Classifications

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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
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  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
  • C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
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  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/91—Polymers modified by chemical after-treatment
  • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/916—Dicarboxylic acids and dihydroxy compounds
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
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  • 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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  • 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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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2300/00—Characterised by the use of unspecified polymers
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2383/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2383/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
  • C08K2003/222—Magnesia, i.e. magnesium oxide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
  • C08K2003/265—Calcium, strontium or barium carbonate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/001—Conductive additives
• • C—CHEMISTRY; METALLURGY
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids

Definitions

• the present invention relates to an inorganic filler fluidity modifier, an inorganic filler-containing composition, and a thermally conductive silicone sheet.
• Building materials, automobile parts, sanitary absorbent articles, stone paper, heat dissipating materials, etc. are molded from compositions containing inorganic fillers, and the inorganic fillers improve impact resistance, bending resistance, dimensional stability, moisture permeability, and heat dissipation properties.
• Various functions such as
• calcium carbonate is generally used as an inorganic filler, but increasing the amount of calcium carbonate increases the problem of increased viscosity and poor moldability and handling.
• Patent Document 1 As a means to solve the problem that the moldability of the composition is impaired due to the addition of filler, a method has been proposed in which the fluidity of the composition is improved by further adding a fluidity modifier that improves the fluidity of the filler. (For example, Patent Document 1).
• the problem to be solved by the present invention is to provide an inorganic filler fluidity modifier that suppresses viscosity changes over time and improves the fluidity of an inorganic filler.
• Another problem to be solved by the present invention is to provide an inorganic filler-containing composition in which changes in viscosity over time are suppressed and the fluidity of the inorganic filler is improved.
• Another problem to be solved by the present invention is to provide a molded article and a thermally conductive silicone sheet whose flexibility is not impaired even when filled with an inorganic filler at a high concentration.
• polyester having a specific structure and specific physical properties exhibits an excellent effect of suppressing viscosity change and improving fluidity with respect to inorganic fillers.
• the present invention has been completed.
• an inorganic filler fluidity modifier that is a polyester represented by the following general formula (1-1) or (1-2), An inorganic filler fluidity modifier in which the polyester has an acid value in the range of 3 to 400 mgKOH/g and a hydroxyl value of less than 9 mgKOH/g.
• G is an aliphatic diol residue having 2 to 20 carbon atoms
• A is an aliphatic dicarboxylic acid residue having 2 to 10 carbon atoms
• X 1 and X 2 are each independently an aliphatic polybasic acid residue having 2 to 10 carbon atoms or an aromatic polybasic acid residue having 6 to 15 carbon atoms
• Y is a monocarboxylic acid residue having 1 to 20 carbon atoms
• Z is a monoalcohol residue having 2 to 30 carbon atoms
• p is an integer obtained by subtracting one from the number of basic acid functional groups of the aliphatic polybasic acid residue or aromatic polybasic acid residue of X1
• q is an integer obtained by subtracting one from the number of basic acid functional groups of the aliphatic polybasic acid residue or aromatic polybasic acid residue of X 2
• n represents the number of repetitions.
• the inorganic filler fluidity modifier described in . 9 An inorganic filler-containing composition containing an inorganic filler and the inorganic filler fluidity modifier according to any one of 1 to 8. 10. 9.
• Composition. 11 11.
• a thermally conductive silicone sheet containing a silicone resin, an inorganic filler, and an inorganic filler fluidity modifier is one or more selected from the group consisting of magnesium oxide, alumina, and aluminum hydroxide,
• the inorganic filler fluidity modifier is a polyester represented by the following general formula (1-1) or (1-2), has an acid value in the range of 3 to 400 mgKOH/g, and has a hydroxyl value of 9 mgKOH.
• the mass ratio of the silicone resin and the inorganic filler is in the range of 50:50 to 1:99, A thermally conductive silicone sheet containing the inorganic filler fluidity modifier in an amount of 0.01 to 5 parts by mass based on 100 parts by mass of the total amount of the silicone resin and the inorganic filler.
• G is an aliphatic diol residue having 2 to 20 carbon atoms
• A is an aliphatic dicarboxylic acid residue having 2 to 10 carbon atoms
• X 1 and X 2 are each independently an aliphatic polybasic acid residue having 2 to 10 carbon atoms or an aromatic polybasic acid residue having 6 to 15 carbon atoms
• Y is a monocarboxylic acid residue having 1 to 20 carbon atoms
• Z is a monoalcohol residue having 2 to 30 carbon atoms
• p is an integer obtained by subtracting one from the number of basic acid functional groups of the aliphatic polybasic acid residue or aromatic polybasic acid residue of X1
• q is an integer obtained by subtracting one from the number of basic acid functional groups of the aliphatic polybasic acid residue or aromatic polybasic acid residue of X 2
• n represents the number of repetitions.
• the shear A hardness when the mass ratio of the silicone resin and the inorganic filler [silicone resin: inorganic filler] is 20:80 is defined as H 80 , and the mass ratio [silicone resin: inorganic filler] of the silicone resin and the inorganic filler is 20:80.
• the present invention can provide an inorganic filler fluidity modifier that suppresses viscosity changes over time and improves the fluidity of inorganic fillers. According to the present invention, it is possible to provide an inorganic filler-containing composition in which viscosity change over time is suppressed and the fluidity of the inorganic filler is improved. ADVANTAGE OF THE INVENTION According to the present invention, a molded article and a thermally conductive silicone sheet that do not lose flexibility even when filled with a high concentration of inorganic filler can be provided.
• the inorganic filler fluidity modifier of the present invention is a polyester represented by the following general formula (1-1) or (1-2).
• the polyester that is the inorganic filler fluidity modifier of the present invention may be referred to as "the polyester of the present invention”.
• G is an aliphatic diol residue having 2 to 20 carbon atoms
• A is an aliphatic dicarboxylic acid residue having 2 to 10 carbon atoms
• X 1 and X 2 are each independently an aliphatic polybasic acid residue having 2 to 10 carbon atoms or an aromatic polybasic acid residue having 6 to 15 carbon atoms
• Y is a monocarboxylic acid residue having 1 to 20 carbon atoms
• Z is a monoalcohol residue having 2 to 30 carbon atoms
• p is an integer obtained by subtracting one from the number of basic acid functional groups of the aliphatic polybasic acid residue or aromatic polybasic acid residue of X1
• q is an integer obtained by subtracting one from the number of basic acid functional groups of the aliphatic polybasic acid residue or aromatic polybasic acid residue of X 2
• n represents the number of repetitions.
• the polyester of the present invention can ensure compatibility with the composition by having the carboxyl group at one end adsorbed to the inorganic filler and the polyester chain containing the other end being blocked, thereby improving the fluidity of the inorganic filler. It is thought to be modified.
• diol residue and “alcohol residue” refer to the organic group remaining after removing the hydroxyl group from diol and alcohol.
• carboxylic acid residue refers to the organic group remaining after removing the carboxyl group from carboxylic acid. Regarding the number of carbon atoms in the carboxylic acid residue, carbon atoms in the carboxyl group are not included.
• a "polybasic acid residue” is an organic group obtained by removing the basic acid functional group from a polybasic acid having two or more basic acid functional groups.
• the polybasic acid residue is a dicarboxylic acid residue, a tricarboxylic acid residue, or a tetracarboxylic acid residue
• the dicarboxylic acid residue, the tricarboxylic acid residue, or the tetracarboxylic acid residue has This shows the remaining organic groups after removing the carboxyl group.
• the number of carbon atoms in dicarboxylic acid residues, tricarboxylic acid residues, and tetracarboxylic acid residues does not include carbon atoms in carboxyl groups.
• the aliphatic chain of the aliphatic diol residue having 2 to 20 carbon atoms in G may be linear or branched, and may include an alicyclic structure and/or an ether bond. Further, the fatty chain of the aliphatic diol residue of G may be a saturated fatty chain or an unsaturated fatty chain having a carbon-carbon unsaturated bond.
• the aliphatic diol residue having 2 to 20 carbon atoms in G is preferably an aliphatic diol residue having a branched structure having 3 to 20 carbon atoms, and is more preferably represented by the following general formula (G-1). It is a diol.
• G-1 general formula (G-1)
• p is an integer of 1 or more
• q is an integer of 0 or more
• r is an integer of 1 or more
• R is a hydrogen atom or an alkyl group having 1 or more carbon atoms
• at least one of the r R is an alkyl group having 1 or more carbon atoms
• the total number of carbon atoms of p, q, r and R is an integer of 3 to 20.
• the alkyl group for R is preferably an alkyl group having 7 to 18 carbon atoms, more preferably an alkyl group having 10 to 18 carbon atoms.
