WO2021192883A1 - 無機フィラー分散安定化剤、無機フィラー含有樹脂組成物、成形品及び添加剤 - Google Patents

無機フィラー分散安定化剤、無機フィラー含有樹脂組成物、成形品及び添加剤 Download PDF

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Publication number
WO2021192883A1
WO2021192883A1 PCT/JP2021/008355 JP2021008355W WO2021192883A1 WO 2021192883 A1 WO2021192883 A1 WO 2021192883A1 JP 2021008355 W JP2021008355 W JP 2021008355W WO 2021192883 A1 WO2021192883 A1 WO 2021192883A1
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Prior art keywords
inorganic filler
acid
polyester
resin
dispersion stabilizer
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Ceased
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PCT/JP2021/008355
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English (en)
French (fr)
Japanese (ja)
Inventor
淳子 山本
洋志 吉村
裕輔 田尻
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to EP21777151.8A priority Critical patent/EP4130151A4/en
Priority to US17/912,194 priority patent/US12584012B2/en
Priority to KR1020227030982A priority patent/KR102771573B1/ko
Priority to CN202180022046.1A priority patent/CN115298262B/zh
Priority to JP2022509470A priority patent/JP7127754B2/ja
Publication of WO2021192883A1 publication Critical patent/WO2021192883A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • 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
    • C08G63/91—Polymers modified by chemical after-treatment
    • 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
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C08K2003/282—Binary compounds of nitrogen with 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron

Definitions

  • the present invention relates to an inorganic filler dispersion stabilizer, an inorganic filler-containing resin composition, a molded product, and an additive.
  • Building materials, automobile parts, sanitary absorbent articles, stone paper, etc. are molded from a resin composition containing an inorganic filler, and the inorganic filler has various functions such as impact resistance, bending resistance, dimensional stability, and moisture permeability. Is given.
  • Patent Documents 1 and 2 As a method of increasing the content of the inorganic filler in the resin composition, a method of adding a thickener has been adopted, and various thickeners have been proposed (Patent Documents 1 and 2).
  • the thickener By coating the surface of the inorganic filler, the thickener suppresses the interaction between the inorganic fillers and lowers the viscosity of the composition. On the other hand, by lowering the viscosity of the composition, the inorganic filler precipitates over time to form an agglomerate (hard cake) containing the inorganic filler, and the storage stability is significantly impaired. There was a problem that it would end up. In addition, the thickener may not be able to exhibit a thickening effect depending on the type of binder resin contained in the composition.
  • An object to be solved by the present invention is to provide an inorganic filler dispersion stabilizer capable of lowering the viscosity of a composition containing an inorganic filler and improving storage stability.
  • a polyester having a specific structure can reduce the viscosity of a resin composition containing an inorganic filler and improve storage stability. Find out and complete the invention.
  • the present invention relates to an inorganic filler dispersion stabilizer which is a polyester having carboxyl groups at both ends.
  • an inorganic filler dispersion stabilizer capable of lowering the viscosity of a composition containing an inorganic filler and improving the storage stability of the composition containing the inorganic filler.
  • the inorganic filler dispersion stabilizer of the present invention is a polyester having carboxyl groups at both ends.
  • the inorganic filler dispersion stabilizer of the present invention may be referred to as “dispersion stabilizer of the present invention”
  • the polyester which is the inorganic filler dispersion stabilizer of the present invention may be referred to as "polyester of the present invention”.
  • the "dispersion stabilizer” means a component that prevents the inorganic filler in the composition from aggregating and settling by adding it to the composition containing the inorganic filler.
  • one of the carboxyl groups at both ends is adsorbed on the inorganic filler, and the other carboxyl group is adsorbed on the other inorganic filler to form a three-dimensional network composed of the polyester and the inorganic filler. It is thought that it will be done.
  • the three-dimensional network maintains its morphology and uses the composition while increasing the viscosity of the system and suppressing the sedimentation of the inorganic filler. It is considered that in a state where the shearing force is large, the three-dimensional network is once destroyed and dispersed by the shearing force, and the viscosity of the system can be reduced. This effect can be expected without being affected by various binder resins used in the composition.
  • the polyester of the present invention preferably has a repeating unit represented by the following general formula (1-1) and a repeating unit represented by the following general formula (1-2), or a polyester having the following general formula (1).
  • A is an aliphatic dibasic acid residue having 2 to 12 carbon atoms.
  • G is an aliphatic diol residue having 2 to 9 carbon atoms.
  • L is a hydroxycarboxylic acid residue having 2 to 18 carbon atoms.
  • the polyester of the present invention is more preferably a polyester having a repeating unit represented by the general formula (1-1) and a repeating unit represented by the general formula (1-2) at both ends. It is a polyester having a carboxyl group.
  • the polymerization form of the above is not particularly limited, and a random copolymer of these repeating units may be used, or a block copolymer of these repeating units may be used.
  • the polyester of the present invention is more preferably a polyester represented by the following general formula (1).
  • a 1 is an aliphatic dibasic acid residue having 2 to 12 carbon atoms.
  • a 2 and A 3 are independently aliphatic polybasic acid residues having 2 to 12 carbon atoms or aromatic polybasic acid residues having 6 to 15 carbon atoms.
  • G 1 and G 2 are independently aliphatic diol residues having 2 to 9 carbon atoms.
  • m represents the number of repetitions and is an integer in the range of 1 to 20.
  • p is one minus integer from the number of base the acid functional groups of the aliphatic polybasic acid or an aromatic polybasic acid A 2.
  • q is one minus integer from the number of base the acid functional groups of the aliphatic polybasic acid or an aromatic polybasic acid A 3.
  • a 1 and G 1 may be the same or different for each repeating unit enclosed in parentheses.
  • the "dibasic acid residue” is an organic group obtained by removing a basic acid functional group from a dibasic acid.
  • the dibasic acid residue indicates the remaining organic group excluding the carboxyl group of the dicarboxylic acid.
  • the number of carbon atoms of the dicarboxylic acid residue it is assumed that the carbon atom in the carboxyl group is not included.
  • the "polybasic acid residue” is an organic group obtained by removing a 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 are contained therein. It shows the remaining organic groups excluding the carboxyl group.
  • the carbon atom in the carboxyl group shall not be included.
  • the "diol residue” and the "alcohol residue” indicate the remaining organic group obtained by removing the hydroxyl group from the diol and the alcohol.
  • the "hydroxycarboxylic acid residue” refers to the remaining organic group obtained by removing the hydroxyl group and the carboxyl group from the hydroxycarboxylic acid. Regarding the number of carbon atoms of the hydroxycarboxylic acid residue, it is assumed that the carbon atom in the carboxyl group is not included.
  • Aliphatic dibasic acid residues having 2 to 12 carbon atoms in A and A 1 may contain an alicyclic structure.
  • Aliphatic dibasic acid residue having 2 to 12 carbon atoms of A and A 1 is preferably an aliphatic dicarboxylic acid residue having 2 to 12 carbon atoms, in the 2 to 12 carbon atoms aliphatic dicarboxylic Acid residues include succinic acid residue, adipic acid residue, pimeric acid residue, suberic acid residue, azelaic acid residue, sebacic acid residue, cyclohexanedicarboxylic acid residue, dodecanedicarboxylic acid residue, and hexahydro. Examples include phthalic acid residues.
  • Aliphatic dibasic acid residue having 2 to 12 carbon atoms of A and A 1 is preferably an aliphatic dicarboxylic acid residue having 4 to 10 carbon atoms, more preferably fat 5-10 carbon atoms It is a group dicarboxylic acid residue, more preferably a sebacic acid residue or a dodecanedicarboxylic acid residue.
  • Aliphatic polybasic acid residues having 2 to 12 carbon atoms of A 2 and A 3 may contain an alicyclic structure.
  • the aliphatic polybasic acid residues having 2 to 12 carbon atoms of A 2 and A 3 are preferably aliphatic dicarboxylic acid residues having 2 to 12 carbon atoms, and the aliphatic dicarboxylic acid residues having 2 to 12 carbon atoms.
