TWI878604B - Inorganic filler dispersing stabilizer, resin composition containing inorganic filler and molded product - Google Patents

Abstract

The present invention provides an inorganic filler dispersing stabilizer, which can reduce the viscosity of a composition containing an inorganic filler and improve the storage stability of the composition containing an inorganic filler. Specifically, an inorganic filler dispersing stabilizer is a polyester having carboxyl groups at both ends.

Description

Inorganic filler dispersing stabilizer, resin composition containing inorganic filler and molded products

The present invention relates to an inorganic filler dispersing stabilizer, a resin composition containing an inorganic filler, a molded product and an additive.

Building materials, automotive components, sanitary absorbent products, stone paper, etc. are formed from resin compositions containing inorganic fillers, and various functions such as impact resistance, bending resistance, dimensional stability, and moisture permeability are imparted to the materials by the inorganic fillers.

In order to improve the functionality of the above-mentioned molded products and to achieve cost reduction due to the increase in volume, it is necessary to further increase the amount of inorganic filler. However, if the amount of inorganic filler in the composition is increased, there is a problem that the fluidity of the resin composition is reduced and the moldability is reduced.

For example, in the application of urethane waterproof flooring materials, calcium carbonate is generally used as an inorganic filler, but increasing the amount of calcium carbonate filling will increase the viscosity, and the formability and controllability will deteriorate.

As a method of increasing the inorganic filler content of the resin composition, a method of adding a deviscosity reducing agent is adopted, and various deviscosity reducing agents are proposed (Patent Documents 1 and 2).

[Prior Art Literature] [Patent Literature]

Patent document 1: Japanese Patent Publication No. 2011-079935 Patent document 2: Japanese Patent Publication No. Sho 54-34009

[Problems to be solved by the invention]

The aforementioned deviscosity reducing agent suppresses the interaction between inorganic fillers and reduces the viscosity of the composition by coating the surface of the inorganic filler. On the other hand, due to the reduction of the viscosity of the composition, the inorganic filler precipitates over time, forming agglomerates (hard masses) containing the inorganic filler, and the storage stability is significantly impaired. In addition, the aforementioned deviscosity reducing agent may not show a deviscosity reducing effect depending on the type of adhesive resin contained in the composition.

The problem to be solved by the present invention is to provide an inorganic filler dispersing stabilizer that can reduce the viscosity of a composition containing an inorganic filler and improve storage stability. [Means for solving the problem]

The inventors of this case have conducted careful research to solve the above problems and found that the viscosity of the resin composition containing inorganic fillers can be reduced and the storage stability can be improved by using polyester with a specific structure, thus completing the present invention.

That is, the present invention relates to an inorganic filler dispersing stabilizer, which is a polyester having carboxyl groups at both ends. [Effects of the invention]

According to the present invention, an inorganic filler dispersing stabilizer can be provided, which can reduce the viscosity of a composition containing an inorganic filler and improve the storage stability of the composition containing an inorganic filler.

[Form used to implement the invention]

The following is an explanation of one embodiment of the present invention. The present invention is not limited to the following embodiment, and can be implemented with appropriate modifications without impairing the effects of the present invention.

[Inorganic filler dispersing stabilizer] The inorganic filler dispersing stabilizer of the present invention is a polyester having carboxyl groups at both ends. Hereinafter, the inorganic filler dispersing stabilizer of the present invention may be referred to as "the dispersing stabilizer of the present invention", and the polyester that is the inorganic filler dispersing stabilizer of the present invention may be referred to as "the polyester of the present invention". In the present invention, "dispersing stabilizer" means a component that is added to a composition containing an inorganic filler to prevent the inorganic filler in the composition from agglomerating and precipitating.

The polyester of the present invention forms a three-dimensional network including polyester and inorganic filler by adsorbing one of the carboxyl groups at the two ends to an inorganic filler and the other carboxyl group to a different inorganic filler. If the shear force between the compositions is kept very small, the three-dimensional network maintains this form, which can increase the viscosity of the system and inhibit the precipitation of the inorganic filler. On the other hand, if the shear force between the compositions is large, the three-dimensional network is destroyed and dispersed due to the shear force, which can reduce the viscosity of the line. This effect can be expected to be unaffected by various adhesive resins used in the composition.

The polyester of the present invention is preferably a polyester having 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 a repeating unit represented by the following general formula (1-1), a repeating unit represented by the following general formula (1-2), and a repeating unit represented by the following general formula (1-3), and is a polyester having carboxyl groups at both ends.

(In the above formulas (1-1), (1-2) and (1-3), 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, and 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 aforementioned general formula (1-1) and a repeating unit represented by the aforementioned general formula (1-2), and having carboxyl groups at both ends.

The polymerization form of the polyester having the repeating units represented by the aforementioned general formula (1-1), the repeating units represented by the aforementioned general formula (1-2), and the repeating units represented by the aforementioned general formula (1-3) is not particularly limited, and may be a random copolymer of the repeating units or a block copolymer of the repeating units.

The polyester of the present invention is preferably a polyester represented by the following general formula (1).

(In the above general formula (1), _A1 is an aliphatic dibasic acid residue having 2 to 12 carbon atoms.

_A2 and _A3 are each independently an aliphatic polybasic acid residue having 2 to 12 carbon atoms or an aromatic polybasic acid residue having 6 to 15 carbon atoms.

_G1 and _G2 are each independently an aliphatic diol residue having 2 to 9 carbon atoms.

m represents the number of repetitions and is an integer ranging from 1 to 20.

p is an integer obtained by subtracting 1 from the number of acid functional groups (hydroxy acid functional groups) of the aliphatic polybasic acid or aromatic polybasic acid of _A2 .

q is an integer obtained by subtracting 1 from the number of acid functional groups of the aliphatic polybasic acid or aromatic polybasic acid of _A3 .

Each of the repeating units _A1 and _G1 enclosed in brackets may be the same or different.)

In the present invention, "diacid residue" refers to an organic group obtained by removing the acid functional group from a dibasic acid. For example, when the dibasic acid residue is a dicarboxylic acid residue, the dicarboxylic acid residue refers to an organic group remaining after removing the carboxyl group of the dicarboxylic acid. The number of carbon atoms in the dicarboxylic acid residue is set to exclude the carbon atoms in the carboxyl group.

In the present invention, "polyacid residue" refers to an organic group obtained by removing an acid functional group from a polyacid having two or more acid functional groups. For example, when the polyacid residue is a dicarboxylic acid residue, a tricarboxylic acid residue or a tetracarboxylic acid residue, the aforementioned dicarboxylic acid residue, the aforementioned tricarboxylic acid residue or the aforementioned tetracarboxylic acid residue represents an organic group remaining after removing the carboxyl groups possessed by the aforementioned dicarboxylic acid residue, the tricarboxylic acid residue and the tetracarboxylic acid residue have carbon atoms that do not include the carbon atoms in the carboxyl groups.

In the present invention, "diol residue" and "alcohol residue" refer to organic groups remaining after removing hydroxyl groups from diols and alcohols.

In the present invention, "hydroxycarboxylic acid residue" refers to the residual organic group after removing the hydroxyl group and the carboxyl group from hydroxycarboxylic acid. The number of carbon atoms in the hydroxycarboxylic acid residue does not include the carbon atoms in the carboxyl group.

The aliphatic dibasic acid residues having 2 to 12 carbon atoms of A and _A1 may also contain an alicyclic structure.

The aliphatic dibasic acid residue having 2 to 12 carbon atoms of A and _A1 is preferably an aliphatic dicarboxylic acid residue having 2 to 12 carbon atoms. Examples of the aliphatic dicarboxylic acid residue having 2 to 12 carbon atoms include succinic acid residue, adipic acid residue, pimelic acid residue, suberic acid residue, azelaic acid residue, sebacic acid residue, cyclohexanedicarboxylic acid residue, dodecanedicarboxylic acid residue, and hexahydrophthalic acid residue.

The aliphatic dibasic acid residue having 2 to 12 carbon atoms of A and _A1 is preferably an aliphatic dicarboxylic acid residue having 4 to 10 carbon atoms, more preferably an aliphatic dicarboxylic acid residue having 5 to 10 carbon atoms, and even more preferably a sebacic acid residue or a dodecanedicarboxylic acid residue.

The aliphatic polyacid residues having 2 to 12 carbon atoms of _A2 and _A3 may also contain an alicyclic structure. The aliphatic polyacid residues having 2 to 12 carbon atoms of _A2 and _A3 are preferably aliphatic dicarboxylic acid residues having 2 to 12 carbon atoms. Examples of the aliphatic dicarboxylic acid residues having 2 to 12 carbon atoms include succinic acid residues, adipic acid residues, pimelic acid residues, suberic acid residues, azelaic acid residues, sebacic acid residues, cyclohexanedicarboxylic acid residues, dodecanedicarboxylic acid residues, hexahydrophthalic acid residues, and maleic acid residues.