• Examples of aliphatic diol residues having 2 to 20 carbon atoms in G include ethylene glycol residues, 1,2-propylene glycol residues, 1,3-propanediol residues, 1,2-butanediol residues, 1,3-butanediol residue, 2-methyl-1,3-propanediol residue, 1,4-butanediol residue, 1,5-pentanediol residue, 2,2-dimethyl-1,3- Propanediol (neopentyl glycol) residue, 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane) residue, 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane) residue, 3-methyl-1,5-pentanediol residue, 1,6-hexanediol residue, 2,2,4-trimethyl 1,3-p
• the aliphatic diol residue having 2 to 20 carbon atoms in G may include an alicyclic structure, and examples of the aliphatic diol residue having 2 to 20 carbon atoms containing the alicyclic structure include, for example, 1,3- Cyclopentanediol residue, 1,2-cyclohexanediol residue, 1,3-cyclohexanediol residue, 1,4-cyclohexanediol residue, 1,2-cyclohexanedimethanol residue, 1,4-cyclohexanedimethanol residue Examples include residues.
• the aliphatic diol residue having 2 to 20 carbon atoms in G may include an ether bond (-O-), and the aliphatic diol residue having 2 to 20 carbon atoms containing the ether bond is, for example, diethylene glycol. residue, triethylene glycol residue, tetraethylene glycol residue, dipropylene glycol residue, tripropylene glycol residue, and the like.
• G is preferably an aliphatic diol residue having 2 to 14 carbon atoms, more preferably an ethylene glycol residue, a diethylene glycol residue, a 1,2-propylene glycol residue, a 1,6-hexanediol residue, 3-methyl-1,5-pentanediol residue, 1,4-butanediol residue, 1,3-butanediol residue, 1,2-tetradecanediol residue, 1,2-dodecanediol residue be.
• the aliphatic chain of the aliphatic dicarboxylic acid residue of A may be linear or branched, and may include an alicyclic structure and/or an ether bond. Further, the fatty chain of the aliphatic dicarboxylic acid residue of A may be a saturated fatty chain or an unsaturated fatty chain having a carbon-carbon unsaturated bond.
• Examples of aliphatic dicarboxylic acid residues having 2 to 10 carbon atoms in A include malonic acid residues, succinic acid residues, glutaric acid residues, adipic acid residues, pimelic acid residues, suberic acid residues, and azelaic acid residues. residues, sebacic acid residues, dodecanedicarboxylic acid residues, maleic acid residues, fumaric acid residues, 1,2-dicarboxycyclohexane residues, 1,2-dicarboxycyclohexene residues, etc., preferably These are succinic acid residue, glutaric acid residue, adipic acid residue or sebacic acid residue.
• the aliphatic dicarboxylic acid residue having 2 to 10 carbon atoms in A is preferably an aliphatic dicarboxylic acid residue having 4 to 10 carbon atoms.
• the aliphatic chains of X 1 and X 2 aliphatic polybasic acid residues having 2 to 10 carbon atoms may be linear or branched, and may include an alicyclic structure and/or an ether bond.
• the aliphatic polybasic acid residues having 2 to 10 carbon atoms of X 1 and X 2 are preferably aliphatic dicarboxylic acid residues having 2 to 10 carbon atoms;
• Dicarboxylic acid residues include succinic acid residue, glutaric acid residue, adipic acid residue, pimelic acid residue, suberic acid residue, azelaic acid residue, sebacic acid residue, dodecanedicarboxylic acid residue, maleic acid residue.
• succinic acid residues preferably succinic acid residues, glutaric acid residues, adipic acid residues, sebacic acid residues, etc. It is an acid residue or a dodecanedicarboxylic acid residue.
• the aromatic polybasic acid residue having 6 to 15 carbon atoms of X 1 and X 2 is preferably an aromatic dicarboxylic acid residue having 6 to 15 carbon atoms, or an aromatic tricarboxylic acid residue having 6 to 15 carbon atoms. group or an aromatic tetracarboxylic acid residue having 6 to 15 carbon atoms, and specific examples thereof include phthalic acid residue, trimellitic acid residue, pyromellitic acid residue, etc.
• X 1 and X 2 are preferably aliphatic dicarboxylic acid residues having 2 to 10 carbon atoms, more preferably aliphatic dicarboxylic acid residues having 5 to 10 carbon atoms.
• the monocarboxylic acid residue having 1 to 20 carbon atoms in Y may be, for example, an aliphatic monocarboxylic acid residue having 1 to 20 carbon atoms or an aromatic monocarboxylic acid residue having 1 to 20 carbon atoms. , preferably an aliphatic monocarboxylic acid residue having 1 to 20 carbon atoms.
• the aliphatic chain of the aliphatic monocarboxylic acid residue having 1 to 20 carbon atoms may be linear or branched; structure and/or may include ether bonds.
• the fatty chain of the aliphatic monocarboxylic acid residue having 1 to 20 carbon atoms may be a saturated fatty chain or an unsaturated fatty chain having a carbon-carbon unsaturated bond.
• Monocarboxylic acid residues having 1 to 20 carbon atoms in Y include acetic acid residues, propionic acid residues, butanoic acid residues, hexanoic acid residues, octanoic acid residues, octyl acid residues, and benzoic acid residues.
• dimethylbenzoic acid residue dimethylbenzoic acid residue, trimethylbenzoic acid residue, tetramethylbenzoic acid residue, ethylbenzoic acid residue, propylbenzoic acid residue, butylbenzoic acid residue, cumic acid residue, paratertiary butylbenzoic acid residue group, orthotoluic acid residue, metatoluic acid residue, paratoluic acid residue, ethoxybenzoic acid residue, propoxybenzoic acid residue, anisic acid residue, and the like.
• the monoalcohol residue having 2 to 30 carbon atoms in Z may be, for example, an aliphatic monoalcohol residue having 2 to 30 carbon atoms or an aromatic monoalcohol residue having 6 to 30 carbon atoms, and is preferably It is an aliphatic monoalcohol residue having 2 to 30 carbon atoms.
• the aliphatic chain of the aliphatic monoalcohol residue having 2 to 30 carbon atoms may be linear or branched, and may have an alicyclic structure or /or may contain an ether bond.
• the fatty chain of the aliphatic monoalcohol residue having 2 to 30 carbon atoms may be a saturated fatty chain or an unsaturated fatty chain having a carbon-carbon unsaturated bond.
• the monoalcohol residue having 2 to 30 carbon atoms in Z is preferably an alkyl alcohol residue having 2 to 10 carbon atoms or an alcohol residue of a polyalkylene glycol monoalkyl ether having 5 to 30 carbon atoms.
• the alkyl alcohol residue having 2 to 10 carbon atoms of Z includes ethanol residue, propanol residue, butanol residue, pentanol residue, hexanol residue, cyclohexanol residue, heptanol residue, octanol residue, Examples include nonanol residues and decanol residues.
• the alcohol residue of the polyalkylene glycol alkyl ether having 5 to 30 carbon atoms in Z is polyethylene glycol alkyl ether such as diethylene glycol monomethyl ether or triethylene glycol monomethyl ether; polypropylene such as polypropylene glycol monomethyl ether or polypropylene glycol monoethyl ether; Glycol alkyl ether; Alcohol residues such as (polyethylene glycol/polypropylene glycol) monoalkyl ether can be mentioned.
• the average value of the number of repetitions of n is preferably in the range of 0 to 20, more preferably in the range of 0.2 to 15, and even more preferably in the range of 0.5 to 10.
• the average value of the number of repeats of n can be calculated from the number average molecular weight of the polyester of the present invention.
• p is an integer obtained by subtracting one from the number of basic acid functional groups of the aliphatic polybasic acid residue or aromatic polybasic acid residue of X 1
• q is the number of basic acid functional groups of the aliphatic polybasic acid residue or aromatic polybasic acid residue of X 2 . It is an integer obtained by subtracting one from the number of basic acid functional groups in the group polybasic acid residue. Therefore, for example, when X 1 and X 2 are each independently aliphatic dicarboxylic acid residues having 2 to 10 carbon atoms, the number of basic acid functional groups (carboxyl groups) that X 1 and X 2 have is 2, p and q each become 1, and the general formulas (1-1) and (1-2) become as follows.
• the polyester of the present invention may be any polyester that satisfies the above general formula (1-1) or (1-2), and may be used as a mixture of two or more polyesters having different structures.
• the number average molecular weight (Mn) of the polyester of the present invention is, for example, in the range of 500 to 5,000, preferably in the range of 1,000 to 4,000, more preferably in the range of 1,500 to 4,000. , more preferably from 1,500 to 3,500.
• the above number average molecular weight (Mn) is a value converted to polystyrene based on gel permeation chromatography (GPC) measurement, and is measured by the method described in Examples.
• the acid value of the polyester of the present invention is in the range of 3 to 400 mgKOH/g, preferably in the range of 3 to 100 mgKOH/g, and more preferably in the range of 3 to 50 mgKOH/g.
• the acid value of the polyester of the present invention is within this range, the fluidity improving effect is effectively expressed through interaction with the inorganic filler.
