalysts may be used alone or as a condensation reaction catalyst comprising a mixture of two or more catalysts as the component (C). The content of the component (C) is an amount sufficient to harden the above composition by a condensation reaction; it is generally desirable that the content is in the range of 0.01 to 10 parts by weight per 100 parts by weight of the component (A), and it is particularly desirable that it is 0.1 to Content in the range of 5 parts by weight. If the content of the component (C) is lower than the lower limit of the above range, it tends to become difficult to obtain sufficient hardening of the resulting composition by condensation reaction; on the other hand, if the content exceeds the upper limit of the above range, the storage stability of the resulting composition is stable Force tends to degrade, as do the processing and processing characteristics of the composition. In addition, the platinum-type catalyst of the component (D) is used for accelerating the calcination reaction of the hydrogen stone between the alkenyl group bonded to the silicon atom in the component (A) and the hydrogen atom bonded to the silicon atom in the component (B). catalyst. Examples of the catalyst that can be used as the starting catalyst of the component (D) include the starting solution of starting black, "starting on activated carbon," and supporting platinum, aeroplatinic acid, and chloroplatinic acid. The match between platinum and olefins

Page 17 555811 V. Description of the invention (13), complex of platinum and ethylene siloxane, and finely divided catalysts, including thermoplastic resins containing these platinum-type catalysts. Examples of usable thermoplastic resins include silicone resins, polycarbonate resins, acrylic resins, nylon resins, and polyester resins. In addition, it is desirable that the softening point of this thermoplastic resin is 5 to 200 ° C, and the particle size of the resin is 0.01 to 1 0 // m. 01 至 The content of component (D) is an amount sufficient to harden the above composition by a hydrosilylation reaction; it is generally desirable that this content is such that the amount of platinum metal in component (D) is from 0.01 to the silicone component in the above composition. An amount in the range of 100 ppm (weight unit), and it is particularly desirable to make the amount of the metal in the range of 0.5 to 200 ppm. If the content of ingredient (D) is lower than the lower limit of the above range, it tends to become difficult to obtain sufficient hardening of the resulting composition by the hydrosilylation reaction; on the other hand, if the content exceeds the upper limit of the above range, the amount of the resulting composition The hardening reaction cannot be significantly accelerated, and there is a risk of causing problems such as discoloration in the resulting composition. In addition, the air-oxidatively hardenable unsaturated compound of the component (E) is a component that is used to impart sufficient matte texture to the hardened product obtained by hardening the above-mentioned composition. This unsaturated compound is hardened by oxidizing unsaturated bonds in the molecule with oxygen in the air, and is generally an aliphatic compound having at least two unsaturated bonds per molecule. Examples of this unsaturated compound 4 include unsaturated high-carbon fatty acids, such as hypolinolenic acid and linseed oil; etc .; lipids and oils including unsaturated high-carbon fatty acids and glycerol, such as tung oil, linseed oil, and soybean oil; Esters of unsaturated high-carbon fatty acids and alcohols, such as ethyl linolenate and methyl linoleate; etc .; unsaturated hydrocarbon compounds, such as butadiene, pentadiene, and hexadiene; and the polymerization of such compounds In particular

Page 18 555811 V. Description of the invention (14) 1,3-dioxane linoleic acid, hypolinolenic acid, tung oil, linseed oil and polybutadiene. The content of the component (E) is desirably in the range of 0.01 to 50 parts by weight per 100 parts by weight of the silicone component in the above composition. A content in the range of 0.1 to 20 parts by weight is even more desirable, and a content in the range of 0.1 to 10 parts by weight is particularly desirable. If the content of ingredient (E) is lower than the lower limit of the above range, it tends to become difficult to impart sufficient matte properties to the hardened product produced; on the other hand, if the content exceeds the upper limit of the above range, the mechanical properties of the hardened product produced Features tend to degenerate. The above composition is prepared by mixing ingredients (A) to (E); however, for the purpose of improving the storage stability of the above composition, or for the purpose of improving the adhesive properties of the above composition, the above composition may also contain the following R1aSi (OR2) 4.a (in the above formula, R1 represents a monovalent hydrocarbon group, an epoxy functional group monovalent organic group or a propenyl functional group monovalent organic group, which may be the same or Differently, R2 represents an alkyl group or an alkoxyalkyl group, which may be the same or different, and a represents 0, 1 or 2), or a partial hydrolysis-condensation product thereof, as an optional ingredient. In the above formula, R1 represents a monovalent hydrocarbon group, an epoxy functional group, a monovalent organic group, or a propenyl functional organic group, which may be the same or different. Examples of the monovalent hydrocarbon group include alkyl groups such as fluorenyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and octadecyl, and the like; cycloalkyl such as cyclo Amyl and cyclohexyl, etc .; aryl, such as phenyl, tolyl, diphenyl, and naphthyl; aralkyl, such as T, phenethyl and phenylpropyl; and halogenated alkyl, such as 3 -Chloropropane