  • dicarboxylic acid residues include succinic acid residue, adipic acid residue, pimeric acid residue, suberic acid residue, azelaic acid residue, sebacic acid residue, cyclohexanedicarboxylic acid residue, dodecanedicarboxylic acid residue, and hexa.
  • Examples include hydrophthalic acid residues and maleic acid residues.
  • the aromatic polybasic acid residues having 6 to 15 carbon atoms of A 2 and A 3 are preferably aromatic dicarboxylic acid residues having 6 to 15 carbon atoms and aromatic tricarboxylic acid residues having 6 to 15 carbon atoms. It is an aromatic tetracarboxylic acid residue having a group or 6 to 15 carbon atoms, and examples thereof include a phthalic acid residue, a trimellitic acid residue, and a pyromellitic acid residue.
  • Examples of the aliphatic diol residues having 2 to 9 carbon atoms of G, G 1 and G 2 include ethylene glycol residues, 1,2-propylene glycol residues, 1,3-propanediol residues, and 1,2-. Butanediol residue, 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-dimethylolheptan) residue, 3-methyl-1,5-pentanediol residue, 1,6-hexanediol residue, 2,2,
  • Aliphatic diol residues having 2 to 9 carbon atoms of G, G 1 and G 2 may contain an alicyclic structure and / or an ether bond.
  • Examples of the aliphatic diol residue having 2 to 9 carbon atoms containing the alicyclic structure include 1,3-cyclopentanediol residue, 1,2-cyclohexanediol residue, and 1,3-cyclohexanediol residue. Examples thereof include 1,4-cyclohexanediol residue, 1,2-cyclohexanedimethanol residue, and 1,4-cyclohexanedimethanol residue.
  • Examples of the aliphatic diol residue having 2 to 9 carbon atoms containing the ether bond include diethylene glycol residue, triethylene glycol residue, tetraethylene glycol residue, dipropylene glycol residue, and tripropylene glycol residue. Can be mentioned.
  • the aliphatic diol residues having 2 to 9 carbon atoms of G, G 1 and G 2 are preferably aliphatic diol residues having 3 to 8 carbon atoms, and more preferably 2-methyl-1,3-.
  • the hydroxycarboxylic acid residues of L having 2 to 18 carbon atoms include propionic acid, butyric acid, valeric acid, caproic acid, capric acid enanthate, undesic acid, lauric acid, tridecyl acid, myristic acid, pentadecic acid, and palmitic acid. , Margaric acid, stearic acid and other aliphatic carboxylic acids having 3 to 19 carbon atoms, and hydroxycarboxylic acid residues in which one hydroxyl group is substituted. Specific examples thereof include lactic acid residues and 9-hydroxy. Examples thereof include stearic acid residues, 12-hydroxystearic acid residues, and 6-hydroxycaproic acid residues.
  • the hydroxycarboxylic acid residue of L having 2 to 18 carbon atoms is preferably an aliphatic hydroxycarboxylic acid residue having 4 to 18 carbon atoms, and more preferably a 12-hydroxystearic acid residue.
  • p is one minus integer from the number of base the acid functional groups of the aliphatic polybasic acid or an aromatic polybasic acid A 2.
  • q is one minus integer from the number of base the acid functional groups of the aliphatic polybasic acid or an aromatic polybasic acid A 3. Therefore, when A 2 and A 3 are independently aliphatic dicarboxylic acid residues having 2 to 12 carbon atoms or aromatic dicarboxylic acid residues having 6 to 15 carbon atoms, A 2 and A 3 are The number of basic acid functional groups (carboxyl groups) contained is 2, each of p and q is 1, and the general formula (1) is represented by the following.
  • the polyester of the present invention may be used, for example, as a mixture of two or more kinds of polyesters in which at least one of each residue and m value in the general formula (1) is different from each other.
  • the average value of m is preferably in the range of 2 to 15.
  • the average value of m can be confirmed from the number average molecular weight of polyester.
  • the number average molecular weight (Mn) of the polyester of the present invention is, for example, in the range of 100 to 6,000, preferably in the range of 300 to 5,000, and more preferably in the range of 500 to 5,000. , More preferably in the range of 800-4,500.
  • the number average molecular weight (Mn) is a polystyrene-converted value 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 preferably in the range of 20 to 400 mgKOH / g, more preferably in the range of 30 to 150 mgKOH / g, and even more preferably in the range of 40 to 150 mgKOH / g.
  • the acid value of the polyester is confirmed by the method described in Examples.
  • the properties of the polyester of the present invention differ depending on the number average molecular weight, composition, etc., but are usually liquid, solid, paste, etc. at room temperature.
  • the polyester of the present invention can be obtained using a reaction material containing an aliphatic dibasic acid, an aliphatic polybasic acid and / or an aromatic polybasic acid, an aliphatic diol, and any hydroxycarboxylic acid.
  • the reaction raw material means a raw material constituting the polyester of the present invention, and does not contain a solvent or a catalyst that does not constitute the polyester.
  • "arbitrary hydroxycarboxylic acid” means that hydroxycarboxylic acid may or may not be used.
  • 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 later.
  • the reaction raw material of the polyester of the present invention may include aliphatic dibasic acid, aliphatic polybasic acid and / or aromatic polybasic acid, aliphatic diol, and arbitrary hydroxycarboxylic acid, and may include other raw materials. good.
  • the reaction raw material of the polyester of the present invention preferably contains 90% by mass or more based on the total amount of the reaction raw material, such as aliphatic dibasic acid, aliphatic polybasic acid and / or aromatic polybasic acid, aliphatic diol, and any of them.
  • hydroxycarboxylic acid is a hydroxycarboxylic acid, more preferably composed of only aliphatic dibasic acids, aliphatic polybasic acids and / or aromatic polybasic acids, aliphatic diols, and arbitrary hydroxycarboxylic acids.
  • the aliphatic dibasic acid used for producing the polyester of the present invention is an aliphatic dibasic acid corresponding to an aliphatic dibasic acid residue having 2 to 12 carbon atoms of A and A 1, and is used as an aliphatic dibasic acid.
  • the basic acid may be used alone or in combination of two or more.
  • the aliphatic polybasic acid used in the production of the polyester of the present invention is an aliphatic polybasic acid corresponding to an aliphatic polybasic acid residue having 2 to 12 carbon atoms of A 2 and A 3, and is an aliphatic polybasic acid to be used.
  • the polybasic acid may be used alone or in combination of two or more.
  • the aromatic polybasic acid used in the production of the polyester of the present invention is an aromatic polybasic acid corresponding to an aromatic polybasic acid residue having 6 to 15 carbon atoms of A 2 and A 3, and is an aromatic polybasic acid to be used.
  • the polybasic acid may be used alone or in combination of two or more.
  • the aliphatic diol used in the production of the polyester of the present invention is an aliphatic diol corresponding to an aliphatic diol residue having 2 to 9 carbon atoms of G, G 1 and G 2, and one kind of aliphatic diol is used. It may be used alone or in combination of two or more.
  • the hydroxycarboxylic acid used in the production of the polyester of the present invention is a hydroxycarboxylic acid corresponding to a hydroxycarboxylic acid residue having 2 to 18 carbon atoms in L, and the hydroxycarboxylic acid used may be used alone. Two or more types may be used in combination.
  • the reaction raw materials used also include derivatives such as the above-mentioned esterified products, the above-mentioned acid chlorides, and the above-mentioned acid anhydrides.
  • hydroxycarboxylic acid also includes compounds having a lactone structure such as ⁇ -caprolactone.
  • the polyester of the present invention reacts with aliphatic dibasic acids, aliphatic polybasic acids and / or aromatic polybasic acids, aliphatic diols, and arbitrary hydroxycarboxylic acids constituting each residue of the polyester of the present invention. It can be produced by reacting under conditions where the equivalent of carboxyl groups contained in the raw material is larger than the equivalent of hydroxyl groups.