• the acid value of the above polyester is confirmed by the method described in Examples.
• the hydroxyl value of the polyester of the present invention is less than 9 mgKOH/g, preferably 8 mgKOH/g or less, and more preferably 7 mgKOH/g or less. Since the hydroxyl value of the polyester of the present invention is less than 9.0 mgKOH/g, the affinity and reactivity of the polyester with respect to the base component contained in the inorganic filler-containing composition described below is reduced, and the viscosity of the entire composition is reduced. Can be suppressed.
• the lower limit of the hydroxyl value of the polyester of the present invention is, for example, 0 mgKOH/g or more or 1 mgKOH/g or more. The hydroxyl value of the above polyester is confirmed by the method described in Examples.
• the properties of the polyester of the present invention vary depending on the number average molecular weight, composition, etc., but are preferably liquid at room temperature.
• liquid at room temperature means that the polyester of the present invention exhibits fluidity at room temperature of 25°C.
• the polyester of the present invention is obtained using a reaction raw material containing an aliphatic diol, an aliphatic dicarboxylic acid, an aliphatic polybasic acid and/or an aromatic polybasic acid, and a monoalcohol and/or a monocarboxylic acid.
• the reaction raw material means a raw material constituting the polyester of the present invention, and does not include a solvent or a catalyst that does not constitute the polyester.
• the method for producing the polyester of the present invention is not particularly limited, and it can be produced by a known method, and can be produced by the production method described below.
• the reaction raw materials for the polyester of the present invention may include aliphatic diols, aliphatic dicarboxylic acids, aliphatic polybasic acids and/or aromatic polybasic acids, monoalcohols and/or monocarboxylic acids, and other raw materials. May include.
• the reaction raw materials for the polyester of the present invention preferably contain at least 90% by mass of aliphatic diols, aliphatic dicarboxylic acids, aliphatic polybasic acids and/or aromatic polybasic acids, and monoalcohols based on the total amount of the reaction raw materials.
• a monocarboxylic acid more preferably consisting only of an aliphatic diol, an aliphatic dicarboxylic acid, an aliphatic polybasic acid and/or an aromatic polybasic acid, and a monoalcohol and/or a monocarboxylic acid.
• the aliphatic diol used in the production of the polyester of the present invention is an aliphatic diol corresponding to the aliphatic diol residue having 2 to 20 carbon atoms in G, and the aliphatic diol used may be used alone. , two or more types may be used in combination.
• the aliphatic dicarboxylic acid used in the production of the polyester of the present invention is an aliphatic dicarboxylic acid corresponding to the aliphatic dicarboxylic acid residue having 2 to 10 carbon atoms in A, and the aliphatic dicarboxylic acid used is one type alone. It may be used or two or more types may be used in combination.
• the aliphatic polybasic acid used in the production of the polyester of the present invention is an aliphatic polybasic acid corresponding to the aliphatic polybasic acid residues of X 1 and X 2 having 2 to 10 carbon atoms, and the aliphatic polybasic acid used One type of polybasic acid may be used alone, or two or more types may be used in combination.
• the aromatic polybasic acid used in the production of the polyester of the present invention is an aromatic polybasic acid corresponding to the aromatic polybasic acid residues of X 1 and X 2 having 6 to 15 carbon atoms, and One type of polybasic acid may be used alone, or two or more types may be used in combination.
• the monocarboxylic acid used in the production of the polyester of the present invention is a monocarboxylic acid corresponding to the monocarboxylic acid residue having 1 to 20 carbon atoms in Y, and the monocarboxylic acid used may be used alone. , two or more types may be used in combination.
• the monoalcohol used in the production of the polyester of the present invention is a monoalcohol corresponding to the monoalcohol residue having 2 to 30 carbon atoms in Z, and the monoalcohol used may be used alone or in combination of two or more. may be used together.
• reaction raw material polybasic acid aliphatic polybasic acid and/or aromatic polybasic acid
• the reaction raw material is an aliphatic diol, aliphatic dicarboxylic acid, monoalcohol and/or monocarboxylic acid. Just include acid.
• Hydrogenated vegetable oil fatty acids may be used as monocarboxylic acids for producing the polyester of the present invention.
• the hydrogenated vegetable oil fatty acids include hydrogenated coconut oil fatty acids, hydrogenated palm kernel oil fatty acids, hydrogenated palm oil fatty acids, hydrogenated olive oil fatty acids, hydrogenated castor oil fatty acids, hydrogenated rapeseed oil fatty acids, and the like. These are obtained by hydrolyzing and hydrogenating oils obtained from coconut, palm kernel, palm, olive, castor, and rapeseed, respectively, and all of them contain aliphatic monocarboxylic acids having 8 to 21 carbon atoms. It is a mixture of two or more types of long chain aliphatic monocarboxylic acids.
• the above-mentioned vegetable oil fatty acid that is not hydrogenated may be used as long as the effects of the present invention are not impaired.
• vegetable oil fatty acids are not limited to those mentioned above.
• polyester of the present invention is a polyester using an aliphatic diol, an aliphatic dicarboxylic acid, an aliphatic polybasic acid and/or an aromatic polybasic acid, and a hydrogenated vegetable oil fatty acid as reaction raw materials, there are two types of polyesters obtained. It is obtained as a mixture of polyesters represented by the above general formula (1-1).
• aliphatic diol aliphatic dicarboxylic acid, aliphatic polybasic acid, aromatic polybasic acid, monoalcohol, and monocarboxylic acid used in the production of the polyester of the present invention
• derivatives thereof can be used.
• the derivatives include esters, acid chlorides, acid anhydrides, and cyclic esters.
• epoxy compounds since epoxy compounds ring-open to form diols when reacted with carboxylic acids, aliphatic epoxy compounds may be used as derivatives of aliphatic diols used in the reaction raw materials of the present invention.
• the polyester represented by the general formula (1-1) can be prepared by combining, for example, an aliphatic diol, an aliphatic dicarboxylic acid, an aliphatic polybasic acid and/or an aromatic polybasic acid, and a monocarboxylic acid, each having an equivalent weight of carboxyl groups. It can be produced by setting the amount to be larger than the equivalent of the hydroxyl group, charging it all at once, and reacting it.
• the polyester represented by the general formula (1-1) can be prepared by, for example, reacting an aliphatic diol and an aliphatic dicarboxylic acid in an arbitrary equivalent ratio, and then converting the terminal hydroxyl group of the obtained polyester into a monocarboxylic acid and an aliphatic dicarboxylic acid. It can also be produced by reacting with a group polybasic acid and/or an aromatic polybasic acid and capping the hydroxyl group with a carboxylic acid residue.
• the polyester represented by the general formula (1-2) can be prepared by combining, for example, an aliphatic diol, an aliphatic dicarboxylic acid, an aliphatic polybasic acid and/or an aromatic polybasic acid, and a monoalcohol, such that the equivalent of the carboxyl group is a hydroxyl group. It can be produced by setting the amount to be larger than the equivalent of , charging it all at once and reacting it.
• the polyester represented by the general formula (1-2) can be prepared by, for example, reacting an aliphatic diol and an aliphatic dicarboxylic acid in an arbitrary equivalent ratio, and then adding a monoalcohol and an aliphatic polyester to the ends of the resulting polyester. It can also be produced by reacting with a basic acid and/or an aromatic polybasic acid.
• the reaction of the reaction raw materials is preferably carried out in the presence of an esterification catalyst if necessary, for example, at a temperature of 170 to 250°C for 10 to 25 hours.
• an esterification catalyst for example, at a temperature of 170 to 250°C for 10 to 25 hours.
• conditions such as temperature and time for the esterification reaction are not particularly limited and may be set as appropriate.
• esterification catalyst examples include titanium catalysts such as tetraisopropyl titanate and tetrabutyl titanate; zinc catalysts such as zinc acetate; tin catalysts such as tin octylate and dibutyltin oxide; and p-toluenesulfonic acid.
• titanium catalysts such as tetraisopropyl titanate and tetrabutyl titanate
• zinc catalysts such as zinc acetate
• tin catalysts such as tin octylate and dibutyltin oxide
• p-toluenesulfonic acid examples include organic sulfonic acid catalysts.
• the amount of the esterification catalyst to be used may be set as appropriate, but it is usually used in the range of 0.0001 to 0.1 part by mass based on 100 parts by mass of the total amount of reaction raw materials.
• the inorganic filler fluidity modifier of the present invention can function as a fluidity modifier for an inorganic filler in a composition containing an inorganic filler (inorganic filler-containing composition).
• inorganic filler-containing composition By including the inorganic filler fluidity modifier of the present invention, the amount of inorganic filler filled in the composition can be increased, and handling properties, moldability, etc. can also be improved.
• Each component contained in the inorganic filler-containing composition of the present invention will be explained below.