The aromatic polyacid residue having 6 to 15 carbon atoms of _A2 and _A3 is preferably an aromatic dicarboxylic acid residue having 6 to 15 carbon atoms, an aromatic tricarboxylic acid residue having 6 to 15 carbon atoms, or an aromatic tetracarboxylic acid residue having 6 to 15 carbon atoms, and examples thereof include phthalic acid residue, trimellitic acid residue, pyromellitic acid residue, and the like.

Examples of the aliphatic diol residue having 2 to 9 carbon atoms of G, _G1 and _G2 include ethylene glycol residue, 1,2-propylene glycol residue, 1,3-propylene glycol residue, 1,2-butylene glycol residue, 1,3-butylene glycol residue, 2-methyl-1,3-propylene glycol residue, 1,4-butylene glycol residue, 1,5-pentanediol residue, 2,2-dimethyl-1,3-propylene glycol (neopentyl glycol) residue, 2,2-diethyl-1,3 -propylene glycol (3,3-dihydroxymethylpentane) residue, 2-n-butyl-2-ethyl-1,3-propylene glycol (3,3-dihydroxymethylheptane) residue, 3-methyl-1,5-pentanediol residue, 1,6-hexanediol residue, 2,2,4-trimethyl-1,3-pentanediol residue, 2-ethyl-1,3-hexanediol residue, 2-methyl-1,8-octanediol residue, 1,9-nonanediol residue, etc.

The aliphatic diol residue having 2 to 9 carbon atoms of G, _G1 and _G2 may also contain an alicyclic structure and/or an ether bond. Examples of the aliphatic diol residue having 2 to 9 carbon atoms containing an alicyclic structure include 1,3-cyclopentanediol residue, 1,2-cyclohexanediol residue, 1,3-cyclohexanediol residue, 1,4-cyclohexanediol residue, 1,2-cyclohexanedimethanol residue, 1,4-cyclohexanedimethanol residue, and the like.

As the aforementioned aliphatic diol residue with 2 to 9 carbon atoms and containing an ether bond, for example: diethylene glycol residue, triethylene glycol residue, tetraethylene glycol residue, dipropylene glycol residue, tripropylene glycol residue, etc. can be cited.

The aliphatic diol residue having 2 to 9 carbon atoms represented by G, _G1 and _G2 is preferably an aliphatic diol residue having 3 to 8 carbon atoms, more preferably 2-methyl-1,3-propanediol residue, 3-methyl-1,5-pentanediol, 1,3-propanediol, propylene glycol residue or diethylene glycol residue.

As the hydroxy carboxylic acid residue with 2 to 18 carbon atoms as L, there can be cited propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, pearly acid, stearic acid, etc., and as specific examples, there can be cited the hydroxy carboxylic acid residue in which one hydroxyl group is substituted in the aliphatic chain of aliphatic carboxylic acid with 3 to 19 carbon atoms, such as lactic acid residue, 9-hydroxystearic acid residue, 12-hydroxystearic acid residue, 6-hydroxycaproic acid residue, etc.

L is a hydroxy carboxylic acid residue having 2 to 18 carbon atoms, preferably an aliphatic hydroxy carboxylic acid residue having 4 to 18 carbon atoms, and more preferably a 12-hydroxy stearic acid residue.

p is an integer obtained by subtracting 1 from the number of acid functional groups of the aliphatic polybasic acid or aromatic polybasic acid of _A2 . Similarly, q is an integer obtained by subtracting 1 from the number of acid functional groups of the aliphatic polybasic acid or aromatic polybasic acid _of A3. Therefore, when _A2 and _A3 are each independently an aliphatic dicarboxylic acid residue having 2 to 12 carbon atoms or an aromatic dicarboxylic acid residue having 6 to 15 carbon atoms, the number of acid functional groups (carboxyl groups) possessed by _A2 and _A3 is 2, and p and q are 1, respectively, and the aforementioned general formula (1) is represented as follows.

The polyester of the present invention can be used, for example, as a mixture of two or more polyesters having at least one different value of each residual group and m in the general formula (1). In this case, the average value of m is preferably in the range of 2 to 15.

Furthermore, the average value of m can be confirmed by 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, more preferably in the range of 500 to 5,000, and even more preferably in the range of 800 to 4,500.

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 the examples.

The acid value of the polyester of the present invention is preferably in the range of 20~400 mgKOH/g, more preferably in the range of 30~150 mgKOH/g, and even more preferably in the range of 40~150 mgKOH/g.

The acid value of the above polyester is confirmed by the method described in the embodiment.

The properties of the polyester of the present invention vary depending on the number average molecular weight or composition, but are usually liquid, solid, paste, etc. at room temperature.

The polyester of the present invention is obtained using a reaction raw material containing an aliphatic dibasic acid, an aliphatic polybasic acid and/or an aromatic polybasic acid, an aliphatic diol, and an arbitrary hydroxycarboxylic acid. Here, the reaction raw material means a raw material constituting the polyester of the present invention, and means that a solvent or catalyst that does not constitute the polyester is not included. In addition, "arbitrary hydroxycarboxylic acid" means that the hydroxycarboxylic acid may be used or not. The production method of the polyester of the present invention is not particularly limited, and it can be produced by a well-known method, and can be produced by the production method described below.

The reaction raw materials of the polyester of the present invention may contain aliphatic dibasic acid, aliphatic polybasic acid and/or aromatic polybasic acid, aliphatic diol, and any hydroxy carboxylic acid, and may also contain other raw materials. The reaction raw materials of the polyester of the present invention preferably contain aliphatic dibasic acid, aliphatic polybasic acid and/or aromatic polybasic acid, aliphatic diol, and any hydroxy carboxylic acid in an amount of 90% by mass or more relative to the total amount of the reaction raw materials, and more preferably contain only aliphatic dibasic acid, aliphatic polybasic acid and/or aromatic polybasic acid, aliphatic diol, and any hydroxy carboxylic acid.

The aliphatic dibasic acid used in the production of the polyester of the present invention is an aliphatic dibasic acid corresponding to the aliphatic dibasic acid residues having 2 to 12 carbon atoms of A and _A1. The aliphatic dibasic acid used 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 the aliphatic polybasic acid residues having 2 to 12 carbon atoms of _A2 and _A3 . The aliphatic polybasic acid used 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 the aromatic polybasic acid residues having 6 to 15 carbon atoms of _A2 and _A3 . The aromatic polybasic acid used 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 having a carbon number of 2 to 9 corresponding to the aliphatic diol residue of G, _G1 and G2 _. The aliphatic diol used 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 having a carbon number of 2 to 18 corresponding to the hydroxycarboxylic acid residue of L. The hydroxycarboxylic acid used may be used alone or in combination of two or more. The reaction raw materials used also include derivatives such as the above-mentioned esterification products, the above-mentioned acid chlorides, and the above-mentioned acid anhydrides. For example, the hydroxycarboxylic acid also includes compounds having a lactone structure such as ε-caprolactone.

The polyester of the present invention can be produced by reacting the aliphatic dibasic acid, aliphatic polybasic acid and/or aromatic polybasic acid, aliphatic diol, and any hydroxy carboxylic acid constituting the respective residual groups of the polyester of the present invention under the condition that the equivalent of the carboxyl group contained in the reaction raw material becomes more than the equivalent of the hydroxyl group. The polyester of the present invention can also be produced by reacting the aliphatic dibasic acid, aliphatic polybasic acid, and any hydroxy carboxylic acid constituting the respective residual groups of the polyester of the present invention under the condition that the equivalent of the hydroxyl group contained in the reaction raw material becomes more than the equivalent of the carboxyl group, and obtaining 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.

In the production of the polyester of the present invention, the reaction of the above-mentioned reaction raw materials can be carried out in the presence of an esterification catalyst as needed, for example, at a temperature range of 180 to 250°C for 10 to 25 hours. Furthermore, the temperature, time and other conditions of the esterification reaction are not particularly limited and can be appropriately set.

Examples of the esterification catalyst include titanium-based catalysts such as tetraisopropyl titanium and tetrabutyl titanium; 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.

The amount of the esterification catalyst used can be appropriately set, but is usually in the range of 0.001 to 0.1 parts by mass relative to 100 parts by mass of the total amount of the reaction raw materials.