P.19 555811 V. Description of the Invention Examples of the (15) group and the 3, 3, 3-triyl group include 8-oxetanyloxypropyl and 4-such as] 2-(3,4- ring. In addition, the above monovalent epoxy functional groups include butylalkyl, such as 4-oxetanylbutyl and glycidyloxyalkyl, such as 3-glycidoxybutyl, etc .; and [other groups, Base) vinyl, etc. In addition, the above-mentioned examples of propenyl include fluorenylpropenyloxy and 4-methyl. In the above formula, R2 represents a carbamoyl group or an alkoxy group such as methyl'ethyl'propyl'butyl'fluorene, nonyl. , Decyl and octadecyl, etc., and oxo, ethoxyethyl, methoxypropyl, and methoxy should not be fluorenyl. In addition, in the above formula, it is 1. Examples of the partially hydrolyzed condensation products include alkoxyalkane, tetraethoxysilane, fluorenylcellulose, sylvanoxane's methyl triethoxyl, acetyl trimethoxyl, phenyltrimethoxyl, Burned, alkane, dimethyldimethoxysilane and diphenyl functional alkoxysilane, such as 4-oxetanyl, 8-oxetanyloctyltrimethoxysilyltrimethoxysilane And 2-(3, 4- epoxy epoxy silane, etc .; propenyl functional alkoxy silanes, such as 3- methacryloxypropyl trimethoxy silane and 4-methacryloxy silane etc. ; Partial hydrolysis and condensation of these alkoxysilanes, and more kinds of these alkoxysilanes or partial hydrolysis of condensation to produce functional propyloxy groups; Ester methoxymethyltrimethoxybutane, 3-monovalent butyl butyl group examples, heptyl, such as fluorene, etc. Special 1 or 2, alkoxy, such as tetrakis, fluorenyl stone yaki, Methoxysilane silyltrifluoroglycidyl and other octyl octyl, etc .; glycidyl oxycyclohexyl etc. Including alkyl, aryl, octyloxyethyl, other, particularly and preferably silane and its alkoxysilyl triethoxyvinyltriethoxysilyl; etc .; epoxyoxysilyl oleyloxycyclocyclohexyl ) Ethyl butyl trimethoxy product; and two or

Page 20 555811 V. Description of the invention (16) A mixture of substances. It is desirable that the content of such an alkoxysilane or a partially hydrolyzed condensation product thereof is in the range of 0.01 to 20 parts by weight per 100 parts by weight of the component (A) of the above composition, and it is particularly desirable to be 0.1 to Content in the range of 10 parts by weight. If the content of this alkoxysilane or its partially hydrolyzed condensation product is below the lower limit of the above range, the storage stability of the resulting composition tends to decrease and the adhesive properties tend to deteriorate; on the other hand, if the content exceeds the above At the upper limit of the range, the hardening of the resulting composition tends to be significantly hindered. In addition, it is possible to add dihydroxyformate, an optional ingredient to improve the processing and processing characteristics of the above-mentioned composition; etc .; Cyclocyclotetrasiloxane reaction inhibitor, and it is generally 10 to additional materials, such as micronized oxidation Titanium hydroxide includes acetylene-type compounds such as 3-methyl-1-butyn-3-ol, 3, 5-yl-1-hexan-3-ol and 3-phenyl-1-butyn-3-ol Alcohols, etc., such as 3-fluorenyl-3-pentene-1-yne and 3,5-difluorenyl-3-hexene-1-yne dilute crushed siloxanes, etc .; content of three preparations, Often hope 1,000, the above fuming silica carbonate, fine I Lu, fine oxygen burn, such as compound with 1, 3, 5, salivary compounds such as phosphine treatment according to this inhibitor ppm (weight composition Yishi 'fine, fine powder Powdered diatoms, micronized zinc 1,3,5,7-tetramethyl-1,3,5,7_tetraethyl 7-tetramethyl-1,3,5,7-tetrahexyl ring tetra , Such as benzotriazole, etc .; and other hydrosilylates, hydrogen sulfur compounds, hydrazine compounds, etc. This varies with processing conditions and hardening conditions; however, it is used in an amount relative to the silicone composition range unit of the above composition). May contain the following as optional ingredients: inorganic powder-filled wet silica, finely-powdered quartz, fine-powdered magnesium carbonate, iron oxide, fine-powdered clay, fine-powdered oxide, fine-powdered oxide and fine Pulverized zinc carbonate, etc .;