• the inorganic filler contained in the inorganic filler-containing composition of the present invention is not particularly limited, and includes, for example, calcium carbonate, talc, silica, clay, antimony oxide, alumina, aluminum hydroxide, magnesium hydroxide, hydrotalcite, and calcium silicate. , magnesium oxide, potassium titanate, barium titanate, titanium oxide, calcium oxide, manganese dioxide, boron nitride, aluminum nitride, and the like.
• the inorganic fillers may be used alone or in combination of two or more.
• the inorganic filler is preferably one or more selected from the group consisting of calcium carbonate, silica, alumina, aluminum hydroxide, barium titanate, talc, magnesium oxide, boron nitride, and aluminum nitride, and more preferably calcium carbonate. , alumina, aluminum hydroxide, talc, and magnesium oxide.
• the particle size, fiber length, fiber diameter, and other shapes of the inorganic filler are not particularly limited, and may be adjusted as appropriate depending on the intended use.
• the surface treatment state of the inorganic filler is not particularly limited, and the surface may be modified with, for example, saturated fatty acids depending on the intended use.
• the content of the inorganic filler is not particularly limited, but is, for example, 40 to 98% by mass, preferably 45 to 95% by mass, more preferably 55 to 95% by mass, based on the total solid content of the inorganic filler-containing composition.
• solid content refers to components in the inorganic filler-containing composition other than volatile substances such as water and solvents. Note that the solid content includes those that are liquid, syrupy, or waxy at room temperature around 25°C, and does not necessarily mean solid.
• the content of the inorganic filler fluidity modifier of the present invention is not particularly limited, but is, for example, in the range of 0.01 to 30 parts by mass of the inorganic filler fluidity modifier of the present invention per 100 parts by mass of the inorganic filler. , preferably in the range of 0.05 to 10 parts by mass of the inorganic filler fluidity modifier of the present invention per 100 parts by mass of the inorganic filler, more preferably in the range of 0.05 to 10 parts by mass of the inorganic filler fluidity modifier of the present invention per 100 parts by mass of the inorganic filler.
• the content of the property modifier is in the range of 0.1 to 5.0 parts by mass.
• the inorganic filler-containing composition of the present invention preferably contains a plasticizer.
• the plasticizer include benzoic acid esters such as diethylene glycol dibenzoate; dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and phthalate.
• Phthalic acid esters such as diundecyl acid (DUP) and ditridecyl phthalate (DTDP); Terephthalic acid esters such as bis(2-ethylhexyl) terephthalate (DOTP); Isophthalic acids such as bis(2-ethylhexyl) isophthalate (DOIP) Esters; Pyromellitic acid esters such as tetra-2-ethylhexyl pyromellitate (TOPM); di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2 sebacate - Aliphatic dibasic acid esters such as ethylhexyl (DOS) and diisononyl sebacate (DINS); phosphoric acid esters such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphat
• the content of the plasticizer is not particularly limited, but is, for example, in the range of 5 to 300 parts by mass of plasticizer per 100 parts by mass of inorganic filler, preferably 10 to 200 parts by mass of plasticizer per 100 parts by mass of inorganic filler. This is within the scope of the department.
• the additives contained in the inorganic filler-containing composition of the present invention are not limited to the inorganic filler fluidity modifier of the present invention and the plasticizer, but may include other additives other than these.
• the other additives include thinners, flame retardants, stabilizers, stabilizing aids, colorants, processing aids, fillers, antioxidants (antiaging agents), ultraviolet absorbers, and light stabilizers. , a lubricant, an antistatic agent, a crosslinking aid, and the like.
• the inorganic filler-containing composition of the present invention preferably contains a resin as a base component, and examples of the resin include, but are not limited to, polyolefin, polyester, polysulfide, polyvinyl chloride, modified polysulfide, silicone resin, modified silicone resin, acrylic resin, etc. Examples include urethane resin, epoxy resin, polyurethane, polyisocyanate, acrylic resin, polyester, and unsaturated polyester.
• the resin to be used may be determined depending on the intended use, and the above resins may be used alone or in combination of two or more.
• the fluidity improving effect of the inorganic filler fluidity modifier of the present invention can be particularly expected.
• the base component of the inorganic filler-containing resin composition of the present invention is not limited to resin, and the inorganic filler fluidity modifier of the present invention can be suitably used even if it is a viscous compound such as castor oil or asphalt.
• the content of the base component is not particularly limited, but is, for example, in the range of 2 to 150 parts by mass per 100 parts by mass of the inorganic filler, preferably in the range of 2 to 150 parts by mass per 100 parts by mass of the inorganic filler.
• the range is from 5 to 85 parts by mass.
• the inorganic filler-containing composition of the present invention can be suitably used as a paste-like resin composition that requires fluidity during use.
• the inorganic filler fluidity modifier of the present invention can reduce the viscosity of the composition and increase the amount of inorganic filler filled, so it can be applied to paints, adhesives, structural materials, etc. It is suitable for structural materials (building materials) for which an increase in filler content is desired and for polysulfide sealing materials that have a particularly high filler content.
• composition examples for each use when the inorganic filler-containing composition of the present invention is used as a paste-like resin composition will be explained.
• the resin contained in the inorganic filler-containing composition used for the structural material examples include polyolefin, polyurethane, unsaturated polyester, and the like.
• the resin used for structural materials (building materials) differs depending on the purpose; for example, for waterproof materials, polyurethane is mainly used as the resin component, and for artificial marble, unsaturated polyester is mainly used.
• the inorganic filler-containing composition used for the waterproof material includes, for example, a base component containing an isocyanate group-containing compound, an aromatic polyamine,
• the composition is a polyurethane composition containing a curing agent component containing one or more selected from the group consisting of polyol, water, and moisture.
• the isocyanate group-containing compound contained in the main component is preferably an isocyanate group-terminated polyurethane prepolymer obtained by reacting a polyisocyanate having a diphenylmethane diisocyanate structure with a polyol.
• the polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 2,2'-diphenylmethane diisocyanate.
• an isocyanate mixture consisting of 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and/or 2,2'-diphenylmethane diisocyanate is preferred.
• polyol polyoxypropylene polyol is preferable, and polyoxypolypropylene diol alone or a mixture of polyoxypropylene diol and polyoxypropylene triol is more preferable.
• the ratio of polyisocyanate to polyol in the isocyanate group-terminated urethane prepolymer is preferably in the range of 1.8 to 2.5 in terms of the molar ratio of isocyanate groups to hydroxyl groups (NCO/OH). Further, the isocyanate group content (NCO group content) in the isocyanate group-terminated urethane prepolymer is preferably in the range of 2 to 5% by mass.
• aromatic polyamine contained in the curing agent component examples include 4,4'-methylenebis(2-chloroaniline), dimethylthiotoluenediamine, diethyltoluenediamine, and the like.
• 4,4'-methylenebis(2-chloroaniline) is known as "MOCA” and is widely used.
• the polyol contained in the curing agent component is preferably a polyether polyol, and particularly preferably a polyoxypropylene polyol.
• the number of functional groups in this polyol is preferably in the range of 2 to 4, more preferably in the range of 2 to 3.
• the mixing ratio of the main resin and the curing agent is such that the molar ratio of the isocyanate group contained in the main resin to the active hydrogen-containing group contained in the curing agent (NCO/(NH 2 +OH)) is, for example, 1.
• the range is from .0 to 2.0, preferably from 1.0 to 1.8, and more preferably from 1.0 to 1.3.
• the curing agent component may contain an inorganic filler, and examples of the inorganic filler include calcium carbonate, talc, clay, silica, and carbon.
• the content of the inorganic filler in the polyurethane composition is preferably in the range of 10 to 60 parts by weight, and preferably in the range of 20 to 50 parts by weight, based on 100 parts by weight of the resin component. By setting the content of the inorganic filler within the range, a good balance can be achieved between the curability of the composition and the performance of the resulting waterproof material.
• the viscosity of both the base resin and curing agent is usually high (base resin: for example, in the range of 7 to 10 Pa.S, curing agent: for example, in the range of 10 to 30 Pa.S), and in winter when the temperature drops, Since the viscosity further increases, the inorganic filler fluidity modifier of the present invention is useful because it can improve the dispersibility and content of the inorganic filler.
• the inorganic filler fluidity modifier of the present invention may be included in the composition for waterproofing material.
• the inorganic filler fluidity modifier of the present invention may be included in at least one of the main component and the curing agent component.
• the curing agent component may contain a known curing catalyst.
• the curing catalyst include organic acid lead, organic acid tin, and tertiary amine compounds.
• curing agent components include the above-mentioned thinners, plasticizers, pigments such as chromium oxide, titanium oxide, and phthalocyanine; stabilizers such as antioxidants, ultraviolet absorbers, and dehydrating agents. May include.
• Examples of waterproof materials obtained by molding the composition for waterproof materials include rooftop waterproof materials.