  • the polyester of the present invention contains an aliphatic dibasic acid, an aliphatic diol, and an arbitrary hydroxycarboxylic acid constituting each residue of the polyester of the present invention, and the equivalent of the hydroxyl group contained in the reaction raw material is larger than the equivalent of the carboxyl group. It can also be produced by reacting under many conditions to obtain a polyester having a hydroxyl group at the end of the main chain, and then further reacting the obtained polyester with an aliphatic polybasic acid and / or an aromatic polybasic acid.
  • the reaction of the reaction raw material may be an esterification reaction in the presence of an esterification catalyst, for example, in a temperature range of 180 to 250 ° C. for 10 to 25 hours. ..
  • the conditions such as the temperature and time of the esterification reaction are not particularly limited and may be set as appropriate.
  • esterification catalyst examples include titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; zinc-based catalysts such as zinc acetate; tin-based catalysts such as dibutyltin oxide; and organic sulfonic acid-based catalysts such as p-toluenesulfonic acid. Examples include catalysts.
  • the amount of the esterification catalyst used may be appropriately set, but is usually used in the range of 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the reaction raw material.
  • the dispersion stabilizer of the present invention can function as a dispersion stabilizer for the inorganic filler of the resin composition containing the inorganic filler and the resin (the resin composition containing the inorganic filler), lowers the viscosity of the composition, and lengthens the composition. It is possible to prevent the inorganic filler from aggregating and settling when stored for a period of time.
  • the dispersion stabilizer of the present invention can particularly function as a storage stabilizer for the inorganic filler-containing resin composition because it can prevent the formation of aggregates (hard cakes) containing the inorganic filler.
  • aggregates hard cakes
  • the inorganic filler contained in the inorganic filler-containing resin composition of the present invention is not particularly limited, and is, for example, calcium carbonate, talc, silica, alumina, clay, antimony oxide, aluminum hydroxide, magnesium hydroxide, hydrotalcite, silicate. Calcium, magnesium oxide, potassium titanate, barium titanate, titanium oxide, calcium oxide, magnesium oxide, manganese dioxide, boron nitride, aluminum hydroxide and the like can be mentioned.
  • the inorganic filler 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, boron nitride and aluminum nitride, and more preferably calcium carbonate, alumina, and the like.
  • the shape of the inorganic filler such as particle size, fiber length, and fiber diameter is not particularly limited, and may be appropriately adjusted according to the intended use. Further, the surface treatment state of the inorganic filler is not particularly limited, and the surface may be modified with, for example, saturated fatty acid, depending on the intended use.
  • the content of the dispersion stabilizer of the present invention is not particularly limited, but is, for example, in the range of 0.1 to 30 parts by mass of the dispersion stabilizer of the present invention with respect to 100 parts by mass of the inorganic filler, preferably the inorganic filler 100.
  • the dispersion stabilizer of the present invention is in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5.0 parts by mass of the dispersion stabilizer of the present invention with respect to 100 parts by mass of the inorganic filler. It is the range of the part.
  • the inorganic filler-containing resin composition of the present invention preferably contains a thickener.
  • the filling amount of the inorganic filler can be increased, and the handleability and the like can be improved.
  • the thickener may induce the formation of agglomerates (hard cakes) containing an inorganic filler by thinning the composition, but the dispersion stabilizer of the present invention can prevent the formation of hard cakes. Therefore, in the inorganic filler-containing resin composition of the present invention, it is preferable to use the dispersion stabilizer of the present invention and the thickener in combination.
  • the thickening agent is not particularly limited, and examples thereof include an anionic wet dispersant, a cationic wet dispersant, and a polymer wet dispersant.
  • Specific examples of the thickener include alkyl ethers, mineral spirits, alkylbenzenes, paraffins, higher fatty acid esters, sorbitan fatty acid esters, glycerin fatty acid esters, polycarboxylates (for example, polycarboxylic acid alkylammonium salts), and polyesteric acids.
  • Salts eg polyesteric acid unsaturated polyaminoamide salts
  • higher fatty acid amides polyethylene oxide derivatives, sulfate esters, hydrostearic acid derivatives, polyalkylene polyimine alkylene oxides, polyallylamine derivatives, polyether ester acid amines, polyether phosphoric acid ester amines , Polyether phosphoric acid ester, polycarboxylic acid polyester, polyester having a carboxyl group only at one end, and the like can be used.
  • polycarboxylic acid alkylammonium salts, higher fatty acid amides, polyesteric acid unsaturated polyaminoamide salts, and polyesters having a carboxyl group only at one end are preferable.
  • the thickener may be used alone or in combination of two or more.
  • a commercially available product can be used as the thickener, and the commercially available product includes the ANTI-TERRA series such as ANTI-TERRA-U / U100, ANTI-TERRA-204, and ANTI-TERRA-250; DISPERBYK-106, DISPERBYK series such as DISPERBYK-108, DISPERBYK-140, BYK series such as BYK-9076, BYK-9077 (all manufactured by Big Chemie); Florencys such as Floren DOPA-15B, Floren DOPA-17HF, Floren DOPA-22; Fronon series such as Fronon RCM-100 (above, manufactured by Kyoeisha Chemical Co., Ltd.); Disparon series such as Disparon DA-325 and Disparon DA-375 (manufactured by Kusumoto Kasei Co., Ltd.); , Philanol PA-107P and other Philanol series; Marialim SC-1015F, Marialim SC-0708
  • Demor series such as Demor P and Demor EP
  • Poise series such as Poise 520, Poise 521, Poise 530
  • Homogenol series such as Homogenol L-18 (all manufactured by Kao Corporation)
  • Examples thereof include the Ajispar series (all manufactured by Ajinomoto Fine-Techno Co., Ltd.) such as PB824, Ajispar PB881, Ajispar PN411, and Ajispar PA111.
  • the polyester thickener is preferably a polyester represented by the following general formula (I) or the following general formula (II).
  • a 11 is an aliphatic dicarboxylic acid residue having 2 to 12 carbon atoms.
  • G 11 and G 12 are independently aliphatic diol residues having 2 to 9 carbon atoms.
  • X is a dicarboxylic acid residue having 1 to 8 carbon atoms.
  • Y is a hydrogen atom or a monocarboxylic acid residue having 1 to 9 carbon atoms.
  • Z is a monoalcohol residue having 2 to 10 carbon atoms.
  • t represents the number of repetitions and is an integer in the range of 0 to 30.
  • u represents the number of repetitions and is an integer in the range of 0 to 30.
  • a 11 and G 11 may be the same or different for each repeating unit enclosed in parentheses.
  • the polyester represented by the general formula (I) or (II) is preferable in that the repeating unit of the polyester is common to the polyester of the present invention and can be produced from the same raw material.
  • the aliphatic dicarboxylic acid residue having 2 to 12 carbon atoms of A 11, as well as aliphatic diol residues of G 11 and C 2 -C 9 G 12 is, It is the same as the polyester of the present invention.
  • the dicarboxylic acid residue having 1 to 8 carbon atoms of X may be any of an aliphatic dicarboxylic acid residue, an alicyclic dicarboxylic acid residue and an aromatic dicarboxylic acid residue.
  • the aliphatic dicarboxylic acid residue include malonic acid residue, succinic acid residue, glutaric acid residue, adipic acid residue, pimeric acid residue, suberic acid residue, azelaic acid residue, and sebacic acid residue.
  • the aromatic dicarboxylic acid residue include a group, a maleic acid residue, a fumaric acid residue, a 1,2-dicarboxycyclohexane residue, a 1,2-dicarboxycyclohexene residue and the like.
  • Examples include groups, isophthalic acid residues, terephthalic acid residues and the like.
  • the dicarboxylic acid residue having 1 to 8 carbon atoms of X is preferably a succinic acid residue, an adipic acid residue, a maleic acid residue or a phthalic acid residue.
  • the monocarboxylic acid residue having 1 to 9 carbon atoms in Y may be any of an aliphatic monocarboxylic acid residue, an alicyclic monocarboxylic acid residue, and an aromatic monocarboxylic acid residue, for example.
  • the monoalcohol residue having 2 to 10 carbon atoms in Z may be either an aliphatic monoalcohol residue or an alicyclic monoalcohol residue.