P.21 555811 V. Description of the invention (17) Acetone, methyl ethyl organopolysiloxane obtained by burning with organic alkoxy, such as trimethane, or methyl ethene such as dimethylsilylphenyl Polydimethylene-based closed polymethyl methacrylate and other additives, internal and anti-molding agents can be used to make kneading devices, mixers, etc. The present invention can be formed at the appropriate time. Oxygen-based burning in silicon-based gas Oxy-based burning of water-based ketones in silicon, burning, silicon benzene, mold release, etc. Create a bi-homogeneous alkane, such as silane and other sub-chains. Polymers such as oxane and inorganic fillers such as alkane, or siloxanes such as flame retardants, and plastic-based tri 'organic ends, Among them, or its polymer and other materials; there is butyl ketone molecular chain which is burned; pigment, resistance agent, methoxyorganosilyl group seals the molecules in the molecular chain, and the solvent on the machine is burned to the two terminals The materials of the chain, such as thermally modified denatured oxalate, and the closed two chains are not described, such as three-terminal carbon black agent, and the end, etc. Alkyl and other fluorenyl groups are tri- or red-sensitizing agents, organic halomethyldioxane oligomeric hydroxy groups are sealed on the surface of hydroxy materials, dimethyl; unbreakable oxymethyl silicon oxide agents, polyadhesion-promoting silicon-silicon-nitrogen compounds, closed Blocking treatment of benzene, cross-linking blocking oxygen, etc. The method of combining the composition includes mixing the ingredients (A) to (E) with a roller, Banbury mixer, among which a well-known kneading mixer or turnover and the above-mentioned selected ingredients Can be hardened; mayone combination By the hydrogen; 5 evening burnt condensation reaction to react with the matte side having a hardened product excellent in the properties. Therefore, this composition, such as an LED display device, is used as a filler or a stick in a display device. Description of a preferred embodiment A particularly preferred embodiment of the present invention relates to a hardenable silicone composition

Page 22 555811 V. Description of the invention (18), which includes: (A) 1 0 0 parts by weight of an organic polysiloxane (4-n) / 2

R ^ SiO wherein R1 is a substituted or unsubstituted monovalent hydrocarbon group, which may be the same or different, and η is a positive number of 1.6 to 2.4; (B) 0.01 to 50 parts by weight of an organic compound, which It has an air-oxidizable hardenable unsaturated group; and (C) a hardener (used in an amount effective to harden the above-mentioned component (A)). The component (A) is an organopolysiloxane, which is represented by the following formula:) / 2 In the above formula, R1 represents a substituted or unsubstituted monovalent hydrocarbon group, which may be the same or different. Examples of this group include alkyl groups such as methyl, ethyl, propyl and butyl, etc .; cycloalkyl groups such as cyclopentyl and cyclohexyl, etc .; alkenyl groups such as vinyl, allyl, butenyl and Hexenyl, etc .; aryl, such as phenyl and tolyl, etc .; and halogenated alkyl, such as hydrazone and 3, 3, 3-trifluoropropyl, etc. In the case where the composition is a composition hardened by an organic peroxide, there is no limitation on the group bonded to the silicon atom in the component (A); however, in which the composition is hardened by a hydrosilylation reaction In the case of a composition, at least two groups bonded to the silicon atom in the component (A) are the above-mentioned alkenyl groups. In addition, η in the above formula is a positive number in a range of 1.6 to 2.4. It indicates that the molecular structure of the organic polysiloxane of this component is substantially linear. However, a part of the molecular structure may be branched or have a branched configuration; in addition, an organic polysiloxane having a branched or branched configuration may be used in combination with the above-mentioned organic polysilica.