• the rooftop waterproofing material can be obtained, for example, by applying a composition in which a main component and a curing agent component are mixed to a desired location to form a coating film, and then reacting and curing the composition.
• the polysulfide resin used in the polysulfide sealant is not particularly limited as long as it has a sulfide bond in its molecule; for example, a resin in which a hydrocarbon group such as an alkyl group is bonded to a sulfide bond. can be mentioned.
• the polysulfide resin may have, for example, an ether bond, an ester bond, an amide bond, or an imide group in its skeleton.
• polysulfide resin When a polysulfide resin has an ether bond in its skeleton, it becomes a polysulfide polyether resin.
• the polysulfide resin may have a functional group such as a thiol group, hydroxy group, or amino group at one or both ends.
• the polysulfide resin contains, for example, a structural unit represented by -(C 2 H 4 OCH 2 OC 2 H 4 -Sx)- (x is an integer from 1 to 5) in the main chain, Also, those having a thiol group represented by -C 2 H 4 OCH 2 OC 2 H 4 -SH at the end can be mentioned.
• the polysulfide resin has fluidity at room temperature, specifically at 25°C.
• the number average molecular weight (Mn) of the polysulfide resin is usually 100 to 200,000, preferably 400 to 50,000 or less.
• examples of the polysulfide resin include polysulfide polyether resin.
• Specific examples of the polysulfide polyether resin include thiol group-containing polysulfide polyether resins.
• n is an integer of 6 to 200
• (4) "-C 2 H 4 Examples include those having a thiol group represented by "OCH 2 OC 2 H 4 --SH” or "-CH 2 CH(OH)CH 2 --SH".
• the number average molecular weight of the polysulfide polyether resin is usually 600 to 200,000, preferably 800 to 50,000.
• polysulfide resin there are no restrictions on the manufacturing method of the polysulfide resin, and those manufactured by various known methods can be used. Furthermore, commercially available polysulfide resins can also be used. Commercially available polysulfide resins include, for example, “Thiocol LP-23, LP-32” (manufactured by Toray Fine Chemical Co., Ltd.), “THIOPLAST Polymer” (manufactured by AKZO NOBEL), and the like. Polysulfide resins may be used alone or in combination of two or more.
• additives can be used in combination with the polysulfide sealant containing the inorganic filler fluidity modifier of the present invention.
• additives include the thinners, plasticizers, adhesion agents, pigments, dyes, antioxidants, antioxidants, antistatic agents, flame retardants, tackifying resins, stabilizers, dispersants, etc. can be mentioned.
• a silane coupling agent such as aminosilane is preferably mentioned because it is particularly effective in improving adhesion to a glass surface and is also a general-purpose compound.
• the aminosilane include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, and bistriethoxysilylpropyl.
• Amine bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane , N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylethyldiethoxysilane, and the like.
• pigments examples include organic pigments such as azo pigments and copper phthalocyanine pigments.
• Examples of the dye include black dye, yellow dye, red dye, blue dye, and brown dye.
• anti-aging agent examples include hindered phenol compounds, hindered amine compounds, and the like.
• antioxidant examples include butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), and the like.
• antistatic agent examples include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.
• Examples of the flame retardant include chloroalkyl phosphate, dimethyl methyl phosphonate, bromine phosphorus compound, ammonium polyphosphate, neopentyl bromide polyether, brominated polyether, and the like.
• Examples of the tackifying resin include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, epoxy resins, alkyl titanates, and organic polyisocyanates.
• the stabilizer examples include fatty acid silyl esters, fatty acid amide trimethylsilyl compounds, and the like.
• a dispersant is a substance that makes solid particles into fine particles and disperses them in a liquid, and examples include sodium hexametaphosphate, sodium condensed naphthalene sulfonate, and surfactants.
• the polysulfide sealant is usually mixed with a curing agent just before use.
• a curing agent for example, curing agents commonly used in polysulfide resin sealing materials can be used, such as metal oxides, metal peroxides, organic and inorganic oxidizing agents, epoxy compounds, and isocyanate compounds. Among these, metal peroxides such as lead dioxide and manganese dioxide are preferred, and manganese dioxide is more preferred.
• the fluidity modifier of the present invention is preferably used by being mixed into this curing agent.
• the amount to be used is 2.5 to 2.5 to 100 parts by mass of the polysulfide resin used as the main ingredient to ensure sufficient curing and to obtain a cured product with appropriate elasticity.
• the amount is in the range of 25 parts by weight, and more preferably in the range of 3 to 20 parts by weight.
• the curing agent may also contain other fillers, plasticizers, curing accelerators, and silane coupling agents.
• the curing conditions are usually 20 to 25°C after mixing the main ingredient and curing agent. Further, the curing time is usually in the range of 24 to 168 hours.
• the inorganic filler-containing composition of the present invention is not limited to the above paste-like resin composition, but can also be suitably used as a molding resin composition for injection molding, extrusion molding, etc.
• the properties of molding resin compositions vary; some are liquid at the stage before molding (at room temperature), and others are made liquid by heating during molding, but the inorganic filler fluidity modifier of the present invention Since fluidity can be improved, excessive increase in viscosity due to the inclusion of an inorganic filler can be suppressed, and melt-kneading and the like can be performed smoothly.
• the inorganic filler fluidity modifier of the present invention can also increase the amount of inorganic filler added, it is desired to increase the amount of inorganic filler added to improve physical properties, such as automobile parts and sanitary absorbent articles. It can be suitably used in resin compositions for molding, building materials, stone paper, heat dissipation members, etc.
• composition examples for each use when the inorganic filler-containing composition of the present invention is used as a molding resin composition will be explained.
• the resin component contained in the molding resin composition used for automobile parts is, for example, a thermoplastic resin.
• Polypropylene resin is preferred because it has characteristics such as moldability, high mechanical strength, and economic efficiency.
• the above polypropylene is not particularly limited, but polypropylene resins with an MFR (230° C., 2.16 kg) of 60 to 120 g/10 minutes are preferred.
• the resin composition for automobile parts may further contain an olefin thermoplastic elastomer as a resin component.
• the olefin thermoplastic elastomer is not particularly limited, but one containing an ethylene- ⁇ -olefin copolymer is preferred.
• Inorganic fillers contained in the resin composition for automobile parts include talc, calcium carbonate, and whiskers (materials for the whiskers include graphite, potassium titanate, alumina, silicon carbide, silicon nitride, mullite, magnesia, magnesium borate, and boron). aluminum oxide, magnesium sulfate, zinc oxide, titanium boride, etc.), carbon nanofibers, carbon nanotubes, kaolin clay, mica, etc.
• the resin composition for automobile parts may contain the inorganic filler fluidity modifier of the present invention and various additives other than the inorganic filler, and the additives include the thinner, the plasticizer, the antioxidant, Examples include ultraviolet absorbers, light stabilizers, flame retardants, and colorants.
• the composition ratio of the resin component, inorganic filler, inorganic filler fluidity modifier, etc. contained in the resin composition for automobile parts is not particularly limited, but it is preferably adjusted to a composition that satisfies one or more of the following physical properties.
• the MFR (230° C., 2.16 kg, JIS-K7210-1) of the resin composition for automobile parts is preferably 20 g/10 minutes or more, and more preferably in the range of 20 to 30 g/10 minutes.
• the linear expansion coefficient (JIS-K7197) of the resin composition for automobile parts is preferably 5.0 ⁇ 10 ⁇ 5 /K or less, and preferably 4.0 to 5.0 ⁇ 10 ⁇ 5 /K. More preferred.
• the tensile modulus (JIS-K7161) of the resin composition for automobile parts is preferably 2.5 GPa or more, more preferably in the range of 2.5 to 3.0 GPa.
• the Charpy impact value (JIS-K7111) of the resin composition for automobile parts is preferably 30 kJ/m 2 or more, and more preferably in the range of 30 to 40 kJ/m 2 .
• Examples of automobile parts obtained by molding the resin composition for automobile parts include bonnet hoods, fenders, bumpers, doors, trunk lids, roofs, radiator grills, wheel caps, instrument panels, pillar garnishes, and the like. These automotive parts can be manufactured by injection molding a resin composition for automotive parts.
• the resin component contained in the molding resin composition used for sanitary absorbent articles is, for example, polyolefin, and among these polyolefins, polyethylene, polypropylene, One or more types selected from the group consisting of are preferable, and polyethylene is more preferable.
• polyethylene for example, two or more types of polyethylene with different densities may be used.
• the polyolefin that is the resin component of the resin composition for sanitary absorbent articles is not particularly limited, but preferably has an MFR (190°C, 2.16 kgf) in the range of 0.1 to 20 g/10 minutes, and 0.5 to 5 g/10 A range of minutes is more preferred.
• MFR 190°C, 2.16 kgf
• the resin composition for sanitary absorbent articles may further include a polystyrene elastomer as a resin component.