[Resin composition containing inorganic filler] The dispersing stabilizer of the present invention can function as a dispersing stabilizer of an inorganic filler in a resin composition containing an inorganic filler and a resin (resin composition containing inorganic filler), thereby reducing the viscosity of the composition and preventing the inorganic filler from agglomerating and settling when the composition is stored for a long period of time. Among them, since the formation of agglomerates (hard lumps) containing inorganic fillers can be prevented, the dispersing stabilizer of the present invention can particularly function as a storage stabilizer for the resin composition containing inorganic fillers. The following is an explanation of the components contained in the resin composition containing inorganic fillers of the present invention.

(Inorganic filler) The inorganic filler contained in the resin composition containing an inorganic filler of the present invention is not particularly limited, and examples thereof include: calcium carbonate, talc, silicon dioxide, aluminum oxide, clay, antimony oxide, aluminum hydroxide, magnesium hydroxide, hydrotalcite, calcium silicate, magnesium oxide, potassium titanate, barium titanate, titanium oxide, calcium oxide, magnesium oxide, manganese dioxide, boron nitride, aluminum nitride, etc. The aforementioned inorganic fillers may be used alone or in combination of two or more.

The inorganic filler is preferably at least one selected from the group consisting of calcium carbonate, silica, aluminum oxide, aluminum hydroxide, barium titanium, talc, boron nitride and aluminum nitride, and more preferably at least one selected from the group consisting of calcium carbonate, aluminum oxide, aluminum hydroxide and talc.

The particle size, fiber length, fiber diameter and other shapes of the inorganic filler are not particularly limited and can be appropriately adjusted according to the intended use. In addition, the surface treatment state of the inorganic filler is not particularly limited and can also be modified according to the intended use, for example, by using saturated fatty acids to modify the surface.

The content of the dispersing stabilizer of the present invention is not particularly limited, but for example, it is in the range of 0.1 to 30 parts by mass of the dispersing stabilizer of the present invention relative to 100 parts by mass of the inorganic filler, preferably in the range of 0.1 to 10 parts by mass of the dispersing stabilizer of the present invention relative to 100 parts by mass of the inorganic filler, and more preferably in the range of 0.1 to 5.0 parts by mass of the dispersing stabilizer of the present invention relative to 100 parts by mass of the inorganic filler.

(Deviscosity reducing agent) The resin composition containing inorganic filler of the present invention preferably contains a viscosity reducing agent. By containing a viscosity reducing agent in the resin composition containing inorganic filler, the filling amount of the inorganic filler can be increased, and the handling property can also be improved. The viscosity reducing agent may induce the formation of agglomerates (hard blocks) containing the inorganic filler due to the viscosity reduction of the composition, but the formation of hard blocks can be prevented by the dispersing stabilizer of the present invention. Therefore, the resin composition containing inorganic filler of the present invention preferably uses the dispersing stabilizer of the present invention and the viscosity reducing agent in combination.

The aforementioned deviscosity reducing agent is not particularly limited, and examples thereof include anionic wetting dispersants, cationic wetting dispersants, polymer wetting dispersants, etc. As specific examples of the aforementioned deviscosity reducing agent, for example, alkyl ethers, mineral spirits, alkylbenzenes, waxes, higher fatty acid esters, sorbitan fatty acid esters, glycerol fatty acid esters, polycarboxylates (e.g., polycarboxylic acid alkyl ammonium salts), polyester acid salts (e.g., polyester acid unsaturated and polyaminoamide salts), higher fatty acid amides, oxidized polyethylene derivatives, sulfates, hydrogenated stearic acid derivatives, polyolefin polyimide epoxy alkyls, polyallylamine derivatives, polyether ester acid amines, polyether phosphate amines, polycarboxylic acid polyesters, polyesters having a carboxyl group at only one end, etc. Among them, polycarboxylic acid alkyl ammonium salts, higher fatty acid amides, polyester acid unsaturated and polyaminoamide salts, and polyesters having a carboxyl group at only one end are preferred. The above-mentioned deviscosity reducing agents may be used alone or in combination of two or more.

As the aforementioned viscosity reducing agent, a commercially available product can be used. Examples of the commercially available product include ANTI-TERRA series such as ANTI-TERRA-U/U100, ANTI-TERRA-204, and ANTI-TERRA-250; DISPERBYK series such as DISPERBYK-106, DISPERBYK-108, and DISPERBYK-140; BYK series such as BYK-9076 and BYK-9077 (all manufactured by BYK); Florene series such as Florene DOPA-15B, Florene DOPA-17HF, and Florene DOPA-22; Florene series such as Florene RCM-100 (all manufactured by Kyoeisha Chemicals); Solsperse 3000, Solsperse 20060, Solsperse 40000, and Solsperse 42000, Solsperse 85000 and other Solsperse series (all manufactured by Lubrizol Corporation); DISPARLON DA-234, DISPARLON DA-325, DISPARLON DA-375 and other DISPARLON series (all manufactured by Kusumoto Chemicals Co., Ltd.); ESLEAM 221P, ESLEAM C2093, ESLEAM AD-374M, ESLEAM AD-508E and other ESLEAM series; FILLANOL PA-085C, FILLANOL PA-107P and other FILLANOL series; MALIALIM SC-1015F, MALIALIM SC-0708A, MALIALIM AFB-1521, MALIALIM AAB-0851, MALIALIM AWS-0851 and other MALIALIM series (all manufactured by NOF Corporation); DEMOL P, DEMOL EP and other DEMOL series; POIZ 520, POIZ 521, POIZ 530 and other POIZ series; HOMOGENOL L-18 and other HOMOGENOL series (all made by Kao Corporation); AJISPER PB821, AJISPER PB822, AJISPER PB824, AJISPER PB881, AJISPER PN411, AJISPER PA111 and other AJISPER series (all made by Ajinomoto Fine-Techno Co., Ltd.), etc.

When a polyester having a carboxyl group at only one terminal is used as the above-mentioned detackifier, the polyester detackifier is preferably a polyester represented by the following general formula (I) or the following general formula (II).

(In the above general formulae (I) and (II), A ₁₁ is an aliphatic dicarboxylic acid residue having 2 to 12 carbon atoms. G ₁₁ and G ₁₂ are each independently an aliphatic diol residue 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 a repeating number, which is an integer in the range of 0 to 30. u represents a repeating number, which is an integer in the range of 0 to 30. The repeating units A ₁₁ and G ₁₁ enclosed in parentheses may be the same or different.)

From the viewpoint that the repeating units of the polyester are common to the polyester of the present invention and can be produced from the same raw materials, the polyester represented by the above-mentioned general formula (I) or (II) is preferred.

In the above general formulae (I) and (II), _A11 is an aliphatic dicarboxylic acid residue having 2 to 12 carbon atoms, and _G11 and _G12 are an aliphatic diol residue having 2 to 9 carbon atoms, which are the same as those of the polyester of the present invention.

The dicarboxylic acid residue having 1 to 8 carbon atoms as X may be any of an aliphatic dicarboxylic acid residue, an alicyclic dicarboxylic acid residue, and an aromatic dicarboxylic acid residue. As the above-mentioned aliphatic dicarboxylic acid residue, for example, malonic acid residue, succinic acid residue, glutaric acid residue, adipic acid residue, pimelic acid residue, suberic acid residue, azelaic acid residue, sebacic acid residue, maleic acid residue, fumaric acid residue, 1,2-dicarboxycyclohexane residue, 1,2-dicarboxycyclohexene residue, etc. As the above-mentioned aromatic dicarboxylic acid residue, for example, phthalic acid residue, isophthalic acid residue, terephthalic acid residue, etc. may be cited. X is a dicarboxylic acid residue having 1 to 8 carbon atoms, 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 of Y may be any of an aliphatic monocarboxylic acid residue, an alicyclic monocarboxylic acid residue, and an aromatic monocarboxylic acid residue, for example, a propionic acid residue, a butyric acid residue, a hexanoic acid residue, an octanoic acid residue, an octanoic acid residue, a benzoic acid residue, a dimethylbenzoic acid residue, a trimethylbenzoic acid residue, a tetramethylbenzoic acid residue, Methylbenzoic acid residue, ethylbenzoic acid residue, propylbenzoic acid residue, butylbenzoic acid residue, p-isopropylbenzoic acid residue, p-tert-butylbenzoic acid residue, o-toluic acid residue, m-toluic acid residue, p-toluic acid residue, ethoxybenzoic acid residue, propoxybenzoic acid residue, anisic acid residue, naphthoic acid residue, etc. Y is preferably a hydrogen atom or a benzoic acid residue.