Page 23 555811 V. Description of the invention (19) The organic compound having an air-oxidizable hardenable unsaturated group containing the component (B) is used to impart sufficient matte properties to the hardened product of the composition. This component hardens the reaction caused by the oxygen contained in the air by the unsaturated group in the molecule. Examples of such compounds include unsaturated high-carbon fatty acids, such as hypolinoleic acid and linoleic acid; lipids and oils including unsaturated high-carbon fatty acids and esters of glycerol, such as tung oil, linseed oil, and soybean oil; etc .; unsaturated Esters of high-carbon fatty acids and alcohols, such as ethyl linolenate and ethyl linoleate; and unsaturated hydrocarbon compounds, such as butadiene, pentadiene, and hexadiene; or polymers thereof. Particularly preferred are hypolinolenic acid, linolenic acid linoleate, tung oil, 1,3-hexadiene and 1,4-polybutadiene. The amount of the ingredient (B) added is 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight, and even more in the range of 0.1 to 10 parts by weight per 100 parts by weight of the above-mentioned ingredient (A). the amount. It should be noted that if the amount of the added ingredient (B) is lower than the lower limit of the above range, the hardened product of the obtained hardenable silicone composition cannot be imparted with sufficient matte properties; on the other hand, if the amount added exceeds the above At the upper limit of the range, the mechanical characteristics of the hardened product of the obtained hardenable silicone composition show degradation. The component (C) of the present invention may be a combination of an organic peroxide or an organic hydrogenated polysiloxane and a platinum-type catalyst. When an organic peroxide is selected as the component (C), the obtained hardenable silicone composition becomes an organic peroxide hardenable composition. On the other hand, when an organic hydrogenated polysiloxane and a platinum-type catalyst are selected, In some cases, the obtained hardenable silicone composition becomes a hydrosilylation reaction hardenable composition. Examples of such organic peroxides include phenylfluorenyl peroxide, p-

Page 24 555811 V. Description of the invention (20) Benzyl benzamyl peroxide, 2, 4-dicumyl peroxide, 2, 5-dimethyl-fluorene (2, 5-third Butylperoxy) hexane, di-tert-butyl peroxide and tert-butyl peroxybenzoate. The amount of the organic peroxide added is desirably in the range of 0.1 to 5 parts by weight per 100 parts by weight of the organopolysiloxane.

It should be noted that the organic hydrogenated polysiloxane is a polysiloxane having at least two hydrogen atoms bonded to silicon atoms in each molecule. The molecular structure of the organic hydrogenated polysiloxane can be linear, branched, or ring-shaped. Examples of such organic hydrogenated polysiloxanes include dimethylpolysiloxanes in which both ends of the molecular chain are closed with difluorenylhydrosilyloxy, in which both ends of the molecular chain are closed with difluorenylhydrosilyloxy. Bis fluorinated siloxane-methyl hydridosilane copolymer, in which both ends of the molecular chain are closed with tris fluorinated siloxy dimethyl hydride siloxane, cyclic fluorinated hydride siloxane, cyclic bis A methylsiloxane-fluorenyl hydride fired oxygen copolymer, and a copolymer including a fired oxygen fired unit represented by formula (CH3) 2HSi01 / 2 and a broken fired fired unit represented by formula Si 04/2. 5 至 10 莫尔 的 量。 It is desirable to add the amount of this organic hydrogenated polysiloxane so that the concentration of hydrogen atoms bonded to silicon atoms in this component is 0.5 to 10 moles per mole of the alkenyl group in the above component (A) .

In addition, examples of platinum catalysts that can be used include chloroplatinic acid, alcohol compounds of gas platinum, dilute hydrocarbon complexes, dilute radicals > oxo fired complexes, and initial carbonyl complexes. . It is desirable that the amount of the platinum-type catalyst to be added is such that the amount of the starting metal in the composition is from 0.1 to 1,000 ppm (weight standard) relative to the organic polyoxygen of the component (A). In addition, it is particularly desirable that the amount be in the range of 1 to 500 ppm. 555811 5. Description of the invention (21) As for other optional ingredients, the composition may contain inorganic fillers, such as fumed silica, precipitated silica, crushed quartz, titanium oxide, iron oxide, calcium carbonate and magnesium carbonate; Pigments, such as carbon black and iron oxide red; and other additives, such as heat resistance improvers, reaction control agents, release agents, plasticizers, sensitizers and polymerization inhibitors. There is no limitation on the method for producing the composition; for example, a method may be used in which ingredients are uniformly mixed by a well-known kneading device such as a two-roller device, a Banbury mixer, a kneading mixer, or a revolving mixer ( A), ingredient (B), ingredient (C) and other optional ingredients. In addition, there is no limitation on the use of the composition; since a dull hardened product can be formed, the composition can be suitably used for filling or adhesion in display devices such as LEDs. EXAMPLES The hardenable silicone composition of the present invention will be described in detail with reference to working examples. In addition, the viscosity values shown in the working examples are the values measured at 25 ° C. In addition, by measuring the gloss of the hardened product (measurement angle 60 °), the degree of surface finish of the hardened product was evaluated. Evenly mix 2 5 parts by weight of a difluorenyl polysiloxane with a viscosity of 500 m P a · s, in which both ends of the molecular chain are closed with trimethoxysilane and 75 parts by weight with 2,000 m Pa.s viscosity of dimethyl polysiloxane, in which both ends of the molecular chain are closed with difluorenyl vinyl siloxane, and 5 parts by weight of carbon black; then 7 parts by weight of 10 mPa · s are mixed Viscosity difluorenyl polysiloxane, in which both ends of the molecular chain are closed with dimethylhydrosilyloxy (so that the hydrogen atom pair bonded to the silicon atom in this component is at the two ends of the above molecular chain with