• polystyrene-based elastomers include styrene-olefin-based (SEP, SEBC, etc.), styrene-olefin-styrene-based (SEPS, SEBS, etc.), styrene-diene-based (SIS, SBS, etc.), and hydrogenated styrene-diene-based (HSIS, etc.). , HSBR, etc.) containing a styrene block.
• the styrene component in these polystyrene elastomers is preferably in the range of 10 to 40% by weight, more preferably in the range of 20 to 40% by weight.
• Examples of the inorganic filler included in the resin composition for sanitary absorbent articles include calcium carbonate, calcium sulfate, barium carbonate, titanium oxide, etc., and preferably one or more fillers selected from the group consisting of calcium carbonate and barium sulfate.
• the shape of these inorganic fillers is not particularly limited, but it is preferably particulate, more preferably fine particles with an average particle size in the range of 0.1 to 10 ⁇ m, and fine particles with an average particle size in the range of 0.3 to 5 ⁇ m. More preferably, the particles have an average particle diameter of 0.5 to 3 ⁇ m.
• the content of the inorganic filler is within the above range, all of the moisture permeability, air permeability, and liquid permeation resistance of the resulting sanitary absorbent article can be sufficiently ensured.
• the resin composition for sanitary absorbent articles may contain various additives other than the inorganic filler fluidity modifier and inorganic filler of the present invention, and the additives include the above-mentioned plasticizer, thinner, compatibilizer, Processing aids, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, anti-blocking agents, antifogging agents, matting agents, surfactants, antibacterial agents, deodorants, antistatic agents, water repellents , oil repellent, radiation shielding agent, coloring agent, pigment, etc.
• additives include the above-mentioned plasticizer, thinner, compatibilizer, Processing aids, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, anti-blocking agents, antifogging agents, matting agents, surfactants, antibacterial agents, deodorants, antistatic agents, water repellents , oil repellent, radiation shielding agent, coloring agent, pigment, etc.
• the molded product obtained by molding the resin composition for sanitary absorbent articles can be used as a back sheet (a sheet that has air permeability and moisture permeability but does not allow liquid to pass through) used in sanitary absorbent articles such as disposable diapers and sanitary napkins. It can be suitably used.
• the backsheet can be produced, for example, by melt-kneading a resin composition for sanitary absorbent articles, forming a sheet by a T-die method or an inflation method, and then uniaxially or biaxially stretching the obtained sheet.
• Stone paper is a sheet containing calcium carbonate derived from limestone and polyolefin (polyethylene, polypropylene, etc.), and does not require water or wood to form the sheet, and the raw material limestone is almost inexhaustible on earth.
• This sheet has excellent sustainability as it exists in Stone paper contains a large amount of calcium carbonate, and the inorganic filler fluidity modifier of the present invention can improve the fluidity of calcium carbonate, thereby improving sheet properties.
• Stone paper can be produced, for example, by melt-kneading a stone paper composition containing calcium carbonate, polyolefin, and the inorganic filler fluidity modifier of the present invention, and then performing inflation molding or extrusion molding.
• the content of calcium carbonate is the mass ratio of polyolefin to calcium carbonate (polyolefin: calcium carbonate), for example, from 85:15 to 20:80, preferably from 85:15 to 30:70. , more preferably 85:15 to 35:65, still more preferably 80:20 to 40:60.
• the stone paper composition may further contain the above-mentioned plasticizers, thinners, foaming agents, colorants, lubricants, coupling agents, stabilizers (antioxidants, ultraviolet absorbers, etc.), antistatic agents, etc. as adjuvants. good.
• blowing agent examples include aliphatic hydrocarbon compounds such as propane, normal butane, isobutane, normal pentane, isopentane, and hexane; alicyclic hydrocarbon compounds such as cyclohexane, cyclopentane, and cyclobutane; trifluoromonochloroethane, difluorodichloromethane, etc. Examples include halogenated hydrocarbon compounds.
• lubricant examples include fatty acid lubricants such as stearic acid, hydroxystearic acid, complex stearic acid, and oleic acid; fatty alcohol lubricants, stearamide, oxystearamide, oleylamide, erucylamide, ricinolamide, behenamide, Aliphatic amide lubricants such as methylolamide, methylenebisstearamide, methylenebisstearobehenamide, bisamidic acids of higher fatty acids, and complex amides; n-butyl stearate, methyl hydroxystearate, polyhydric alcohol fatty acid esters , saturated fatty acid esters, aliphatic ester lubricants such as ester waxes; fatty acid metal soap group lubricants, and the like.
• fatty acid lubricants such as stearic acid, hydroxystearic acid, complex stearic acid, and oleic acid
• fatty alcohol lubricants such as
• antioxidants phosphorus antioxidants, phenolic antioxidants, pentaerythritol antioxidants, etc.
• phosphorous antioxidants include phosphorous acid triesters, diesters, and monoesters of phosphorous acid such as triphenyl phosphite, trisnonylphenyl phosphite, and tris(2,4-di-tert-butylphenyl) phosphite.
• Phosphoric esters examples include phosphoric esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl) phosphate, and 2-ethylphenyldiphenyl phosphate.
• phenolic antioxidants include ⁇ -tocopherol, butylated hydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2- tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 2,6-di-tert-butyl-4-(N,N-dimethyl aminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane etc.
• heat dissipation member (heat dissipation member) BACKGROUND ART
• electronic devices such as personal computers, smartphones, and televisions
• heat dissipating members containing thermally conductive fillers are often used to efficiently dissipate the generated heat.
• automobiles such as electric cars and hybrid cars are also equipped with many electronic devices, and many heat dissipation members containing thermally conductive fillers are used.
• resin composition for heat dissipation members examples include thermosetting resins, active energy ray-curable resins, and thermoplastic resins. be.
• thermosetting resin of the resin composition for heat dissipation members known thermosetting resins can be used, such as novolac type phenolic resins such as phenol novolac resin and cresol novolak resin; unmodified resol phenolic resin, tung oil, Phenolic resins such as resol type phenolic resins such as oil-modified resol phenolic resins modified with linseed oil, walnut oil, etc.; Bisphenol type epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin; Fat chain modified bisphenol type epoxy resins, novolak Novolac type epoxy resins such as epoxy resins and cresol novolac epoxy resins; Epoxy resins such as biphenyl type epoxy resins and polyalkylene glycol type epoxy resins; Resins with triazine rings such as urea resins and melamine resins; (meth) Vinyl resins such as acrylic resins and vinyl ester resins: unsaturated polyester resins, bismaleimide resins, polyurethaned
• thermosetting resin may be used together with a curing agent.
• Curing agents used with thermosetting resins include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, and guanidine derivatives; dicyandiamide, linolenic acid, etc.
• Amide compounds such as polyamide resins synthesized from polymer and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride , hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and other acid anhydride compounds; phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin ( Zyrock resin), resorcinol novolak resin, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-con
• thermoplastic resin of the resin composition for heat dissipation members known thermoplastic resins can be used, such as polyethylene resin, polypropylene resin, polymethyl methacrylate resin, polyvinyl acetate resin, ethylene-propylene copolymer, and ethylene.
• Vinyl acetate copolymer polyvinyl chloride resin, polystyrene resin, polyacrylonitrile resin, polyamide resin, polycarbonate resin, polyacetal resin, polyethylene terephthalate resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyether sulfone resin, polyether Etherketone resin, polyallylsulfone resin, thermoplastic polyimide resin, thermoplastic urethane resin, polyamino bismaleimide resin, polyamideimide resin, polyetherimide resin, bismaleimide triazine resin, polymethylpentene resin, fluorinated resin, liquid crystal polymer, Examples include olefin-vinyl alcohol copolymers, ionomer resins, polyarylate resins, acrylonitrile-ethylene-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, acrylonitrile-styrene cop
• Thermal conductive fillers contained in the resin composition for heat dissipation members include alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, calcium oxide, magnesium oxide, zinc oxide, beryllia, aluminum oxide, Examples include aluminum nitride, boron nitride, hydrated metal compounds, fused silica, crystalline silica, amorphous silica, silicon carbide, silicon nitride, titanium carbide, and diamond.
• the thermally conductive filler may be surface-treated with a silane-based, titanate-based, or aluminate-based coupling agent.
• the shape of the thermally conductive filler is not particularly limited, and may be spherical, acicular, flaky, dendritic, or fibrous.
• the content of the thermally conductive filler in the resin composition for a heat dissipating member can be adjusted as appropriate depending on the application, and it is preferable that the amount of the thermally conductive filler is in the range of 30 to 5,000 parts by mass based on 100 parts by mass of the resin component.
• the resin composition for a heat dissipating member may contain various additives other than the inorganic filler fluidity modifier and the thermally conductive filler of the present invention, and the additives include dyes, pigments, antioxidants, polymerization inhibitors, etc. , antifoaming agents, leveling agents, ion scavengers, humectants, viscosity modifiers, preservatives, antibacterial agents, antistatic agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, and the like.