The monoalcohol residue with 2 to 10 carbon atoms of Z may be any of an aliphatic monoalcohol residue and an alicyclic monoalcohol residue. As the monoalcohol residue with 2 to 10 carbon atoms of Z, for example, ethanol residue, propanol residue, butanol residue, pentanol residue, hexanol residue, cyclohexanol residue, heptanol residue, octanol residue, nonanol residue, decanol residue, etc., among which octanol residue, nonanol residue, and decanol residue are preferred.

In the polyester represented by the general formula (I), preferably, Y is a hydrogen atom, an acetyl group or a benzoic acid residue, _G11 and _G12 are each independently a propylene glycol residue, a neopentyl glycol residue or a 1,3-propylene glycol residue, _A11 is an adipic acid residue, and X is an adipic acid residue or a maleic acid residue. In the polyester represented by the general formula (II), preferably, Z is an octanol residue, a nonanol residue or a decanol residue, _G11 is a propylene glycol residue, a neopentyl glycol residue or a 1,3-propylene glycol residue, _A11 is an adipic acid residue, and X is an adipic acid residue or a maleic acid residue.

The polyester represented by the general formula (I) can be used as a mixture of two or more polyesters having at least one different value of each residue and t in the general formula (I). In this case, the average value of t is preferably in the range of 2 to 15. Similarly, the polyester represented by the general formula (II) can be used as a mixture of two or more polyesters having at least one different value of each residue and u in the general formula (II). In this case, the average value of u is preferably in the range of 2 to 15. In addition, it can also 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 by the number average molecular weight of the polyester.

The acid value of the polyester represented by the above general formula (I) or (II) is preferably in the range of 3 to 50, and more preferably in the range of 3 to 35. The acid value of the above polyester is confirmed by the method described in the embodiment.

The number average molecular weight (Mn) of the polyester represented by the above 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 preferably in the range of 400 to 1,500. 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 the Examples.

The properties of the polyester represented by the above general formula (I) or (II) vary depending on the number average molecular weight and composition, but are usually liquid, solid, paste, etc. at room temperature.

The polyester represented by the above general formula (I) or (II) can be produced in the same manner as the polyester of the present invention. Specifically, there can be cited a method of supplying the above diol, dicarboxylic acid, monocarboxylic acid or monoalcohol at once to carry out an esterification reaction; a method of using diol and dicarboxylic acid to obtain a compound having hydroxyl groups at both ends, and then further reacting a monocarboxylic acid with a dicarboxylic acid; a method of using diol and dicarboxylic acid to obtain a compound having carboxyl groups at both ends, and then further reacting a monoalcohol, etc. Among the above, the reaction product of aliphatic dicarboxylic acid having 2 to 12 carbon atoms and aliphatic diol having 2 to 9 carbon atoms and monocarboxylic acid having 1 to 9 carbon atoms or monoalcohol having 2 to 10 carbon atoms can be defined as a mixture of the polyester represented by the aforementioned general formula (1) and the polyester represented by the aforementioned general formula (I) or (II) of the inorganic filler dispersing stabilizer of the present invention, which is preferred from the viewpoint of excellent viscosity reduction effect and storage stabilization effect.

The content of the detackifier is not particularly limited, but for example, it is in the range of 0.1 to 30 parts by mass of the detackifier relative to 100 parts by mass of the inorganic filler, preferably in the range of 0.1 to 10 parts by mass of the detackifier relative to 100 parts by mass of the inorganic filler.

(Plasticizer) The inorganic filler-containing resin composition of the present invention preferably contains a plasticizer. As the aforementioned plasticizer, for example, benzoic acid esters such as diethylene glycol dibenzoate; phthalic acid esters such as dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), di-undecyl phthalate (DUP), di-tridecarboxylic acid (DTDP); terephthalic acid esters such as bis(2-ethylhexyl) terephthalate (DOTP); isophthalic acid esters such as bis(2-ethylhexyl) isophthalate (DOIP); pyromellitic acid esters such as tetra-2-ethylhexyl pyromellitic acid (TOPM); di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), Aliphatic dibasic acid esters such as diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS), and diisononyl sebacate (DINS); phosphoric acid esters such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP); alkyl esters of polyols such as neopentyl tetratol; polyesters with a molecular weight of 800 to 4,000 synthesized by polyesterification of dibasic acids such as adipic acid and diols; epoxidized esters such as epoxidized soybean oil and epoxidized linseed oil; alicyclic dibasic acids such as diisononyl hexahydrophthalate; fatty acid diol esters such as 1,4-butylene glycol dicaprylate; acetyl tributyl citrate (ATBC); chlorinated alkanes obtained by chlorinating wax or normal alkanes; chlorinated fatty acid esters such as chlorostearate; higher fatty acid esters such as butyl oleate, etc. The plasticizer used can be determined according to the intended use. One of the above plasticizers can be used alone or two or more can be used in combination.

The content of the plasticizer is not particularly limited, but for example, it is in the range of 10 to 300 parts by mass of the plasticizer per 100 parts by mass of the inorganic filler, preferably in the range of 30 to 200 parts by mass of the plasticizer per 100 parts by mass of the inorganic filler.

The additives contained in the resin composition containing inorganic fillers of the present invention are not limited to the inorganic filler dispersing stabilizer, the aforementioned viscosity reducing agent, and the aforementioned plasticizer of the present invention, and may also include other additives other than these. As the aforementioned other additives, examples include: flame retardants, stabilizers, stabilizers, colorants, processing aids, fillers, antioxidants (anti-aging agents), ultraviolet absorbers, light stabilizers, lubricants, antistatic agents, crosslinking aids, etc.

(Resin) The resin contained in the resin composition containing inorganic filler of the present invention is not particularly limited, and examples thereof include polyolefin, polyester, polysulfide, polyvinyl chloride, modified polysulfide, silicone resin, modified silicone resin, acrylic urethane resin, epoxy resin, polyurethane, acrylic resin, polyester, unsaturated polyester, etc. The resin used can be determined according to the intended use, and one of the above resins may be used alone, or two or more of them may be used in combination.

The resin composition containing an inorganic filler of the present invention contains a resin, but in a composition containing a viscous compound such as asphalt, the dispersing stabilizer of the present invention can also be appropriately used instead of the resin.

The inorganic filler-containing resin composition of the present invention can be appropriately used as a paste resin composition that requires fluidity when used. From the perspective of reducing the viscosity of the composition and inhibiting the formation of hard lumps to improve the storage stability of the composition, the dispersing stabilizer of the present invention is preferably applied to coatings, adhesives, structural materials, etc. that are mostly used outdoors, and is suitable for two-component urethane flooring material coatings that need to be mixed before coating, structural materials (building materials) that want to increase the filler content, or polysulfide sealants with a particularly high filler content. The following describes composition examples of different uses when the inorganic filler-containing resin composition of the present invention is used as a paste resin composition.

(Structural materials) As resins contained in the resin composition containing inorganic fillers used in the above-mentioned structural materials, polyolefins, polyurethanes, unsaturated polyesters, etc. can be cited. The resins used in structural materials (building materials) vary depending on the purpose. For example, if it is a waterproof material, the resin component mainly uses polyurethane, and if it is artificial marble, unsaturated polyester is mainly used.

When the structural material is a waterproof material, the resin composition containing an inorganic filler used for the waterproof material (hereinafter sometimes referred to as "resin composition for waterproof material") is preferably, for example, a polyurethane composition containing a main agent component including an isocyanate group-containing compound and a hardener component containing one or more selected from the group consisting of aromatic polyamines, polyols, water and hygroscopic water.

The isocyanate group-containing compound included as the main agent component is preferably an isocyanate group-terminated polyurethane prepolymer obtained by reacting a polyisocyanate having a diphenylmethane diisocyanate structure with a polyol. As the above-mentioned polyisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 2,2'-diphenylmethane diisocyanate can be cited. Among them, an isocyanate mixture containing 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate and/or 2,2'-diphenylmethane diisocyanate is preferred. As the above-mentioned polyol, polyoxypropylene polyol is preferred, and polyoxypropylene diol alone or a mixture of polyoxypropylene diol and polyoxypropylene triol is more preferred.

The ratio of polyisocyanate to polyol in the isocyanate-terminated urethane prepolymer is preferably in the range of 1.8 to 2.5 in terms of the molar ratio of isocyanate group to hydroxyl group (NCO/OH). The isocyanate group content (NCO group content) in the isocyanate-terminated urethane prepolymer is preferably in the range of 2 to 5% by mass.

Examples of aromatic polyamines included in the curing agent component include 4,4'-methylenebis(2-chloroaniline), dimethylthiotoluenediamine, diethyltoluenediamine, etc. Among them, 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 of the polyol is preferably in the range of 2 to 4, and more preferably in the range of 2 to 3.