P.26 555811 V. Description of the invention (22) Molar ratio of vinyl group in dimethylpolysiloxane blocked by dimethylvinylsiloxy is 1.6 amount), 1 part by weight of ethynyl vinegar Acetic acid, and isopropyl alcohol solution of chloro I white acid (used in an amount such that the platinum metal content (weight unit) is 100 ppm relative to the estuone component of the composition), and 2 parts by weight of tung oil Thus, a hardenable silicone composition having a viscosity of 1,500 in Pa · s was produced. This hardenable silicone composition is hardened by heating at 80 ° C for 2 hours, thereby producing a silicone rubber. When the gloss of this silicone rubber was measured after the rubber was allowed to stand at room temperature for one week, the resulting gloss value was 0. (Working example 1). Evenly mix 50 parts by weight of dimethyl polysiloxane with a viscosity of 1,500 m Pa and s, in which both ends of the molecular chain are closed with trimethoxysiloxy and 50 parts by weight Dimethylpolysiloxane with a viscosity of 10,000 mPa, in which both ends of the molecular chain are closed with difluorenylvinylsiloxane, 10 parts by weight of fuming silica having a surface area ratio of 200 square meters per gram , Which has undergone a hydrophobic surface treatment with hexamethyldisilazane, and 0.5 parts by weight of diphenyl ketone; and then 0.5 parts by weight of dimethylsilicone having a viscosity of 5 mP a · s Oxyalkane-fluorenyl hydrosiloxane copolymer (mole ratio of difluorenylsiloxane unit to fluorinated hydrosiloxane unit: 3: 5), in which both ends of the molecular chain are trimethylsiloxy Blocking (The amount of this ingredient used is such that the hydrogen atom pair bonded to the silicon atom in this ingredient is in the above-mentioned difluorenyl polysiloxane blocked with difluorenyl vinylsiloxy at both ends of the molecular chain. Molar ratio of vinyl is 0.5 amount), 0.5 parts by weight of aluminum ethynylacetonate, and isopropyl alcohol solution of chloroplatinic acid (to make Perkin The content amount (basis weight) in an amount of 100 ppm relative to silicon using one of the ingredients of the present composition), 1 part by weight of methyl trimethoxy Silane and 3 parts by weight of linseed oil, thus producing one curable silicone composition

Page 27 555811 V. Description of Invention (23). When the silicone rubber obtained by curing the hardenable silicone composition as in Working Example 1 was left to stand at room temperature in the same manner as in Working Example 1 and then the gloss was measured, the gloss value obtained was 36. (Working example 2). Evenly mix 50 parts by weight of a difluorenyl polysiloxane with a viscosity of 1,500 m Pa and s, in which both ends of the molecular chain are closed with trimethoxysiloxy and 50 parts by weight Organic Molybdenum Oxy-Burning Copolymer Mixture (Viscosity = 7, 0 0 0 m P a · s), which includes 57 mol% of siloxane units represented by the formula Si 04/2, 40.5 mol% of Siloxane units represented by the formula ([: 113) 33 丨 01/2, and 2.5 mol% of the formula ((] 113) 2 (〇112 = 〇1〇8 丨 01/2) , And dimethylpolysiloxane with a viscosity of 2,000 mPa .s, in which both ends of the molecular chain are closed with dimethylvinylsiloxy and 5 parts by weight of carbon black; then 3 parts by weight of carbon black are mixed Copolymer of difluorenylsiloxane-methylhydrosiloxane with a viscosity of 5 mPa.s (molar ratio of difluorenylsiloxane units to methylhydrosiloxane units: 3: 5), in which the molecule The two ends of the chain are closed with a trifluorenylsiloxy group (the amount of this component used is such that the hydrogen atom pair bonded to the silicon atom in this component is between the above-mentioned organosiloxane copolymer and the two ends of the above molecular chain Dimethyl vinyl silicon The molar ratio of the vinyl group in the above mixture of the oxygen-blocked difluorenylpolysiloxane is 1.4), 0.1 part by weight of titanium diisopropoxyfluorene (ethyl acetoacetate), and 2 parts by weight Fluorenyltrisoxylate syringa, and isopropyl alcohol solution of chloropic acid (used so that the amount of the starting metal content (weight unit) is 100 ppm relative to the syringone component of the composition), and 0.5 A part by weight of tung oil is used to produce a hardenable stone eve composition. The silicone rubber obtained by hardening the hardenable silicone composition as in Working Example 1 is left at room temperature in the same manner as in Working Example 1 and then measured for gloss. At this time, the obtained gloss value is 0.