• additives include dyes, pigments, antioxidants, polymerization inhibitors, etc. , antifoaming agents, leveling agents, ion scavengers, humectants, viscosity modifiers, preservatives, antibacterial agents, antistatic agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, and the like.
• the heat dissipation member can be molded by heating the resin composition for heat dissipation members.
• the resin composition for a heat dissipating member contains an active energy ray-curable resin, it can be cured and molded by irradiation with active energy rays such as ultraviolet rays and infrared rays.
• the resin composition for a heat dissipation member contains a thermoplastic resin, the heat dissipation member can be obtained by a known molding method such as injection molding, extrusion molding, or press molding.
• a heat radiating member obtained by molding a resin composition for a heat radiating member can be used as a heat sink.
• a heat dissipating member obtained by molding a resin composition for a heat dissipating member can also be used as a heat dissipating bonding member for joining a metal heat dissipating member to a portion where heat is to be dissipated.
• the resin composition for heat dissipation members can also be used as a semiconductor encapsulation material.
• thermally conductive silicone sheet (Thermal conductive silicone sheet)
• thermally conductive silicone sheets using silicone resin are widely used as heat dissipating members for electric vehicles, mobile terminals, wearable terminals, etc. due to their light weight and high thermal conductivity.
• the thermally conductive silicone sheet has a problem in that when it is highly filled with inorganic filler, the flexibility of the sheet is impaired and mounting becomes difficult.
• the inorganic filler fluidity modifier of the present invention the fluidity of the inorganic filler is maintained and the flexibility of the sheet is maintained even when the inorganic filler responsible for heat conduction is highly loaded. It is possible to obtain a sheet with high thermal conductivity and excellent flexibility.
• the thermally conductive silicone sheet of the present invention is a thermally conductive silicone sheet containing a silicone resin, an inorganic filler, and an inorganic filler fluidity modifier of the present invention, wherein the inorganic filler is magnesium oxide, alumina, etc. and aluminum hydroxide.
• the mass ratio of the silicone resin and the inorganic filler is in the range of 50:50 to 1:99
• the inorganic filler fluidity modifier is It is contained in a range of 0.1 to 5 parts by mass based on 100 parts by mass of the total amount of silicone resin and inorganic filler.
• the thermally conductive silicone sheet of the present invention can maintain high flexibility even when filled with a high amount of inorganic filler, and when the mass ratio of silicone resin to inorganic filler [silicone resin: inorganic filler] is 20:80.
• the shear A hardness of the thermally conductive silicone sheet is H80
• the shear A hardness of the thermally conductive silicone sheet when the mass ratio of silicone resin and inorganic filler [silicone resin: inorganic filler] is 10:90 is H90 .
• H 90 /H 80 ⁇ 1.30 can be satisfied.
• the lower limit of H 90 /H 80 is, for example, 1.0, and the shear A hardness is measured by the method described in Examples.
• silicone resin of the thermally conductive silicone sheet of the present invention a known silicone resin used for thermally conductive silicone sheets can be used.
• an alkenyl group-containing organopolysiloxane and an organohydrogenpolysiloxane are added by a hydrosilylation reaction.
• the above alkenyl group-containing organopolysiloxane is preferably an organopolysiloxane having two or more alkenyl groups bonded to a silicon atom in one molecule, and serves as the main ingredient of the silicone resin.
• the main chain portion basically consists of repeating diorganosiloxane units, but this may include a branched structure as part of the molecular structure, or it may be a cyclic structure. Although it may be present, linear diorganopolysiloxane is preferred from the viewpoint of physical properties such as mechanical strength of the cured product.
• alkenyl group examples include alkenyl groups having 2 to 8 carbon atoms, such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, and cyclohexenyl group.
• vinyl group An allyl group is preferred, and a vinyl group is more preferred.
• Groups other than the alkenyl group bonded to the silicon atom of the alkenyl group-containing organopolysiloxane include, for example, alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 18 carbon atoms. may be further substituted with a halogen atom and/or a cyano group.
• groups other than alkenyl groups bonded to the silicon atom of the alkenyl group-containing organopolysiloxane include methyl group, ethyl group, propyl group, chloromethyl group, bromoethyl group, 3,3,3-trifluoropropyl group, Examples include cyanoethyl group, phenyl group, chlorophenyl group, and fluorophenyl group.
• the alkenyl group-containing organopolysiloxane is preferably an organopolysiloxane in which two or more alkenyl groups exist in one molecule, and from the viewpoint of improving the flexibility of the resulting cured product, more preferably silicon at the molecular chain terminal is used. It is an organopolysiloxane in which alkenyl groups are bonded only to atoms, and more preferably an organopolysiloxane having a structure represented by the following general formula (2).
• R 2 is each independently an alkyl group having 1 to 3 carbon atoms or a phenyl group
• X is each independently a vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group or cyclohexenyl group
• n is an integer of 1 or more.
• the alkenyl group-containing organopolysiloxane may have a molecular weight that gives a kinematic viscosity of 10 to 100,000 mm 2 /s at 25°C, preferably a molecular weight that gives a kinematic viscosity of 300 to 50,000 mm 2 /s. It is. Note that the above kinematic viscosity is a value at 25° C. using an Ostwald viscometer.
• the above-mentioned organohydrogenpolysiloxane is an organohydrogenpolysiloxane having 2 or more, preferably 2 to 100, hydrogen atoms (Si-H groups) directly bonded to silicon atoms in one molecule, and contains an alkenyl group.
• the organohydrogenpolysiloxane is, for example, an organohydrogenpolysiloxane having a structure represented by the following general formula (3).
• R 3 is each independently a hydrogen atom or a monovalent group containing no aliphatic unsaturated bond, at least two of R are hydrogen atoms, n is an integer of 1 or more.
• Examples of monovalent groups containing no aliphatic unsaturated bonds include alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 18 carbon atoms, and aralkyl groups having 7 to 18 carbon atoms.
• the alkyl group, aryl group and aralkyl group may be further substituted with a halogen atom and/or a cyano group.
• Specific examples of monovalent groups that do not contain aliphatic unsaturated bonds include methyl group, ethyl group, propyl group, chloromethyl group, bromoethyl group, 3,3,3-trifluoropropyl group, cyanoethyl group, phenyl group. , chlorophenyl group, and fluorophenyl group.
• n may be an integer of 1 or more, preferably an integer in the range of 1 to 200.
• the reaction ratio of the alkenyl group-containing organopolysiloxane and the organohydrogenpolysiloxane is the Si-
• the amount of H groups may be 0.2 to 2.0 per alkenyl group of the alkenyl group-containing organopolysiloxane, preferably 0.3 to 1.5. , more preferably 0.5 to 1.0 pieces.
• a platinum group metal curing catalyst may be used to promote the hydrosilylation reaction, if necessary.
• Known catalysts can be used as platinum group metal curing catalysts, such as H 2 PtCl 4 .nH 2 O, H 2 PtCl 6 .nH 2 O, NaHPtCl 6 .nH 2 O, KaHPtCl 6 .nH 2 O, Na 2 PtCl 6 ⁇ nH 2 O, K 2 PtCl 4 ⁇ nH 2 O, PtCl 4 ⁇ nH 2 O, PtCl 2 , Na 2 HPtCl 4 ⁇ nH 2 O (n is an integer from 0 to 6), etc. can be used.
• platinum group metal curing catalysts such as H 2 PtCl 4 .nH 2 O, H 2 PtCl 6 .nH 2 O, NaHPtCl 6 .nH 2 O, KaHPtCl 6 .nH 2 O, Na 2 PtCl 6 ⁇ nH 2 O, K 2 PtCl 4 ⁇ nH 2 O, PtCl 4 ⁇ nH 2 O,
• the thermally conductive silicone sheet of the present invention is a silicone sheet containing a silicone resin component (for example, alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane), an inorganic filler, and the inorganic filler fluidity modifier of the present invention.
• a silicone resin component for example, alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane
• the composition can be produced by curing while pressing at 100 to 150°C for 1 to 20 minutes.
• the silicone sheet can be cured while the silicone sheet composition is sandwiched between two resin films, and the resin film must have a heat distortion temperature of 100°C or higher and can withstand heat treatment after lamination.
• a film made of PET, PBT, or polycarbonate may be appropriately selected and used.
• the silicone sheet composition only needs to contain a silicone resin component, an inorganic filler, and the inorganic filler fluidity modifier of the present invention. Agents, colorants, antioxidants, etc. may be added.
• the thickness of the silicone sheet may be appropriately set depending on the application, and may be appropriately set, for example, in the range of 0.1 to 10 mm.
• the values of acid value and hydroxyl value are values evaluated by the following method.
• Method of measuring acid value It was measured by a method according to JIS K0070-1992.
• Method for measuring hydroxyl value It was measured by a method according to JIS K0070-1992.