When the polyurethane is a two-component curing type, the mixing ratio of the main agent and the curing agent, the molar ratio of the isocyanate group contained in the main agent to the active hydrogen-containing group contained in the curing agent (NCO/(NH ₂ +OH)), is, for example, in the range of 1.0 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 include an inorganic filler, and examples of the inorganic filler include calcium carbonate, talc, clay, silica, carbon, and the like. The content of the inorganic filler in the polyurethane composition may be set to a range of 10 to 60 parts by mass, preferably 20 to 50 parts by mass, relative to 100 parts by mass of the resin component. By setting the content of the inorganic filler to this range, the balance between the curability of the composition and the performance of the resulting waterproof material can be improved.

In the case of two-component curing polyurethane, the viscosity of the main agent and the curing agent is usually high (main agent: for example, in the range of 7 to 10Pa・S, curing agent: for example, in the range of 10 to 30Pa・S). In winter when the temperature drops, the viscosity further increases, so the dispersibility of the inorganic filler can be improved, and the dispersing stabilizer of the present invention that increases the content is useful. The dispersing stabilizer of the present invention only needs to be included in the resin composition for waterproofing materials. For example, in the case of the above-mentioned two-component curing polyurethane, the dispersing stabilizer of the present invention only needs to be included in at least one of the main agent component and the curing agent component.

In order to promote the urethanization reaction, the hardener component may contain a known hardening catalyst. Examples of the hardening catalyst include organic acid lead, organic acid tin, and tertiary amine compounds.

The hardener components, in addition to the inorganic filler and the hardening catalyst, may also include the aforementioned viscosity reducer, the aforementioned plasticizer, chromium oxide, titanium oxide, phthalocyanine and other pigments; antioxidants, ultraviolet absorbers, dehydrating agents and other stabilizers, etc.

As a waterproof material obtained by forming a waterproof material composition, for example, a roof waterproof material can be cited. The above-mentioned roof waterproof material is obtained by, for example, applying a composition of a mixed main agent component and a hardener component to a desired portion to form a coating film, and reacting and hardening it.

(Sealing material) The polysulfide resin used in the aforementioned polysulfide sealing material is not particularly limited as long as it is a resin having a sulfide bond in the molecule, and examples thereof include a sulfide bond to which a hydrocarbon group such as an alkyl group is bonded. The polysulfide resin may also have, for example, an ether bond, an ester bond, an amide bond, or an imide group in the skeleton.

When the polythioether resin has an ether bond in the skeleton, it is called a polythioether polyether resin. The polythioether resin may also have functional groups such as thiol, hydroxyl, and amine groups at one or both ends.

Examples of the polysulfide resin include those having 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 and having a thiol group represented by -C ₂ H ₄ OCH ₂ OC ₂ H ₄ -SH at the terminal.

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.

Furthermore, as the polysulfide-based resin, polysulfide polyether resins can also be cited. Specific examples of the polythioether polyether resin include thiol group-containing polythioether polyether resins, for example, those comprising in the main chain a polyether portion represented by (1) "-(R ₁ O) _n " (R ₁ represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer of 6 to 200) and structural units represented by (2) "-C ₂ H ₄ OCH ₂ OC ₂ H ₄ -Sx-" and (3) "-CH ₂ CH(OH)CH ₂ -Sx-" (the aforementioned x is an integer of 1 to 5), and further having a thiol group represented by (4) "-C ₂ H ₄ OCH ₂ OC ₂ H ₄ -SH" or "-CH ₂ CH(OH)CH ₂ -SH", etc.

The number average molecular weight of the polysulfide polyether resin is usually 600 to 200,000, preferably 800 to 50,000.

The aforementioned polysulfide resin is not limited in the production method, and those produced by various well-known methods can be used. In addition, commercially available polysulfide resins can also be used. Examples of commercially available polysulfide resins include "THIOKOL LP-23, LP-32" (manufactured by Toray Fine Chemicals Co., Ltd.) and "THIOPLAST polymer" (manufactured by Akzo Nobel Co., Ltd.). The polysulfide resins can be used alone or in combination of two or more.

The polysulfide-based sealing material containing the dispersing stabilizer of the present invention can be used in combination with various other additives. Examples of additives include the aforementioned detackifier, the aforementioned plasticizer, an adhesion-imparting agent, a pigment, a dye, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, an adhesion-imparting resin, a stabilizer, a dispersant, and the like.

From the perspective of being excellent in improving the adhesion to glass surfaces and being a general-purpose compound, suitable examples of the aforementioned adhesion imparting agent include silane coupling agents such as aminosilane. As the aforementioned aminosilane, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylethyldiethoxysilane, etc. can be cited.

Examples of the pigment 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.

Examples of the aforementioned anti-aging agent include hindered phenol compounds, hindered amine compounds, and the like.

Examples of the antioxidant include butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA).

Examples of the antistatic agent include quaternary ammonium salts, hydrophilic compounds such as polyethylene glycol and ethylene oxide derivatives, and the like.

Examples of the flame retardant include chloroalkyl phosphates, dimethyl methyl phosphonates, bromine phosphorus compounds, ammonium polyphosphates, bromoneopentane-polyethers, brominated polyethers, etc. Examples of the adhesive imparting resin include terpene resins, phenolic resins, terpene-phenolic resins, rosin resins, xylene resins, epoxy resins, titanium alkyl esters, organic polyisocyanates, etc.

Examples of the stabilizer include fatty acid silane esters, fatty acid amide trimethylsilyl compounds, and the like.

Dispersants are substances that break solids into fine particles and disperse them in liquids, and examples include sodium hexametaphosphate, sodium condensed naphthalenesulfonate, and surfactants.

The aforementioned polysulfide-based sealant is usually mixed with a hardener and used immediately before use. As the hardener, for example, a hardener generally used for polysulfide resin-based sealants such as metal oxides, metal peroxides, organic and inorganic oxidants, epoxy compounds, and isocyanate compounds can be used. Among them, metal peroxides such as lead dioxide and manganese dioxide are preferred, and manganese dioxide is more preferred. The fluidity improver of the present invention is preferably mixed with the hardener and used.

When manganese dioxide is used as the curing agent, its usage amount is preferably in the range of 2.5 to 25 parts by mass, more preferably in the range of 3 to 20 parts by mass, based on 100 parts by mass of the polysulfide resin used as the main agent, from the viewpoint of obtaining a sufficiently cured product having appropriate elasticity.

The aforementioned hardener may also contain other fillers, plasticizers, hardening accelerators, and silane coupling agents.

The curing condition when used as a sealant is 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 resin composition containing inorganic fillers of the present invention is not limited to the above-mentioned paste resin composition, and can also be appropriately used as a molding resin composition for injection molding, extrusion molding, etc. The properties of the molding resin composition are various. It is liquid in the stage before molding (normal temperature) and becomes liquid due to heating during molding. From the perspective of reducing the viscosity of the composition and inhibiting the formation of hard agglomerates, the dispersing stabilizer of the present invention can inhibit the excessive viscosity increase caused by the inclusion of inorganic fillers, and can smoothly perform melt kneading before molding. From the perspective of increasing the amount of inorganic filler added, the dispersing stabilizer of the present invention can be appropriately used in resin compositions for molding such as automotive components, sanitary absorbents, building materials, stone paper, and heat-releasing components, which require an increased amount of inorganic filler added and improved physical properties. The following describes composition examples of different uses when the resin composition containing an inorganic filler of the present invention is used as a molding resin composition.

(Automotive components) The resin component contained in the molding resin composition used for automotive components (hereinafter sometimes referred to as "automotive component resin composition") is preferably a thermoplastic resin, and among the thermoplastic resins, a polypropylene resin having the characteristics of excellent moldability, high mechanical strength, and economy. The above-mentioned polypropylene is not particularly limited, but preferably a polypropylene resin having an MFR (230°C, 2.16kg) of 60 to 120 g/10 minutes.

The resin composition for automobile parts may further contain an olefinic thermoplastic elastomer as a resin component. The olefinic thermoplastic elastomer is not particularly limited, but preferably contains an ethylene-α-olefin copolymer.

Examples of the inorganic filler included in the resin composition for automobile components include talc, calcium carbonate, crystal whiskers (the material of the crystal whiskers includes graphite, potassium titanium, aluminum oxide, silicon carbide, silicon nitride, aluminum-rich andalusite, magnesium oxide, magnesium borate, aluminum borate, magnesium sulfate, zinc oxide, titanium boride, etc.), carbon nanofibers, carbon nanotubes, kaolin clay, mica, etc.