  • Examples of monoalcohol residues having 2 to 10 carbon atoms in Z include ethanol residues, propanol residues, butanol residues, pentanol residues, hexanol residues, cyclohexanol residues, heptanol residues, and octanol residues.
  • Residues such as groups, nonanol residues, and decanol are mentioned, and among these, octanol residues, nonanol residues, and decanol residues are preferable.
  • Y is preferably a hydrogen atom, an acetyl group or an benzoic acid residue
  • G 11 and G 12 are independently propylene glycol residues and neopentyl glycol residues, respectively. It is a group or a 1,3-propanediol residue
  • a 11 is an adipic acid residue
  • X is an adipic acid residue or a maleic acid residue.
  • Z is preferably an octanol residue, a nonanol residue or a decanol residue
  • G 11 is a propylene glycol residue, a neopentyl glycol residue or 1,3-propane. It is a diol residue
  • a 11 is an adipic acid residue
  • X is an adipic acid residue or a maleic acid residue.
  • the polyester represented by the general formula (I) may be used, for example, as a mixture of two or more kinds of polyesters in which at least one of each residue and the value of t in the general formula (I) is different from each other. At this time, the average value of t is preferably in the range of 2 to 15.
  • the polyester represented by the general formula (II) is used, for example, as a mixture of two or more kinds of polyesters in which at least one of the values of each residue and u in the general formula (II) is different from each other. May be good.
  • the average value of u is preferably in the range of 2 to 15. Further, it may be used as a mixture of the polyester represented by the general formula (I) and the polyester represented by the general formula (II). The average values of t and u can be confirmed from the number average molecular weight of polyester.
  • the acid value of the polyester represented by the general formula (I) or (II) is preferably in the range of 3 to 50, more preferably in the range of 3 to 35.
  • the acid value of the polyester is confirmed by the method described in Examples.
  • the number average molecular weight (Mn) of the polyester represented by the general formula (I) or (II) is preferably in the range of 300 to 3,000, more preferably in the range of 400 to 2,500, and further. It is preferably in the range of 400 to 1,500.
  • the number average molecular weight (Mn) is a polystyrene-converted value based on gel permeation chromatography (GPC) measurement, and is measured by the method described in Examples.
  • polyester represented by the general formula (I) or (II) differ depending on the number average molecular weight, composition, etc., but are usually liquid, solid, paste, etc. at room temperature.
  • the polyester represented by the general formula (I) or (II) can be produced in the same manner as the polyester of the present invention. Specifically, a method in which the above-mentioned diol, dicarboxylic acid, monocarboxylic acid or monoalcohol is charged in a batch to carry out an esterification reaction; after obtaining a compound having hydroxyl groups at both ends using a diol and a dicarboxylic acid. , A method of further reacting a monocarboxylic acid with a dicarboxylic acid; a method of further reacting a monoalcohol after obtaining a compound having carboxyl groups at both ends using a diol and a dicarboxylic acid can be mentioned.
  • the reaction product can be a mixture of the polyester represented by the general formula (1) and the polyester represented by the general formula (I) or (II), which is the inorganic filler dispersion stabilizer of the present invention. It is preferable because it has both an excellent thickening effect and a storage stabilizing effect.
  • the content of the thickener is not particularly limited, but is, for example, in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the inorganic filler, and preferably with respect to 100 parts by mass of the inorganic filler.
  • the agent is in the range of 0.1 to 10 parts by mass.
  • the inorganic filler-containing resin 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.
  • Phthrate esters such as diundecyl acid (DUP) and ditridecyl phthalate (DTDP); terephthalate esters such as bis (2-ethylhexyl) terephthalate (DOTP); isophthalates such as bis (2-ethylhexyl) isophthalate (DOIP) Esters; Pyromellitic esters such as tetra-2-ethylhexyl pyromellitic acid (TOPM); di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2 sebacate An aliphatic dibasic acid ester such as -ethylhexyl (DOS) and diisononyl sebacate (DINS); a phosphate ester such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphat
  • Alkyl esters of alcohols polyesters with a molecular weight of 800 to 4,000 synthesized by polyesterification of dibasic acids such as adipic acid and glycols; epoxidized esters such as epoxidized soybean oil and epoxidized flaxseed oil; hexahydrophthalic acid Alicyclic dibasic acid such as diisononyl ester; fatty acid glycol ester such as dicapric acid 1.4-butanediol; tributyl acetylcitrate (ATBC); chlorinated paraffin chlorinated paraffin wax or n-paraffin; chlorinated stearer Chlorinated fatty acid esters such as acid esters; higher fatty acid esters such as butyl oleate and the like can be mentioned.
  • the plasticizer to be used may be determined according to the intended use, and the above-mentioned plasticizer may be used alone or in combination of two or more.
  • the content of the plasticizer is not particularly limited, but is, for example, in the range of 10 to 300 parts by mass of the plasticizer with respect to 100 parts by mass of the inorganic filler, and preferably 30 to 200 parts by mass of the plasticizer with respect to 100 parts by mass of the inorganic filler. It is the range of the part. ..
  • the additives contained in the inorganic filler-containing resin composition of the present invention are not limited to the inorganic filler dispersion stabilizer of the present invention, the thickener, and the plasticizer, and other additives other than these may be included.
  • the other additives include flame retardants, stabilizers, stabilizing aids, coloring agents, processing aids, fillers, antioxidants (antioxidants), ultraviolet absorbers, light stabilizers, lubricants, and antistatic agents.
  • examples thereof include an inhibitor, a cross-linking aid, and the like.
  • the resin contained in the inorganic filler-containing resin composition of the present invention is not particularly limited, and polyolefin, polyester, polysulfide, polyvinyl chloride, modified polysulfide, silicone resin, modified silicone resin, acrylic urethane resin, epoxy resin, polyurethane, etc. Acrylic resin, polyester, unsaturated polyester and the like can be mentioned.
  • the resin to be used may be determined according to the intended use, and the above resins may be used alone or in combination of two or more.
  • the inorganic filler-containing resin composition of the present invention contains a resin
  • the dispersion stabilizer of the present invention can also be preferably used for a composition containing a viscous compound such as asphalt instead of the resin.
  • the inorganic filler-containing resin composition of the present invention can be suitably used as a paste-like resin composition that requires fluidity when used. Since the dispersion stabilizer of the present invention can reduce the viscosity of the composition, suppress the formation of hard cakes, and improve the storage stability of the composition, it is often used outdoors as a paint or adhesive. It is preferably applied to agents, structural materials, etc., and contains two-component urethane-based flooring paints that need to be mixed before coating, structural materials (building materials) for which an increase in filler content is desired, and fillers. It is suitable for polysulfide-based sealing materials with a particularly high rate.
  • composition examples for each application when the inorganic filler-containing resin composition of the present invention is used as a paste-like resin composition will be described.
  • the resin contained in the inorganic filler-containing resin composition used for the structural material examples include polyolefins, polyurethanes, unsaturated polyesters, and the like.
  • the resin used for the structural material (building material) differs depending on the application.
  • polyurethane is mainly used as the resin component for waterproof materials
  • unsaturated polyester is mainly used for artificial marble.
  • the inorganic filler-containing resin composition used for the waterproof material contains, for example, a main component containing an isocyanate group-containing compound and an aroma.
  • a polyurethane composition containing a curing agent component containing at least one selected from the group consisting of group polyamines, polyols, water and moisture is preferable.
  • an isocyanate group-terminated polyurethane prepolymer obtained by reacting a polyisocyanate having a diphenylmethane diisocyanate structure with a polyol is preferable.
  • 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 and 2,4'-diphenylmethane diisocyanate and / or 2,2'-diphenylmethane diisocyanate is preferable.
  • polyoxypropylene polyol is preferable, and polyoxypolypropylene diol alone or a mixture of polyoxypropylene diol and polyoxypropylene triol is more preferable.