• the number average molecular weight of polyester is a value converted to polystyrene based on GPC measurement, and the measurement conditions are as follows.
• [GPC measurement conditions] Measuring device: High-speed GPC device “HLC-8320GPC” manufactured by Tosoh Corporation Column: "TSK GURDCOLUMN SuperHZ-L” manufactured by Tosoh Corporation + "TSK gel SuperHZM-M” manufactured by Tosoh Corporation + “TSK gel SuperHZM-M” manufactured by Tosoh Corporation + “TSK gel SuperHZ-2000” manufactured by Tosoh Corporation + “TSK gel SuperHZ-2000” manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: “EcoSEC Data Analysis version 1.07” manufactured by Tosoh Corporation Column temperature: 40°C Developing solvent: Tetrahydrofuran Flow rate: 0.35 mL/min Measurement sample: 7.5 mg of the sample was dissolved in 10
• AA adipic acid
• INA isononyl alcohol
• TIPT tetraisopropyl titanate
• fluidity modifier A which is a polyester.
• the obtained fluidity modifier A was a pale yellow liquid at room temperature, had an acid value of 33 mgKOH/g, a hydroxyl value of 4 mgKOH/g, and a number average molecular weight of 2,430.
• fluidity modifier B which is polyester.
• the obtained fluidity modifier B was a pale yellow liquid at room temperature, had an acid value of 40 mgKOH/g, a hydroxyl value of 6 mgKOH/g, and a number average molecular weight of 2,200.
• the temperature was lowered to 125°C, and 67 g of maleic anhydride was added to the reaction system.
• the reaction was carried out at 125° C. for 3 hours, and the disappearance of maleic anhydride was confirmed by IR to obtain a fluidity modifier A′ which is a polyester.
• the obtained fluidity modifier A' was a pale yellow liquid at room temperature, and had an acid value of 33 mgKOH/g, a hydroxyl value of 27 mgKOH/g, and a number average molecular weight of 2,450.
• fluidity modifier D which is a polyester.
• the obtained fluidity modifier D was a pale yellow liquid at room temperature, had an acid value of 35 mgKOH/g, a hydroxyl value of 7 mgKOH/g, and a number average molecular weight of 2,200.
• the obtained fluidity modifier B' was a pale yellow liquid at room temperature, had an acid value of 29 mgKOH/g, a hydroxyl value of 120 mgKOH/g, and a number average molecular weight of 950.
• a fluidity modifier C' which is a polyester having carboxyl groups at both ends.
• the obtained fluidity modifier C' was a pale yellow liquid at room temperature, had an acid value of 55 mgKOH/g, a hydroxyl value of 55 mgKOH/g, and a number average molecular weight of 1,500.
• Comparative modifier D' which is a polyester, was obtained by removing unreacted raw materials and low volatile components at 200° C. under reduced pressure.
• the obtained comparative modifier D' was a pale yellow liquid at room temperature, had an acid value of 0.5 mgKOH/g, a hydroxyl value of 10 mgKOH/g, and a number average molecular weight of 2,300.
• Example 1-4 and Comparative Example 1-5 Preparation and evaluation of aluminum filler-containing composition
• Spherical alumina (“DAW-07”/"DAW-45” manufactured by Denka Corporation) and aluminum hydroxide are used as inorganic fillers
• polypropylene glycol (“PPG1000” manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and polyisocyanate (DIC) are used as base components.
• Example 5-7 and Comparative Example 6-9 Preparation and evaluation of aluminum filler-containing composition
• Spherical alumina (DAW-07"/"DAW-45" manufactured by Denka Corporation) as an inorganic filler, castor oil as a base component, and a fluidity modifier were mixed in the proportions shown in Table 2, and a planetary stirring device (THINKY ARV) was mixed. -310) for 2 minutes at 1,000 rpm and 0.2 Pa to obtain a paste-like inorganic filler-containing composition.
• the fluidity of the obtained paste was evaluated in the same manner as above. The results are shown in Table 2.
• the fluidity modifiers of the Examples have a fluidity improving effect regardless of the type of base component.
• the fluidity modifier of the comparative example has a greatly reduced fluidity when the base component is castor oil.
• the fluidity modifier of the example it is presumed that the fluidity is improved due to the stable presence of a fluidity modifier layer near the surface of the inorganic filler that prevents the fillers from contacting each other.
• the fluidity modifier of the comparative example with a high hydroxyl value has a high affinity with the base component having a hydroxyl group, so it is unevenly distributed near the filler. It can be seen that no improvement in fluidity can be expected.
• Example 8-11 and Comparative Example 10-13 Preparation and evaluation of aluminum filler-containing composition
• Spherical alumina (“DAW-07”/“DAW-45” manufactured by Denka Corporation) is used as an inorganic filler
• silicone resin methylphenyl silicone oil, “KF-54” manufactured by Shin-Etsu Chemical Co., Ltd.
• fluidity improver are used as base components.
• the fillers were blended in the proportions shown in Table 3 and stirred for 2 minutes at 1,000 rpm and 0.2 Pa using a planetary stirrer (THINKY ARV-310) to obtain a paste-like inorganic filler-containing composition.
• the fluidity of the obtained paste was evaluated in the same manner as above. The results are shown in Table 3.
• Example 12-16 and Comparative Example 14-18 Preparation and evaluation of aluminum filler-containing composition
• Spherical alumina (“DAW-07”/"DAW-45” manufactured by Denka Corporation) or aluminum nitride (“AlN20AF” manufactured by Thrutek Corporation) was used as the inorganic filler, and bisphenol A type liquid epoxy resin (manufactured by DIC Corporation) was used as the base component.
• "EPICLON 850-S” and a fluidity modifier in the ratio shown in 4 and stirred for 2 minutes at 1,000 rpm and 0.2 Pa using a planetary stirring device (THINKY ARV-310) to form a paste-like inorganic filler.
• a containing composition was obtained.
• the fluidity of the obtained paste was evaluated in the same manner as above. The results are shown in Table 4.
• the fluidity modifiers of the examples have a fluidity improving effect regardless of the type of base component.
• the fluidity modifier of the comparative example has a greatly reduced fluidity when the base component is an epoxy resin.
• the fluidity modifier of the example it is presumed that the fluidity is improved due to the stable presence of a fluidity modifier layer near the surface of the inorganic filler that prevents the fillers from contacting each other.
• the base component is a highly polar component (for example, an epoxy resin)
• the fluidity modifier of the comparative example with a high hydroxyl value cannot be unevenly distributed near the filler, and no improvement in fluidity can be expected. I understand.
• Example 17-20 and Comparative Example 19-22 Preparation and evaluation of calcium carbonate filler-containing composition
• Calcium carbonate ground calcium carbonate, "Super S” manufactured by Maruo Calcium Co., Ltd.
• DINP diisononyl phthalate
• DETDA diethylmethylbenzenediamine
• a fluidity modifier were blended in the proportions shown in Table 5 and stirred for 2 minutes at 1,000 rpm and 0.2 Pa using a planetary stirrer (THINKY ARV-310) to obtain a paste-like inorganic filler-containing composition.
• the viscosity of the obtained paste was evaluated by the following method. The results are shown in Table 5.
• Example 21-24 and Comparative Examples 23-26 Preparation and evaluation of polyisocyanate-containing composition
• Polyisocyanate ("Burnock DN-980S” manufactured by DIC Corporation) as a base component, an ether ester compound ("Monocizer W-260” manufactured by DIC Corporation) as a plasticizer, and a fluidity modifier in the proportions shown in Table 6.
• the mixture was blended and stirred for 2 minutes at 1,000 rpm and 0.2 Pa using a planetary stirrer (THINKY ARV-310) to obtain a paste-like polyisocyanate-containing composition.
• the resulting paste was evaluated for changes in viscosity over time using the following method. The results are shown in Table 6.
• Spherical alumina mixture of DAW-07 (spherical alumina with a particle size (d50) of 8.1 ⁇ m, manufactured by Denka Corporation) and DAW-45 (spherical alumina with a particle size (d50) of 43.3 ⁇ m, manufactured by Denka Corporation)
• DAW-07/DAW-45 50/50 (mass ratio)
• Silane coupling agent Decyltrimethoxysilane
• the produced silicone sheet was subjected to a tensile test in accordance with JIS K6251:2010 under the following conditions, and the tensile elastic modulus and tensile elongation rate were measured.
• the tensile elongation rate is expressed as a percentage by subtracting the initial chuck distance of 20 mm from the chuck distance when a 0.5 mm sheet is tensilely broken, and dividing the value by the chuck distance of 20 mm.
• Measuring equipment “Tensilon Universal Material Testing Machine” manufactured by Orientech Co., Ltd. Sample shape: Dumbbell size 3 Distance between chucks: 20mm
• thermophysical property measuring device manufactured by Kyoto Electronics Co., Ltd.

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