The resin composition for automobile components may also contain various additives other than the dispersing stabilizer and inorganic filler of the present invention. Examples of such additives include the aforementioned detackifier, the aforementioned plasticizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a flame retardant, a colorant, and the like.

The composition ratio of the resin component, inorganic filler, dispersion stabilizer, etc. contained in the resin composition for automobile parts is not particularly limited, but is preferably adjusted to a composition that satisfies one or more of the following physical properties. The MFR (230°C, 2.16kg, 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 more preferably 4.0 to 5.0×10 ^-5 /K. The tensile modulus of elasticity (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/ ^m2 or more, more preferably in the range of 30 to 40 kJ/ ^m2 .

Examples of automobile components obtained by molding the automobile component resin composition include hoods, fenders, bumpers, doors, trunk lids, roofs, grilles, wheel covers, instrument panels, pillar trims, etc. Such automobile components can be manufactured by injection molding the automobile component resin composition.

(Sanitary absorbent articles) The resin component contained in the resin composition for molding used in sanitary absorbent articles (hereinafter sometimes referred to as "sanitary absorbent article resin composition") is preferably, for example, a polyolefin, and among the polyolefins, one or more selected from the group including polyethylene and polypropylene, more preferably polyethylene. When polyethylene is used as the resin component, for example, two or more polyethylenes with different densities may be used.

The polyolefin as the resin component of the resin composition for sanitary absorbent articles is not particularly limited, but preferably has an MFR (190°C, 2.16kgf) in the range of 0.1 to 20 g/10 minutes, and more preferably in the range of 0.5 to 5 g/10 minutes. By making the MFR 0.1 g/10 minutes or more, the formability of the film can be fully maintained, and by making it 20 g/10 minutes or less, sufficient strength can be obtained.

The resin composition for sanitary absorbent articles may further include a polystyrene elastomer as a resin component. As the above-mentioned polystyrene elastomer, there can be cited elastomers containing styrene blocks of styrene-olefin (SEP, SEBC, etc.), styrene-olefin-styrene (SEPS, SEBS, etc.), styrene-diene (SIS, SBS, etc.), and hydrogenated styrene-diene (HSIS, HSBR, etc.). The styrene component in the polystyrene elastomer is preferably in the range of 10 to 40% by mass, and more preferably in the range of 20 to 40% by mass.

As inorganic fillers included in the resin composition for sanitary absorbent articles, calcium carbonate, calcium sulfate, barium carbonate, titanium oxide, etc. can be cited, preferably one or more selected from the group including calcium carbonate and barium sulfate. The shape of the inorganic fillers is not particularly limited, but preferably particulate, more preferably microparticles with an average particle size in the range of 0.1 to 10 μm, more preferably microparticles with an average particle size in the range of 0.3 to 5 μm, and particularly preferably microparticles with an average particle size in the range of 0.5 to 3 μm.

The content of inorganic filler in the resin composition for sanitary absorbent articles is preferably, for example: polyolefin: inorganic filler = 60-20 parts by mass: 40-80 parts by mass, more preferably polyolefin: inorganic filler = 55-25 parts by mass: 45-75 parts by mass, and further preferably polyolefin: inorganic filler = 50-30 parts by mass: 50-70 parts by mass. If the content of inorganic filler is within the above range, the moisture permeability, breathability and liquid permeability resistance of the obtained sanitary absorbent article can be fully guaranteed.

The resin composition for sanitary absorbent articles may also contain various additives other than the dispersing stabilizer and inorganic filler of the present invention. Examples of such additives include the aforementioned detackifier, the aforementioned plasticizer, a compatibilizer, a processing aid, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an anti-caking agent, an antifogging agent, a matting agent, a surfactant, an antibacterial agent, a deodorant, an antistatic agent, a water repellent, an oil repellent, a radiation shielding agent, a colorant, a pigment, and the like.

The molded product obtained by molding the resin composition for sanitary absorbent articles can be appropriately used as a back sheet (a sheet with air permeability and moisture permeability, but liquid does not pass through) used in sanitary absorbent articles such as diapers and sanitary napkins. The above-mentioned back sheet can be manufactured by, for example: melting and kneading the 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) Stone paper is a sheet made of calcium carbonate and polyolefin (polyethylene, polypropylene, etc.) derived from limestone. Water and wood are not required for the formation of the sheet, and the limestone used as the raw material is almost inexhaustible on the earth, so it is a sheet with excellent sustainability. Stone paper contains a large amount of calcium carbonate, but the fluidity of calcium carbonate can be improved by the dispersing stabilizer of the present invention, thereby improving the physical properties of the sheet.

Stone paper can be produced by, for example, melt-kneading a stone paper composition containing calcium carbonate, polyolefin and the dispersing stabilizer of the present invention, and then performing blow molding or extrusion molding.

In the stone paper composition, the content of calcium carbonate, in terms of the mass ratio of polyolefin to calcium carbonate (polyolefin:calcium carbonate), is, for example, 85:15 to 20:80, preferably 85:15 to 30:70, more preferably 85:15 to 35:65, and even more preferably 80:20 to 40:60.

The stone paper composition may further include the aforementioned detackifier, the aforementioned plasticizer, a foaming agent, a colorant, a lubricant, a coupling agent, a stabilizer (antioxidant, ultraviolet absorber, etc.), an antistatic agent, etc. as auxiliary agents.

Examples of the foaming agent include aliphatic hydrocarbon compounds such as propane, n-butane, isobutane, n-pentane, isopentane, and hexane; alicyclic hydrocarbon compounds such as cyclohexane, cyclopentane, and cyclobutane; and halogenated hydrocarbon compounds such as trifluoromonochloroethane and difluorodichloromethane.

Examples of the lubricant include fatty acid lubricants such as stearic acid, hydroxystearic acid, complex stearic acid, and oleic acid; fatty amide lubricants such as fatty alcohol lubricants, stearamide, oxystearamide, oleamide, erucamide, ricinoleic acid amide, behenamide, hydroxymethyl amide, methylenebisstearylamide, methylenebisstearyl behenamide, diamides of higher fatty acids, and complex amides; fatty ester lubricants such as n-butyl stearate, methyl hydroxystearate, polyol fatty acid esters, saturated fatty acid esters, and ester waxes; fatty acid metal soap family lubricants, and the like.

As the aforementioned antioxidant, phosphorus-based antioxidants, phenol-based antioxidants, pentaerythritol-based antioxidants, etc. can be used. As phosphorus-based antioxidants, phosphites such as triesters, diesters, and monoesters of phosphorous acid such as triphenyl phosphite, tris-nonylphenyl phosphite, and tris-(2,4-di-tert-butylphenyl) phosphite; phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris-(nonylphenyl) phosphate, and 2-ethylphenyl diphenyl phosphate can be cited. As phenolic antioxidants, α-tocopherol, butylhydroxytoluene, 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-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzyl diethyl phosphate, and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, etc. can be cited.

(Heat dissipation components) Electronic devices such as personal computers, smartphones, and televisions generate more heat as their performance improves, and in order to efficiently dissipate the generated heat, heat dissipation components containing heat conductive fillers are often used. In addition, automobiles such as electric vehicles and hybrid vehicles also have many electronic devices and use many heat dissipation components containing heat conductive fillers.

Examples of the resin component contained in the resin composition for molding the exothermic member (hereinafter sometimes referred to as "exothermic member resin composition") include thermosetting resins, active energy ray-hardening resins, and thermoplastic resins.

As the thermosetting resin of the resin composition for the heat release member, a known thermosetting resin can be used, and examples thereof include: phenolic phenolic resins such as phenolic phenolic resins and cresol phenolic resins; unmodified soluble phenolic resins; oil-modified soluble phenolic resins modified with tung oil, linseed oil, walnut oil, etc.; and soluble phenolic resins such as phenolic phenolic resins. Phenolic resins such as bisphenol A epoxy resin and bisphenol F epoxy resin; phenolic epoxy resins such as fatty chain modified bisphenol epoxy resin, phenolic epoxy resin, cresol phenolic epoxy resin; epoxy resins such as biphenyl epoxy resin and polyalkylene glycol epoxy resin; urea resin, melamine resin and other phenolic epoxy resins with tris- Resins of ring type; vinyl resins such as (meth) acrylic resins or vinyl ester resins: unsaturated polyester resins, dimaleimide resins, polyurethane resins, diallyl phthalate resins, silicone resins, benzoic acid Cyclic resins, cyanate resins, etc.