P.28 555811 V. Description of Invention (24) (Working Example 3). Evenly mix 2.5 parts by weight of a difluorenyl polysiloxane having a viscosity of 500 m Pa · s, in which both ends of the molecular chain are closed with trimethoxysiloxy, and 75 parts by weight of 2, 0 0 0 mPa .s viscosity of dimethylpolysiloxane, in which both ends of the molecular chain are closed with difluorenylvinylsiloxy, and 5 parts by weight of carbon black; then 7 parts by weight of 10 mPa · Dimethylpolysiloxane with s viscosity, in which both ends of the molecular chain are closed with dimethylhydrosilyloxy (so that the hydrogen atom pair bonded to the silicon atom in this component is at both ends of the above molecular chain The molar ratio of vinyl group in difluorenyl polysiloxane blocked with dimethylvinylsiloxy is 1.6)), 1 part by weight of ethynyl vinegar is acidic, and the difference between clodronic acid A solution of propanol (used in an amount such that the content of the metal (in weight) relative to the same component of the composition of the present invention is 100 ppm) and 0.2 parts by weight of linoleic acid, so that it can be hardened. Ketone composition. When the silicone rubber obtained by curing the hardenable silicone composition as in Working Example 1 was left at room temperature in the same manner as in Working Example 1 and then the gloss was measured, the gloss value obtained was 0. (Working example 4). Evenly mix 25 parts by weight of dimethylpolysiloxane with a viscosity of 500 mPa · s, in which both ends of the molecular chain are closed with trimethoxysiloxy, and 75 parts by weight with a viscosity of 2,000 mPa Dimethylpolysiloxane, in which both ends of the molecular chain are closed with dimethylvinylsiloxy, and 5 parts by weight of carbon black; and then 7 parts by weight of difluorenyl group having a viscosity of 10 mPa · s Polysilane, in which both ends of the molecular chain are closed with difluorinated hydrosiloxy (so that the hydrogen atom pair bonded to the silicon atom in this component is dimethylvinylsilicon at both ends of the molecular chain Vinyl molybdenum in dimethyl polysiloxane

Page 29 555811 V. Description of the invention (25) Ear ratio is 1.6 amount), 1 part by weight of ethynylacetonate, isopropyl alcohol solution of platinum gas (to make the amount of platinum metal content (weight The unit) is used in an amount of 100 ppm based on the lithone ketone component of the composition, and 0.5 parts by weight of linoleic acid vinegar, thereby producing a hardenable crushed ketone composition. When the silicone rubber obtained by curing the hardenable silicone composition as in Working Example 1 was left at room temperature in the same manner as in Working Example 1 and then the gloss was measured, the obtained gloss value was 0. (Working example 5). Evenly mix 2.5 parts by weight of dimethyl polyxoxane with a viscosity of 500 m P a · s, in which both ends of the molecular chain are closed with trimethoxysiloxy, and 75 parts by weight 2,000 mPa.s viscosity dimethylpolysiloxane, in which both ends of the molecular chain φ are closed with dimethyl vinyloxy group, and 5 parts by weight of carbon black; then 7 parts by weight of 10 m P a · s viscosity of dimethyl polylithium sintering, in which both ends of the molecular chain are closed with difluorinated hydrosilyloxy (so that the hydrogen atom pair bonded to the silicon atom in this component is in the above Wherein the molecular chain is terminated with difluorenylvinylsiloxy at the two ends of the difluorenylpolysiloxane, the molar ratio of vinyl in the difluorenylpolysiloxane is 1.6)), and 1 part by weight of ethynylacetone , Isopropanol solution of chloroarsolic acid (used in an amount such that the platinum metal content (weight unit) is 100 ppm relative to the azulone component of the present composition), and 1,3-hexadecane Diene, thus making a hardenable silicone composition. When the silicone rubber obtained by curing this hardenable silicone composition as in Working Example 1 was left at room temperature in the same manner as in Working Example 1 and then the gloss was measured, the gloss value obtained was _0. (Working example 6). Evenly mix 2 5 parts by weight of dimethylpolysparoxane with a viscosity of 5000 m P a · s, in which both ends of the molecular chain are closed with trimethoxysiloxy, 75 weight