  • the ratio of the polyisocyanate to the polyol in the above-mentioned isocyanate group-terminated urethane prepolymer is preferably in the range of 1.8 to 2.5 in terms of the molar ratio (NCO / OH) of the isocyanate group to the hydroxyl group.
  • 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. Of these, 4,4'-methylenebis (2-chloroaniline) is known as "MOCA" and is widely used.
  • a polyether polyol is preferable, and a polyoxypropylene polyol is particularly preferable.
  • the number of functional groups of this polyol is preferably in the range of 2 to 4, and more preferably in the range of 2 to 3.
  • the mixing ratio of the main agent and the curing agent is such that the molar ratio (NCO / (NH 2 + OH)) of the isocyanate group contained in the main agent and the active hydrogen-containing group contained in the curing agent is 1, for example. It is in the range of 0.0 to 2.0, preferably in the range of 1.0 to 1.8, and more preferably in the range of 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, for example, preferably in the range of 10 to 60 parts by mass, preferably in the range of 20 to 50 parts by mass with respect to 100 parts by mass of the resin component.
  • the viscosities of both the main agent and the curing agent are usually high (main agent: 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 is further increased, the dispersion stabilizer of the present invention capable of improving the dispersibility of the inorganic filler and improving the content is useful.
  • the dispersion stabilizer of the present invention may be contained in the resin composition for a waterproof material.
  • the dispersion stabilizer of the present invention may be contained in at least one of the main agent component and the curing agent component.
  • the curing agent component may contain a known curing catalyst.
  • the curing catalyst include lead organic acid, tin organic acid, and tertiary amine compounds.
  • the curing agent component includes the thickener, the plasticizer, pigments such as chromium oxide, titanium oxide, and phthalocyanine; and stabilizers such as antioxidants, ultraviolet absorbers, and dehydrating agents. It may be included.
  • Examples of the waterproof material obtained by molding the composition for the waterproof material include a rooftop waterproof material.
  • the rooftop waterproofing material is obtained, for example, by applying a composition in which a main ingredient and a curing agent component are mixed to a desired portion to form a coating film, and then reaction-curing.
  • the polysulfide-based resin used for the polysulfide-based sealing material is not particularly limited as long as it is a resin having a sulfide bond in the molecule.
  • a hydrocarbon group such as an alkyl group is bonded to the sulfide bond.
  • the polysulfide resin may have, for example, an ether bond, an ester bond, an amide bond, or an imide group in the skeleton.
  • the polysulfide resin When the polysulfide resin has an ether bond in the skeleton, it becomes a polysulfide polyether resin.
  • the polysulfide resin may have a functional group such as a thiol group, a hydroxy group, or an amino group at one end 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 of 1 to 5) in the main chain.
  • a structural unit represented by-(C 2 H 4 OCH 2 OC 2 H 4- Sx)-(x is an integer of 1 to 5) in the main chain.
  • 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 preferably has fluidity at room temperature, specifically 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.
  • a polysulfide polyether resin can also be mentioned.
  • Specific examples of the polysulfide polyether resin include a thiol group-containing polysulfide polyether resin.
  • Examples thereof 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.
  • the polysulfide-based resin is not limited in the production method, and those produced by various known methods can be used. Further, as the polysulfide resin, a commercially available product can also be used. Examples of commercially available polysulfide resins include "thiocol LP-23, LP-23" (manufactured by Toray Fine Chemicals Co., Ltd.) and "THIOPLAST polymer” (manufactured by AKZO NOBEL). The polysulfide-based resin may be used alone or in combination of two or more.
  • additives and the like can be used in combination with the polysulfide-based sealing material containing the dispersion stabilizer of the present invention.
  • the additive include the thickener, the plasticizer, an adhesive-imparting agent, a pigment, a dye, an antioxidant, an antioxidant, an antistatic agent, a flame retardant, a tackifier resin, a stabilizer, a dispersant and the like. Can be mentioned.
  • a silane coupling agent such as aminosilane is excellent in the effect of improving the adhesiveness to the glass surface, and is preferably 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.
  • the pigment 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, brown dye and the like.
  • anti-aging agent examples include hindered phenol-based compounds and hindered amine-based compounds.
  • antioxidants examples include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
  • antistatic agent examples include quaternary ammonium salts; hydrophilic compounds such as polyglycol 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 resin, phenol resin, terpene-phenol resin, rosin resin, xylene resin, epoxy resin, alkyl titanates, and organic polyisocyanates.
  • stabilizer examples include fatty acid silyl ester and fatty acid amide trimethylsilyl compound.
  • the dispersant refers to a substance that disperses a solid into fine particles in a liquid, and examples thereof include sodium hexametaphosphate, condensed sodium naphthalene sulfonate, and a surfactant.
  • the polysulfide-based sealant is usually mixed with a curing agent immediately before use.
  • a curing agent for example, a curing agent generally used for a polysulfide resin-based sealing material such as a metal oxide, a metal peroxide, an organic-inorganic oxidizing agent, an epoxy compound, and an isocyanate compound can be used.
  • metal peroxides such as lead dioxide and manganese dioxide are preferable, and manganese dioxide is more preferable.
  • the fluidity modifier of the present invention is preferably used by mixing it in this curing agent.
  • the amount used is 2.5 to 2.5 because a cured product having sufficient elasticity and appropriate elasticity can be obtained with respect to 100 parts by mass of the polysulfide resin used as the main agent.
  • the range is preferably in the range of 25 parts by mass, and more preferably in the range of 3 to 20 parts by mass.
  • 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 agent and the curing agent.
  • the curing time is usually in the range of 24 to 168 hours.
  • the inorganic filler-containing resin composition of the present invention is not limited to the above-mentioned paste-like resin composition, and can be suitably used as a molding resin composition for injection molding, extrusion molding, and the like.
  • the properties of the resin composition for molding are various, and it may be liquid at the stage before molding (normal temperature) or liquid by heating at the time of molding.
  • the dispersion stabilizer of the present invention reduces the viscosity of the composition.
  • an excessive increase in viscosity due to the inclusion of the inorganic filler can be suppressed, and the melt-kneading and the like performed before molding can be smoothly performed.
  • the dispersion stabilizer of the present invention can also increase the amount of the inorganic filler added, it is desired to increase the amount of the inorganic filler added to improve the physical properties. It can be suitably used for molding resin compositions such as stone paper and heat radiating members.
  • molding resin compositions such as stone paper and heat radiating members.
  • the resin component contained in the molding resin composition used for the automobile member (hereinafter, may be simply referred to as “the resin composition for the automobile member”) is, for example, a thermoplastic resin, which is excellent among the thermoplastic resins.
  • a thermoplastic resin which is excellent among the thermoplastic resins.
  • Polypropylene resins having features such as moldability, high mechanical strength, and economy are preferable.
  • the polypropylene is not particularly limited, but a polypropylene resin having an MFR (230 ° C., 2.16 kg) of 60 to 120 g / 10 minutes is preferable.
  • the resin composition for automobile parts may further contain an olefin-based thermoplastic elastomer as a resin component.
  • the olefin-based thermoplastic elastomer is not particularly limited, but one containing an ethylene- ⁇ -olefin copolymer is preferable.
  • Inorganic fillers contained in the resin composition for automobile parts include talc, calcium carbonate, and whiskers (the whiskers are made of graphite, potassium titanate, alumina, silicon carbide, silicon nitride, mulite, magnesia, magnesium borate, and hoe. (Aluminum acid acid, magnesium sulfate, zinc oxide, titanium boride, etc.), carbon nanofibers, carbon nanotubes, kaolin clay, mica, etc. can be mentioned.
  • the resin composition for automobile parts may contain various additives other than the dispersion stabilizer and the inorganic filler of the present invention, and the additives include the thickener, the plasticizer, the antioxidant, and the ultraviolet absorber. , Light stabilizers, flame retardants, colorants and the like.
  • the composition ratio of the resin component, the inorganic filler, the dispersion stabilizer and the like contained in the resin composition for automobile members is not particularly limited, but it is preferable to adjust the composition so as to satisfy one or more of the following physical properties.