The above-mentioned thermosetting resin can also be used together with a hardener. Examples of the hardener used together with the thermosetting resin include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, and guanidine derivatives; amide compounds such as polyamide resin synthesized from dicyandiamide, dimer of linolenic acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, and the like. anhydride), hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride and other anhydride compounds; phenolic phenolic resins, cresol phenolic resins, aromatic hydrocarbon formaldehyde resin modified phenolic resins, dicyclopentadienol addition resins, phenol aralkyl resins (ZYLOK resins), resorcinol phenolic resins, naphthol aralkyl resins, trihydroxymethylmethane resins, tetraphenylethane resins, naphthol phenolic resins, naphthol-phenol co-phenolic resins, naphthol-cresol co-phenolic resins, biphenyl modified phenolic resins, biphenyl modified naphthol resins, aminotriphenylene glycol resins, Modified phenolic resins, alkoxy-containing aromatic ring-modified phenolic resins and other phenolic compounds.

As the thermoplastic resin of the resin composition for the heat release member, known thermoplastic resins can be used, and examples thereof include polyethylene resins, polypropylene resins, polymethyl methacrylate resins, polyvinyl acetate resins, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polyvinyl chloride resins, polystyrene resins, polyacrylonitrile resins, polyamide resins, Polycarbonate resin, polyacetal, polyethylene terephthalate resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfide resin, polyethersulfide resin, polyetheretherketone resin, polyallylsulfide resin, thermoplastic polyimide resin, thermoplastic urethane resin, polyamino dimaleimide resin, polyamide imide resin, polyetherimide resin, dimaleimide tris(III) Resin, polymethylpentene resin, fluorinated resin, liquid crystal polymer, olefin-vinyl alcohol copolymer, ionic polymer resin, polyarylate resin, acrylonitrile-ethylene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, etc.

Examples of heat conductive fillers contained in the resin composition for heat dissipating components include aluminum oxide, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, calcium oxide, magnesium oxide, zinc oxide, curium oxide, aluminum oxide, aluminum nitride, boron nitride, hydrometallurgical compounds, fused silica, crystalline silica, amorphous silica, silicon carbide, silicon nitride, titanium carbide, diamond, and the like. The above heat conductive fillers may be surface treated with silane-based, titanium ester-based, and aluminate-based coupling agents.

The shape of the thermally conductive filler is not particularly limited, and may be any of spherical, needle-like, flake-like, branch-like, and fiber-like.

The content of the thermally conductive filler in the resin composition for heat release components can be appropriately adjusted according to the application, and is preferably set in the range of 30 to 500 parts by mass of the thermally conductive filler relative to 100 parts by mass of the resin component.

The resin composition for the exothermic member may also contain various additives other than the inorganic filler dispersing stabilizer and the heat conductive filler of the present invention. Examples of such additives include dyes, pigments, antioxidants, polymerization inhibitors, defoaming agents, leveling agents, ion scavengers, humectants, viscosity regulators, preservatives, antibacterial agents, antistatic agents, anti-caking agents, ultraviolet absorbers, infrared absorbers, and the like.

When the resin composition for the exothermic component contains a thermosetting resin, the exothermic component can be molded by heating the resin composition for the exothermic component. When the resin composition for the exothermic component contains an active energy ray-hardening resin, it can be hardened and molded by irradiating active energy rays such as ultraviolet rays or infrared rays. When the resin composition for the exothermic component contains a thermoplastic resin, the exothermic component can be obtained by a known molding method such as injection molding, extrusion molding, and press molding.

The heat dissipation member obtained by molding the heat dissipation member resin composition can be used as a heat sink. The heat dissipation member obtained by molding the heat dissipation member resin composition can also be used as a heat dissipation joining member for joining a portion to be heat dissipated with a metal heat dissipation member.

The resin composition for heat dissipation components can also be used as semiconductor packaging materials.

The above description is directed to a resin composition containing an inorganic filler, but the inorganic filler dispersing stabilizer of the present invention can improve the storage stability even for a composition containing an inorganic filler that does not contain a resin. For example, by adding the dispersing stabilizer of the present invention to a composition containing an organic solvent such as acetone and an inorganic filler, the precipitation rate of the inorganic filler can be reduced, and the formation of agglomerates (hard blocks) containing the inorganic filler can be suppressed. [Example]

The present invention is described in detail below based on embodiments and comparative examples. In addition, the present invention is not limited to the following embodiments.

In the present embodiment, the acid value and the hydroxyl value are values evaluated by the following method. [Acid value measurement method] Measured by the method in accordance with JIS K0070-1992. [Hydroxy value measurement method] Measured by the method in accordance with JIS K0070-1992.

In the present embodiment, 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] Measurement device: High-speed GPC device "HLC-8320GPC" manufactured by Tosoh Co., Ltd. Column: "TSK GURDCOLUMN SuperHZ-L" manufactured by Tosoh Co., Ltd. + "TSK gel SuperHZM-M" manufactured by Tosoh Co., Ltd. + "TSK gel SuperHZM-M" manufactured by Tosoh Co., Ltd. + "TSK gel SuperHZ-2000" manufactured by Tosoh Co., Ltd. + "TSK gel SuperHZ-2000" manufactured by Tosoh Co., Ltd. Detector: RI (differential refractometer) Data processing: "EcoSEC Data Analysis Version 1.07" manufactured by Tosoh Co., Ltd. Column temperature: 40℃ Development solvent: tetrahydrofuran Flow rate: 0.35mL/min Test sample: 7.5 mg of the sample was dissolved in 10 ml of tetrahydrofuran and the solution obtained by filtering with a microfilter was used as the test sample. Sample injection volume: 20 μl Standard sample: According to the measurement manual of the aforementioned "HLC-8320GPC", the following monodisperse polystyrene with a known molecular weight was used.

(Monodisperse polystyrene) Tosoh Co., Ltd. "A-300" Tosoh Co., Ltd. "A-500" Tosoh Co., Ltd. "A-1000" Tosoh Co., Ltd. "A-2500" Tosoh Co., Ltd. "A-5000" Tosoh Co., Ltd. "F-1" Tosoh Co., Ltd. "F-2" Tosoh Co., Ltd. "F-4" Tosoh Co., Ltd. "F-10" Tosoh Co., Ltd. "F-20" Tosoh Co., Ltd. "F-40" Tosoh Co., Ltd. "F-80" Tosoh Co., Ltd. "F-128" Tosoh Co., Ltd. "F-288"

(Example 1: Synthesis of Dispersing Stabilizer A) In a 3-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux cooler, 531.8 g of 3-methyl-1,5-pentanediol, 1235.1 g of sebacic acid, and 0.0053 g of tetraisopropyl titanium ester as an esterification catalyst were supplied, and the temperature was gradually raised to 220°C while stirring under a nitrogen flow, so as to carry out a condensation reaction for a total of 10 hours. After the reaction was completed, the unreacted components were distilled off under reduced pressure to obtain a dispersing stabilizer A (acid value 110, hydroxyl value 0, number average molecular weight 1,000) containing a polyester having carboxyl groups at both ends.

(Example 2: Synthesis of Dispersing Stabilizer B) In a 3-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux cooler, 1702.5 g of 3-methyl-1,5-pentanediol, 625.5 g of 1,12-dodecanedioic acid, and 0.069 g of tetraisopropyl titanium ester as an esterification catalyst were supplied, and the temperature was gradually raised to 220°C while stirring under a nitrogen flow, so as to carry out a condensation reaction for a total of 10 hours. After the reaction was completed, the unreacted components were distilled off under reduced pressure to obtain a dispersing stabilizer B (acid value 108.5, hydroxyl value 0.01, number average molecular weight 1,000) containing a polyester having carboxyl groups at both ends.

(Example 3: Synthesis of Dispersing Stabilizer C) In a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux cooler, 1214 g of 3-methyl-1,5-pentanediol, 966 g of sebacic acid, and 0.07 g of tetraisopropyl titanium as an esterification catalyst were supplied, and the temperature was gradually raised to 220°C while stirring under a nitrogen flow, so as 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 supplied at 150°C to terminate the reaction, thereby obtaining a dispersing stabilizer C (acid value 24.7, hydroxyl value 64, number average molecular weight 1,700) containing a polyester having carboxyl groups at both ends.

The inclusion of polyester with carboxyl groups at both ends in the dispersion stabilizer C was confirmed by MALDI-TOF/MS measurement. 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). In the polyester using sebacic acid, 3-methyl-1,5-pentanediol and maleic acid as reaction raw materials, molecular weights of 621 (M+Na) ⁺ and 905 (M+Na) ⁺ were detected when both ends were carboxyl groups. The measurement results are shown in Figure 1.