Page 30 555811 V. Description of the invention (26) parts of dimethyl polysiloxane with a viscosity of 2,000 mPa .s, in which both ends of the molecular chain are closed with dimethyl vinyl siloxane and 5 weight Parts of carbon black; then mixed 7 parts by weight of dimethylpolyoxygen with 10 m P a · s viscosity, where both ends of the molecular chain are closed with dimethylhydrosilyloxy (so that in this component The molar ratio of the hydrogen atom bonded to the silicon atom to the vinyl group in the above-mentioned difluorenyl polysiloxane, in which the two ends of the molecular chain are closed with a difluorenyl vinylsiloxy group, is an amount of 1.6), 1 part by weight of ethynylacetone acid, chlorochain acid in isopropanol solution (used so that the amount of platinum metal content (weight unit) is 100 ppm relative to the Shixiyan I component of the composition), And 1 part by weight of polybutadiene in liquid form, thereby producing a hardenable silicone composition. When the silicone rubber obtained by curing the hardenable silicone composition as in Working Example 1 was left at room temperature in the same manner as in Working Example 1 and then the gloss was measured, the obtained gloss value was 0. (Working example 7). In contrast, a hardenable silicone composition was prepared in the same manner as in Working Example 1, except that tung oil was not added. The silicone rubber obtained by hardening the hardenable chopped I composition as in Working Example 1 was prepared as in Working Example 1. When the gloss was left at room temperature in the same manner and the gloss was measured, the gloss value obtained was 90. A hardenable silicone composition was prepared in the same manner as in Working Example 1, except that olive oil (the same amount) was added instead of tung oil. When the stone ketone rubber obtained by hardening the hardenable stone copper copper composition as in Working Example 1 was allowed to stand at room temperature in the same manner as in Working Example 1 and then the gloss was measured, a gloss value of 7 7 was obtained. A hardenable lithone composition was prepared in the same manner as in Working Example 2 except that no diphenyl ketone or linseed oil was added. In the same manner as in Working Example 2, the stone ketone rubber obtained by hardening the hardenable silicone composition as in Working Example 2

Page 31 555811 V. Description of the invention (27) When the temperature is left to stand and the gloss is measured, the gloss value obtained is 8 2. A hardenable silicone composition was prepared in the same manner as in Working Example 3 except that tung oil was not added. When the silicone rubber obtained by curing the hardenable > ketone composition as in Working Example 3 was left to stand at room temperature in the same manner as in Working Example 3 and then the gloss was measured, the gloss value obtained was 89. A hardenable silicone composition was prepared in the same manner as in Operation 裥 6, except that n-hexane (the same amount) was added instead of 1,3-hexadiene. When the silicone rubber obtained by hardening this hardenable silicone composition as in Working Example 6 was allowed to stand at room temperature in the same manner as in Working Example 6 and then the gloss was measured, a gloss value of 90 was obtained. Evenly mix 2 5 parts by weight of dimethyl polyxoxane with a viscosity of 500 m P a · s, in which both ends of the molecular chain are closed with trimethoxysiloxy, 75 parts by weight of 2, 000 mPa .s viscosity of dimethylpolysiloxane, in which both ends of the molecular chain are closed with difluorenyl vinylsiloxy, 5 parts by weight of carbon black and 30 parts by weight with an average of 5 // m Powdered mica with particle size; then 7 parts by weight of dimethylpolysiloxane with 10 m Pa .s viscosity is mixed, in which both ends of the molecular chain are closed with dimethylhydrosilyloxy (so that in this component 6 的 量 量） The hydrogen mole ratio of the hydrogen atom bonded to the silicon atom to the vinyl group in the dimethyl polysiloxane blocked by dimethylvinylsiloxy at both ends of the molecular chain described above is 1.6 amount), 1 part by weight of an ethynylacetone acid file, and an isopropanol solution of chloroplatinic acid (used so that the amount of platinum metal content (weight unit) is 100 ppm relative to the silicone content of the composition), so Manufacture of a hardenable silicone composition with a viscosity of 3, 500 mPa .s. When the silicone rubber obtained by curing the hardenable silicone composition as in Working Example 1 was left at room temperature in the same manner as in Working Example 1 and then the gloss was measured, a gloss value of 57 was obtained.