  • the MFR (230 ° C., 2.16 kg, JIS-K7210-1) of the resin composition for automobile members is preferably 20 g / 10 minutes or more, and more preferably 20 to 30 g / 10 minutes.
  • the coefficient of linear expansion (JIS-K7197) of the resin composition for automobile members is preferably 5.0 ⁇ 10-5 / K or less, and preferably 4.0 to 5.0 ⁇ 10-5 / K. More preferred.
  • the tensile elastic modulus (JIS-K7161) of the resin composition for automobile members is preferably 2.5 GPa or more, and more preferably 2.5 to 3.0 GPa.
  • the Charpy impact value (JIS-K7111) of the resin composition for automobile members is preferably 30 kJ / m 2 or more, and more preferably 30 to 40 kJ / m 2 .
  • Examples of the automobile member obtained by molding the resin composition for the automobile member include a bonnet hood, a fender, a bumper, a door, a trunk lid, a roof, a radiator grill, a hubcap, an instrument panel, a pillar garnish and the like. These automobile members can be manufactured by injection molding a resin composition for automobile members.
  • the resin component contained in the molding resin composition used for the sanitary absorption article (hereinafter, may be simply referred to as "resin composition for sanitary absorption article") is, for example, polyolefin, and among the polyolefins, polyethylene and polypropylene are used. One or more selected from the above group is preferable, and polyethylene is more preferable. When polyethylene is used as the resin component, for example, two or more types of polyethylene having different densities may be used.
  • the polyolefin which is the resin component of the resin composition for sanitary absorption articles is not particularly limited, but the MFR (190 ° C., 2.16 kgf) is preferably in the range of 0.1 to 20 g / 10 minutes, and 0.5 to 5 g / 10. The minute range is more preferred.
  • the MFR is 0.1 g / 10 minutes or more, the moldability of the thin film film can be sufficiently maintained, and when the MFR is 20 g / 10 minutes or less, sufficient strength can be obtained.
  • the resin composition for sanitary absorption articles may further contain a polystyrene-based elastomer as a resin component.
  • a polystyrene-based elastomer examples 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). , HSBR, etc.) styrene block-containing elastomers.
  • the styrene component in these polystyrene-based elastomers is preferably in the range of 10 to 40% by mass, more preferably in the range of 20 to 40% by mass.
  • Examples of the inorganic filler contained in the resin composition for sanitary absorption articles include calcium carbonate, calcium sulfate, barium carbonate, titanium oxide and the like, and one or more selected from the group consisting of calcium carbonate and barium sulfate is preferable.
  • the shape of these inorganic fillers is not particularly limited, but it is preferably in the form of particles, more preferably fine particles having an average particle diameter in the range of 0.1 to 10 ⁇ m, and fine particles having an average particle diameter in the range of 0.3 to 5 ⁇ m. Is more preferable, and fine particles having an average particle diameter in the range of 0.5 to 3 ⁇ m are particularly preferable.
  • the content of the inorganic filler is within the above range, all of the moisture permeability, breathability and liquid permeability resistance of the obtained sanitary absorbent article can be sufficiently ensured.
  • the resin composition for sanitary absorption articles may contain various additives other than the dispersion stabilizer and the inorganic filler of the present invention, and the additives include the thickener, the plasticizer, the compatibilizer, and processing aid.
  • additives include the thickener, the plasticizer, the compatibilizer, and processing aid.
  • oils agents include oil agents, radiation shielding agents, colorants, pigments and the like.
  • the molded product obtained by molding the resin composition for sanitary absorbent articles is used as a back sheet (a sheet having breathability and moisture permeability but not allowing liquid to pass through) used in sanitary absorbent articles such as disposable diapers and sanitary napkins. It can be preferably used.
  • the back sheet can be produced, for example, by melt-kneading a resin composition for a sanitary absorbing article, forming a sheet by a T-die method or an inflation method, and then stretching the obtained sheet uniaxially or biaxially.
  • Stone paper is a sheet containing calcium carbonate derived from limestone and polyolefin (polyethylene, polypropylene, etc.). It does not require water or wood to form the sheet, and the raw material limestone is almost inexhaustible on the earth. It is a highly sustainable sheet because it is present in. Although stone paper contains a large amount of calcium carbonate, the flowability of calcium carbonate can be increased by the dispersion stabilizer of the present invention, so that the physical characteristics of the sheet can be improved.
  • Stone paper can be produced, for example, by melt-kneading a stone paper composition containing calcium carbonate, polyolefin, and the dispersion stabilizer of the present invention, and inflating or extruding.
  • the content of calcium carbonate is, for example, 85:15 to 20:80, preferably 85:15 to 30:70, in terms of mass ratio of polyolefin to calcium carbonate (polyformate: calcium carbonate). , More preferably 85:15 to 35:65, and even more preferably 80:20 to 40:60.
  • the stone paper composition further contains the thickener, the plasticizer, the foaming agent, the coloring agent, the lubricant, the coupling agent, the stabilizer (antioxidant, the ultraviolet absorber, etc.), the antistatic agent and the like as auxiliary agents. It may be.
  • effervescent 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, difluoro dichloromethane, and the like. Halogenized hydrocarbon compounds and the like.
  • lubricant examples include fatty acid-based lubricants such as stearic acid, hydroxystearic acid, composite stearic acid, and oleic acid; aliphatic alcohol-based lubricants, stearoamides, oxystearoamides, oleylamides, elcilamides, ricinolamides, behenamides, and the like.
  • Aliphatic amide lubricants such as methylolamide, methylene bisstearoamide, methylene bisstearobehenamide, higher fatty acid bisamide acid, complex amide; stearate-n-butyl, methyl hydroxystearate, polyhydric alcohol fatty acid ester , Fatty acid ester-based lubricants such as saturated fatty acid esters and ester waxes; fatty acid metal soap-based lubricants and the like can be mentioned.
  • a phosphorus-based antioxidant As the antioxidant, a phosphorus-based antioxidant, a phenol-based antioxidant, a pentaerythritol-based antioxidant, or the like can be used.
  • Phosphorus-based antioxidants include triesters of phosphoric acids such as triphenylphosphite, trisnonylphenylphosphite, and tris (2,4-di-tert-butylphenyl) phosphite, and subesters such as diesters and monoesters.
  • Phosphoric acid ester Phosphate ester such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate and the like can be mentioned. ..
  • phenolic antioxidants include ⁇ -tocopherol, butylhydroxytoluene, cinapyl 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 And so on.
  • Heat dissipation member In electronic devices such as personal computers, smartphones, and televisions, the amount of heat generated is increasing as the performance is improved, and a heat radiating member containing a heat conductive filler is often used in order to efficiently dissipate the generated heat.
  • automobiles such as electric vehicles and hybrid vehicles are also equipped with many electronic devices, and heat-dissipating members containing a heat conductive filler are often used.
  • resin composition for heat radiating member examples include a thermosetting resin, an active energy ray curable resin, and a thermoplastic resin. be.
  • thermocurable resin of the resin composition for the heat radiating member a known thermocurable resin can be used, for example, novolak-type phenol resins such as phenol novolac resin and cresol novolac resin; Phenol resins such as resol-type phenol resins such as oil-modified resol-phenol resins modified with flaxseed oil and walnut oil; bisphenol-type epoxy resins such as bisphenol A epoxy resin and bisphenol F epoxy resin; Novolac type epoxy resin such as epoxy resin and cresol novolac epoxy resin; epoxy resin such as biphenyl type epoxy resin and polyalkylene glucol type epoxy resin; resin having triazine ring such as urea (urea) resin and melamine resin; (meth) Vinyl resins such as acrylic resins and vinyl ester resins: Examples thereof include unsaturated polyester resins, bismaleimide resins, polyurethane resins, diallyl phthalate resins, silicone resins, resins having a benzoxazine ring, and
  • the thermosetting resin may be used together with a curing agent.
  • the curing agent used together with the thermocurable resin include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, and guanidine derivative; dicyandiamide and linolenic acid.
  • Amid compounds such as polyamide resins synthesized from the body 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 novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadienephenol addition type resin, phenol aralkyl resin ( Zyroc resin), resorcin novolac resin, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-shrink novolak resin, naphthol-cresol co-sh
  • thermoplastic resin of the resin composition for the heat radiating member a known thermoplastic resin can be used, for example, polyethylene resin, polypropylene resin, polymethyl methacrylate resin, polyvinyl acetate resin, ethylene-propylene copolymer, 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, polyethersulfone resin, polyether Etherketone resin, polyallyl sulfone resin, thermoplastic polyimide resin, thermoplastic urethane resin, polyaminobismaleimide resin, polyamideimide resin, polyetherimide resin, bismaleimide triazine resin, polymethylpentene resin, fluororesin, liquid crystal polymer, Examples thereof include olefin-vinyl alcohol copolymers, ionomer resins, polyarylate resins, acrylonitrile-ethylene-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, acrylonitrile-sty
  • Examples of the heat conductive filler contained in the resin composition for the heat radiating member include alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, calcium oxide, magnesium oxide, zinc oxide, berylia, and aluminum oxide. Examples thereof include aluminum oxide, boron nitride, hydrated metal compounds, fused silica, crystalline silica, non-crystalline silica, silicon carbide, silicon nitride, titanium carbide, and diamond.
  • As the heat conductive filler one that has been surface-treated with a silane-based, titanate-based, aluminate-based coupling agent, or the like may be used.
  • the shape of the heat conductive filler is not particularly limited, and may be spherical, needle-shaped, flake-shaped, dendritic-shaped, or fibrous.
  • the content of the heat conductive filler in the resin composition for the heat radiating member can be appropriately adjusted depending on the application, and it is preferable that the heat conductive filler is in the range of 30 to 500 parts by mass with respect to 100 parts by mass of the resin component.
  • the resin composition for a heat radiating member may contain various additives other than the inorganic filler dispersion stabilizer and the heat conductive filler of the present invention, and the additives include dyes, pigments, antioxidants, polymerization inhibitors, and the like. Examples thereof include defoaming agents, leveling agents, ion collecting agents, moisturizing agents, viscosity modifiers, preservatives, antibacterial agents, antistatic agents, antiblocking agents, ultraviolet absorbers, infrared absorbers and the like.
  • the heat-dissipating member resin composition contains a thermosetting resin
  • the heat-dissipating member can be molded by heating the heat-dissipating member resin composition.
  • the resin composition for a heat radiating member contains an active energy ray-curable resin
  • it can be cured and molded by irradiating it with active energy rays such as ultraviolet rays and infrared rays.
  • the resin composition for a heat radiating member contains a thermoplastic resin
  • the heat radiating member can be obtained by a known molding method such as injection molding, extrusion molding, or press molding.
  • the heat radiating member obtained by molding the resin composition for the heat radiating member can be used as a heat sink.
  • the heat radiating member obtained by molding the resin composition for the heat radiating member can also be used as a heat radiating joining member for joining the portion to be radiated and the metal heat radiating member.
  • the resin composition for the heat radiating member can also be used as a semiconductor encapsulating material.
  • the inorganic filler dispersion stabilizer of the present invention can improve the storage stability even in the inorganic filler-containing composition containing no resin. For example, by adding the dispersion stabilizer of the present invention to a composition containing an organic solvent such as acetone and an inorganic filler, the sedimentation rate of the inorganic filler is reduced and an aggregate (hard cake) containing the inorganic filler is formed. It can be suppressed.
  • an organic solvent such as acetone and an inorganic filler
  • the acid value and the hydroxyl value are the values evaluated by the following methods.
  • 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 velocity: 0.35 mL / min Measurement sample: 7.5 mg of the sample was
  • Example 1 Synthesis of dispersion stabilizer A
  • 0.0053 g of isopropyl titanate was charged, and the temperature was gradually raised to 220 ° C. with stirring under a nitrogen stream to cause a condensation reaction for a total of 10 hours.
  • the unreacted components were distilled off under reduced pressure to obtain a dispersion stabilizer A (acid value 110, hydroxyl value 0, number average molecular weight 1,000) containing a polyester having a carboxyl group at both ends.
  • Example 2 Synthesis of dispersion stabilizer B 1702.5 g of 3-methyl-1,5-pentanediol and 625.5 g of 1,12-dodecanedioic acid in a 4-neck flask with an internal volume of 3 liters equipped with a thermometer, agitator, and a reflux condenser. , 0.069 g of tetraisopropyl titanate was charged as an esterification catalyst, and the temperature was gradually raised to 220 ° C. with stirring under a nitrogen stream to carry out a condensation reaction for a total of 10 hours.
  • Example 3 Synthesis of dispersion stabilizer C
  • 1214 g of 3-methyl-1,5-pentanediol, 966 g of sebacic acid, and tetraisopropyl titanate as an esterification catalyst were placed in a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. 0.07 g was charged, and the temperature was gradually raised to 220 ° C. while stirring under a nitrogen stream to carry out a condensation reaction for a total of 12 hours. After the reaction, 0.11 g of hydroquinone and 203 g of maleic anhydride were charged at 150 ° C. to complete the reaction, so that the dispersion stabilizer C (acid value 24.7, hydroxyl value) containing polyester having a carboxyl group at both ends was charged. 64, number average molecular weight 1,700) was obtained.
  • the dispersion stabilizer C contained polyester having carboxyl groups at both ends. Specifically, the dispersion stabilizer C was evaluated using a matrix-assisted laser desorption / ionization time-of-flight mass spectrometer (AXIMA TOF2 manufactured by Shimadzu Corporation), and sebacic acid, 3-methyl-1,5-pentane was evaluated. In polyesters using diol and maleic acid as reaction raw materials, the molecular weights of 621 (M + Na) + and 905 (M + Na) + observed when both ends are carboxyl groups were detected. The measurement results are shown in FIG.
  • Example 4 Synthesis of dispersion stabilizer D
  • 395.7 g of propylene glycol, 809.0 g of sebacic acid, and 0.07 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser.
  • the condensation reaction was carried out for a total of 12 hours by gradually raising the temperature to 220 ° C. with stirring under a nitrogen stream.
  • 0.06 g of hydroquinone and 109.8 g of maleic anhydride were charged at 150 ° C. to complete the reaction, so that the dispersion stabilizer D containing polyester having a carboxyl group at both ends (acid value 44.8, A hydroxyl value of 38.0 and a number average molecular weight of 1,840) were obtained.
  • Example 5 Synthesis of dispersion stabilizer E 1214 g of 3-methyl-1,5-pentanediol, 966 g of sebacic acid, and tetraisopropyl titanate as an esterification catalyst were placed in a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. 0.07 g was charged, and the temperature was gradually raised to 220 ° C. while stirring under a nitrogen stream to carry out a condensation reaction for a total of 12 hours. After the reaction, 306.7 g of phthalic anhydride was charged at 150 ° C. to complete the reaction, so that the dispersion stabilizer E containing polyester having a carboxyl group at both ends (acid value 49.0, hydroxyl value 48.4, A number average molecular weight of 1,170) was obtained.
  • Example 6 Synthesis of dispersion stabilizer F 459.3 g of 1,3-butanediol, 48.7 g of neopentyl glycol, 616.2 g of adipic acid, in a 4-necked flask with an internal volume of 2 liters equipped with a thermometer, agitator, and a reflux condenser. 0.112 g of tetraisopropyl titanate was charged as an esterification catalyst, and the temperature was gradually raised to 220 ° C. with stirring under a nitrogen stream to cause a condensation reaction for a total of 10 hours.
  • a thickener A (acid value 29.7, hydroxyl value 19.), which is a polyester having a carboxyl group at one end and a hydroxyl group at the other end. 1. Number average molecular weight 1,800) was obtained.
  • Examples 7-15 and Comparative Example 1-5 Preparation and evaluation of calcium carbonate-containing composition
  • Calcium carbonate (heavy calcium carbonate, "Super S” manufactured by Maruo Calcium Co., Ltd.) as an inorganic filler
  • DINP diisononyl phthalate
  • DETDA diethyltoluenediamine
  • the agents were blended in the ratios shown in Tables 1 and 2 and stirred with a planetary stirrer (THINKY ARV-310) at 1000 rpm and 0.2 Pa for 2 minutes to obtain a paste-like inorganic filler-containing composition.