Page 32 555811 V. Description of the invention (28) A specific example of the hardenable silicone composition of the present invention will be described in detail through working examples. In addition, the viscosity value shown in this working example is the value measured at 25 ° C. The matt degree of the hardened product was evaluated by measuring the gloss of the hardened product (measurement angle: 60 °). 100 parts by weight of an organic polysiloxane having a viscosity of 40 mPa · s is uniformly mixed, which includes 99 mol% of amidinosiloxane unit and 1 mol% of dimethylvinylsiloxane Unit, and 100 parts by weight of powdered silica with an average particle size of 5 // m. Then add an isopropanol solution of chloroplatinic acid (the amount of chloroplatinic acid added is such that the platinum metal concentration is 0.001% by weight relative to the above dimethylpolysiloxane), and 12 parts by weight has a viscosity of 10 mPa .s Difluorenylpolysiloxane, in which both ends of the molecular chain are closed with dimethylhydrosilyloxy, and 1 part by weight of difluorenylsilane-fluorenylhydrogensiloxane copolymerized with 5 mPa · s viscosity (Mole ratio of difluorenylsiloxane units to fluorenylhydrogensiloxane units: 3: 5), in which both ends of the molecular chain are closed with trimethylsiloxy, and 1.5 parts by weight of tung oil In this way, a hardenable Shixi Brew 1 composition was produced. Secondly, this hardenable silicone composition is hardened by heating at 80 ° C for 2 hours, thus manufacturing a hardened product in the form of a rubber. When the glossiness of the hardened product was measured after standing at room temperature for one week, the gloss value obtained was zero. In contrast, a hardenable silicone composition was prepared in the same manner as in the above example, except that tung oil was not added. When the composition was hardened in this way and the gloss of the hardened product was measured, a gloss value of 60 was obtained. The hardenable crushed ketone composition of the present invention is characterized by the fact that the composition can form a hardened product with matte properties when hardened.

Claims (1)

55581Γ 'Report case 9103375 Six years, please Lifan ar Jk supplement IS Xiaochong 丨 1. A hardenable crushed ketone composition containing (A) (a) at least two alkane bonded to a silicon atom in each molecule And it does not contain any alkenyl groups bonded to silicon atoms, and at least two alkenyl groups bonded to silicon atoms in each molecule, and it does not contain any bonds to silicon atoms Alkoxy organic polysiloxane, or (b) organic polysiloxane containing at least two alkoxy groups bonded to a silicon atom and two alkenyl groups bonded to a silicon atom in each molecule Mixture, (B) an organopolysiloxane containing at least two hydrogen atoms bonded to a silicon atom in each molecule, (C) a condensation reaction catalyst, (D) a chain catalyst, and (E) an air oxidation catalyst Hardened unsaturated compounds selected from unsaturated high-carbon fatty acids, lipids and oils including unsaturated high-carbon fatty acids and glycerol esters, unsaturated high-carbon fatty acids and alcohol esters, unsaturated hydrocarbon compounds, and compounds of this type A group of polymers, wherein the content of component (B) is such that The molar ratio of the hydrogen atom linked to the silicon atom to the alkenyl group linked to the silicon atom in the component (A) is in the range of 0.3 to 20, and the content of the component (C) is sufficient to combine the above by a condensation reaction The amount of the material hardened, the content of the component (D) is an amount sufficient to harden the above composition by the hydrogen crushing reaction, and the content of the component (E) is 0 in 100 parts by weight of the silicone component in the above composition. A range of 0.01 to 50 parts by weight. 2. The hardenable silicone composition according to item 1 of the patent application, wherein the air-oxidizable hardenable unsaturated compound has at least two molecules per molecule O: \ 62 \ 62752-920129.ptc P.35 555811 _Case No. 89103375_f: > Year i Month __ Sixth, the scope of patent application aliphatic compounds of unsaturated bonds. 3. The hardenable silicone composition according to item 1 of the scope of the patent application, wherein the air-oxidizable hardenable unsaturated compound is hypolinolenic acid, hypolinolenic acid, and tung oil, linseed oil, 1,3-hexane Difluorene or polybutadiene. 4. The hardenable silicone composition according to item 1 of the scope of patent application, wherein the composition is a filler or an adhesive for a display device. 5. A hardenable crushed ketone composition comprising: (A) 100 parts by weight of an organopolysiloxane R, S i 〇 (4-n) / 2 wherein R1 is substituted or unsubstituted Monovalent hydrocarbon groups, which may be the same or different, and η is a positive number from 1.6 to 2.4; (B) (K01 to 50 parts by weight of an organic compound having an air oxidation hardenable unsaturated group, which is selected from the group consisting of unsaturated High-carbon fatty acids, lipids and oils including unsaturated high-carbon fatty acids and esters of glycerol, unsaturated high-carbon fatty acids and esters of alcohols, groups of unsaturated hydrocarbon compounds and polymers of such compounds; and (C) hardening 6. The hardenable silicone composition according to item 5 of the scope of patent application, wherein the organopolysiloxane of component (A) has at least two unsaturated groups per molecule, and the hardener of component (C) includes Organic hydrogenated polysiloxane and platinum-type catalyst. 7. The hardenable silicone composition according to item 5 of the patent application scope, wherein the composition is used as a display device filler or an adhesive. O: \ 62 \ 62752-920129.ptc Page 36