  • the viscosity and storage stability of the obtained paste composition were evaluated by the following methods. The results are shown in Tables 1 and 2.
  • the paste using both the inorganic filler dispersion stabilizer and the thickener of the present invention has a slightly increased viscosity but remarkable storage stability. It can be read that it has improved. Further, from the evaluation results of Examples 11-15 and Comparative Example 1-3, it can be seen that the inorganic filler dispersant stabilizer of the present invention can sufficiently exhibit not only a storage stabilizing effect but also a thickening effect. Can be read.
  • Example 16-18 and Comparative Example 6-8 Preparation and evaluation of calcium carbonate-containing resin composition
  • Table 3 shows calcium carbonate (heavy calcium carbonate, "Super S” manufactured by Maruo Calcium Co., Ltd.) as an inorganic filler, polyethylene (“UMERIT 2040F” manufactured by Ube Kosan Co., Ltd.) as a binder resin, dispersion stabilizer and thickener.
  • a containing resin composition was prepared.
  • the torque value and internal temperature of melt-kneading during the preparation of the inorganic filler-containing resin composition were evaluated. The results are shown in Table 3.
  • the torque value and the internal temperature are values obtained by reading the displayed values of the kneader at a kneading time of 8 minutes.
  • the resin composition containing the inorganic filler dispersion stabilizer of the present invention has a reduced torque value and suppressed temperature rise. It can be read that the resin composition is reduced in viscosity by the inorganic filler dispersant stabilizer.
  • Example 19 and Comparative Example 9-10 Preparation and evaluation of talc-containing resin composition
  • a dispersion stabilizer and a thickener a thickener.
  • the resin composition containing the inorganic filler dispersion stabilizer of the present invention has a reduced torque value and suppressed temperature rise, and the inorganic filler of the present invention is suppressed. It can be read that the resin composition is reduced in viscosity by the dispersant stabilizer.
  • Example 20 Synthesis of dispersion stabilizer G
  • 0.125 g of tetraisopropyl titanate was charged as a catalyst, and the temperature was gradually raised to 220 ° C. with stirring under a nitrogen stream to cause a condensation reaction for a total of 16 hours.
  • 373 g of maleic anhydride was charged at 125 ° C. to complete the reaction, and a dispersion stabilizer G (acid value 55, hydroxyl value 53, number average molecular weight 1190) containing polyester having a carboxyl group at both ends was obtained.
  • Example 21 Synthesis of dispersion stabilizer H
  • 0.126 g of tetraisopropyl titanate was charged as a catalyst, and the temperature was gradually raised to 220 ° C. with stirring under a nitrogen stream to cause a condensation reaction for a total of 17 hours.
  • 387 g of maleic anhydride was charged at 125 ° C. to complete the reaction, and a dispersion stabilizer H (acid value 56, hydroxyl value 43, number average molecular weight 1550) containing polyester having a carboxyl group at both ends was obtained.
  • Example 22 Synthesis of dispersion stabilizer I
  • 1,214 g of 3-methyl-1,5-pentanediol, 966 g of sebacic acid, and tetraisopropyl as an esterification catalyst.
  • 0.07 g of titanate was charged, and the temperature was gradually raised to 220 ° C. with stirring under a nitrogen stream to cause a condensation reaction for a total of 12 hours.
  • 271 g of maleic anhydride was charged at 125 ° C. to complete the reaction, so that the dispersion stabilizer I (acid value 65, hydroxyl value 35, number average molecular weight 1,540) containing polyester having carboxyl groups at both ends was charged. )
  • the dispersion stabilizer I (acid value 65, hydroxyl value 35, number average molecular weight 1,540) containing polyester having carboxyl groups at both ends was charged. )
  • the dispersion stabilizer I (acid value 65, hydroxyl value 35, number average molecular weight 1,540)
  • Example 23 Synthesis of dispersion stabilizer J
  • a dispersion stabilizer J (acid) containing polyester having a carboxyl group at both ends was subjected to a condensation reaction for a total of 13 hours by charging .04 g and gradually raising the temperature to 220 ° C. while stirring under a nitrogen stream.
  • a value of 22, a hydroxyl value of 1, and a number average molecular weight of 4320) were obtained.
  • Example 24-27 Preparation and evaluation of calcium carbonate-containing composition
  • Calcium carbonate (heavy calcium carbonate, "Super S” manufactured by Maruo Calcium Co., Ltd.) as an inorganic filler
  • DINP diisononyl phthalate
  • DETDA diethyltoluenediamine
  • the agents were blended at the ratios shown in Table 5 and stirred with a planetary stirrer (THINKY ARV-310) at 1000 rpm and 0.2 Pa for 2 minutes to obtain a paste-like inorganic filler-containing composition.
  • the resulting paste was evaluated for viscosity and storage stability in the same manner as described above. The results are shown in Table 5.
  • Example 28-30 and Comparative Example 11-16 Preparation and evaluation of alumina-containing composition
  • Alumina high-purity alumina, "AKP-3000” manufactured by Sumitomo Chemical Co., Ltd.
  • alicyclic epoxy resin "Selokiside 2021P” manufactured by Daicel Co., Ltd.) or bisphenol A type epoxy resin (manufactured by DIC Co., Ltd.) as a binder resin.
  • Epoxy 850-S dispersion stabilizer and thickener are blended in the proportions shown in Table 6, and the mixture is stirred with a planetary stirrer (THINKY ARV-310) at 1000 rpm and 0.2 Pa for 2 minutes to obtain an inorganic filler.
  • the containing composition was obtained.
  • the obtained composition was evaluated for fluidity and complex viscosity by the method shown below, and storage stability was evaluated by the same method as above. The results are shown in Tables 6 and 7.
  • the obtained composition was subjected to frequency-dependent measurement by a dynamic viscoelasticity measurement method using MCR-302 (manufactured by Anton Pearl Co., Ltd.). Specifically, when a parallel plate (diameter: 20 mm) is used, the measurement temperature is 25 ° C., the shear strain is 0.01%, the angular frequency is in the range of 0.1 to 100 rad / s, and the angular frequency is 1 rad / s. The complex viscosity of was determined.
  • Examples 31-32 and Comparative Examples 17-19 Preparation and evaluation of alumina-containing compositions
  • Alumina high-purity alumina, "AKP-3000” manufactured by Sumitomo Chemical Co., Ltd.
  • acetone a dispersion stabilizer and a thickener
  • a planetary stirrer TINKY ARV-310
  • the mixture was stirred at 1000 rpm and 0.2 Pa for 2 minutes to obtain an inorganic filler-containing composition.
  • the obtained composition was evaluated for fluidity and storage stability by the methods shown below. The results are shown in Table 8.

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WO2023204033A1 (ja) * 2022-04-21 2023-10-26 Dic株式会社 無機フィラー流動性改質剤、無機フィラー含有組成物および熱伝導性シリコーンシート
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JP7509329B2 (ja) 2022-04-21 2024-07-02 Dic株式会社 無機フィラー流動性改質剤、無機フィラー含有組成物および熱伝導性シリコーンシート
TWI919063B (zh) 2022-04-21 2026-03-21 日商Ｄｉｃ股份有限公司 無機填料流動性改質劑、含有無機填料之組成物及熱傳導性聚矽氧薄片
EP4516860A4 (en) * 2022-04-28 2026-04-29 Dainippon Ink & Chemicals BIODEGRADABLE RESIN DEGRADATION ACCELERATOR, BIODEGRADABLE RESIN COMPOSITION, MOLDED BODY AND BIODEGRADABLE RESIN DEGRADATION PROCESS

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JPWO2021192883A1 (https=) 2021-09-30
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EP4130151A1 (en) 2023-02-08
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JP7127754B2 (ja) 2022-08-30
CN115298262A (zh) 2022-11-04

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