(Example 4: Synthesis of Dispersing Stabilizer D) In a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux cooler, 395.7 g of propylene glycol, 809.0 g of sebacic acid, and 0.07 g of tetraisopropyl titanium as an esterification catalyst were supplied, and the temperature was gradually raised to 220°C while stirring under a nitrogen flow, so as to carry out a condensation reaction for a total of 12 hours. After the reaction, 0.06 g of hydroquinone and 109.8 g of maleic anhydride were supplied at 150°C to terminate the reaction, thereby obtaining a dispersing stabilizer D (acid value 44.8, hydroxyl value 38.0, number average molecular weight 1,840) containing a polyester having carboxyl groups at both ends.

(Example 5: Synthesis of Dispersing Stabilizer E) In a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux cooler, 1214 g of 3-methyl-1,5-pentanediol, 966 g of sebacic acid, and 0.07 g of tetraisopropyl titanium as an esterification catalyst were supplied, and the temperature was gradually raised to 220°C while stirring under a nitrogen flow, so as to carry out a condensation reaction for a total of 12 hours. After the reaction, 306.7 g of phthalic anhydride was supplied at 150°C to terminate the reaction, thereby obtaining a dispersing stabilizer E (acid value 49.0, hydroxyl value 48.4, number average molecular weight 1,170) containing a polyester having carboxyl groups at both ends.

(Example 6: Synthesis of Dispersing Stabilizer F) In a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux cooler, 459.3 g of 1,3-butanediol, 48.7 g of neopentyl glycol, 616.2 g of adipic acid, and 0.112 g of tetraisopropyl titanium acid as an esterification catalyst were supplied, and the temperature was gradually raised to 220°C while stirring under a nitrogen flow, so as to carry out a condensation reaction for a total of 10 hours. After the reaction, 0.056 g of hydroquinone and 44.2 g of maleic anhydride were supplied at 150°C to terminate the reaction, and a dispersing stabilizer F (acid value 29.1, hydroxyl value 121, number average molecular weight 900) containing a polyester having carboxyl groups at both ends was obtained.

(Synthesis Example 1: Synthesis of Deviscosity Reducer A) In a 3-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux cooler, 1680 g of 12-hydroxystearic acid and 0.252 g of tetraisopropyl titanium as an esterification catalyst were supplied, and the temperature was gradually raised to 210°C while stirring under a nitrogen flow, so as to carry out a condensation reaction for a total of 15 hours. After the reaction was completed, the unreacted components were distilled off under reduced pressure to obtain a polyester deviscosity reducer A (acid value 29.7, hydroxyl value 19.1, number average molecular weight 1,800) having a carboxyl group at one end and a hydroxyl group at the other end.

(Example 7-15 and Comparative Example 1-5: Preparation and evaluation of a composition containing calcium carbonate) Calcium carbonate (heavy calcium carbonate, "SUPER S" manufactured by Maruo Calcium Co., Ltd.) as an inorganic filler, DINP (diisononyl phthalate) as a plasticizer, DETDA (diethyltoluenediamine) as an active hydrogen compound, a dispersing stabilizer and a viscosity reducing agent were mixed in the proportions shown in Tables 1 and 2, and stirred for 2 minutes at 1000 rpm and 0.2 Pa using a planetary stirring device (THINKY ARV-310) to obtain a paste-like composition containing an inorganic filler. The viscosity and storage stability of the obtained paste composition were evaluated by the following method. The results are shown in Tables 1 and 2.

[Viscosity measurement method] The viscosity of the obtained paste was measured using an E-type viscometer (TV-25H manufactured by Toyo Sangyo Co., Ltd.) and a standard rotor (1°34’×R24, shear rate [1/S] 3.83×N, N is the rotor speed [rpm]). Specifically, the obtained paste was treated at a measuring temperature of 25°C and a rotation speed of 10 rpm, and the viscosity value of the composition was read after 3 minutes of treatment.

[Evaluation of storage stability] 12 g of the obtained composition was stored in a 50 cc glass bottle and placed in a thermostat at 50°C for 2 weeks. The composition after placement was visually and tactilely confirmed and evaluated according to the following criteria. ○: The presence of inorganic filler aggregates (hard lumps) could not be confirmed ×: The presence of inorganic filler aggregates (hard lumps) could be confirmed

[Table 1] Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15 blend[g] Calcium carbonate 60 60 60 60 60 60 60 60 60 DINP 33 33 33 33 33 33 33 33 33 DETDA 7 7 7 7 7 7 7 7 7 Viscosity reducer n-Hexyl ether Mineral Oil Viscosity Reducing Agent A 0.3 0.22 0.3 0.22 Dispersing Stabilizer A 0.1 0.08 Dispersing stabilizer B 0.1 0.08 Dispersing Stabilizer C 0.3 Dispersing stabilizer D 0.3 1.0 Dispersing Stabilizer E 0.3 Dispersing stabilizer F 1.0 Viscosity [mPa・s] 1,200 1,100 1,200 1,100 1,000 1,270 1,400 1,810 1,950 Storage stability ○ ○ ○ ○ ○ ○ ○ ○ ○

[Table 2] Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 blend[g] Calcium carbonate 60 60 60 60 60 DINP 33 33 33 33 33 DETDA 7 7 7 7 7 Viscosity reducer n-Hexyl ether 0.3 Mineral Oil 0.3 Viscosity Reducing Agent A 0.3 1.0 Dispersing Stabilizer A Dispersing stabilizer B Dispersing Stabilizer C Dispersing stabilizer D Dispersing Stabilizer E Dispersing stabilizer F Viscosity [mPa・s] ＞5,120 ＞5,120 ＞5,120 900 1080 Storage stability ○ ○ ○ × ×

From the evaluation results of Examples 7-10 and Comparative Examples 4-5, it can be seen that the paste using both the inorganic filler dispersant stabilizer and the viscosity reducing agent of the present invention has a slightly increased viscosity, but the storage stability is significantly improved. In addition, from the evaluation results of Examples 11-15 and Comparative Examples 1-3, it can be seen that the inorganic filler dispersant stabilizer of the present invention can not only show the storage stabilization effect, but also fully show the viscosity reducing effect.

(Examples 16-18 and Comparative Examples 6-8: Preparation and Evaluation of Calcium Carbonate-Containing Compositions) Calcium carbonate (heavy calcium carbonate, "SUPER S" manufactured by Maruo Calcium Co., Ltd.) as an inorganic filler, polyethylene ("UMERIT 2040F" manufactured by Ube Industries, Ltd.) as an adhesive resin, a dispersing stabilizer and a viscosity reducing agent were mixed in the proportions shown in Table 3 and fed into a batch mixer ("LABO PLASTOMILL 4C150" manufactured by Toyo Seiki Seisaku-sho), and melt-kneaded at a set temperature of 170°C, a blade speed of 50 r/min, and a kneading time of 10 minutes to prepare a resin composition containing an inorganic filler. The torque value and internal temperature of melt kneading during the preparation of the resin composition containing an inorganic filler were evaluated. The results are shown in Table 3. The torque value and internal temperature are the values obtained by reading the display values of the above kneading machine at a kneading time of 8 minutes.

[Table 3] Embodiment 16 Embodiment 17 Embodiment 18 Comparison Example 6 Comparative Example 7 Comparative Example 8 blend[g] Calcium carbonate 10.8 10.8 10.8 10.8 10.8 10.8 Polyethylene 36 36 36 36 36 36 Viscosity reducer Calcium stearate 0.72 Hardened castor oil 0.72 Viscosity Reducing Agent A 0.72 Dispersing Stabilizer A 0.72 Dispersing Stabilizer C 0.72 Dispersing stabilizer D 0.72 Torque value [N・m] 10 11 9 15 14 14 Internal temperature [℃] 173 174 172 177 175 177

From the evaluation results of Examples 16-18 and Comparative Examples 6-8, it can be seen that the resin composition containing the inorganic filler dispersant stabilizer of the present invention reduces the torque value, suppresses the temperature rise, and the resin composition is detackified by the inorganic filler dispersant stabilizer of the present invention.

(Example 19 and Comparative Examples 9-10: Preparation and Evaluation of Resin Compositions Containing Talc) 10.8 g of talc ("RL217" manufactured by Fuji Talc Industry Co., Ltd.) as an inorganic filler, 36 g of polypropylene (homopolymer of polypropylene, "J106G" manufactured by Prime Polymer Co., Ltd.) as an adhesive resin, a dispersing stabilizer and a viscosity reducing agent were mixed in the proportions shown in Table 4 and fed into a batch mixer ("LABO PLASTOMILL 4C150" manufactured by Toyo Seiki Seisakusho), and melt-kneaded at a set temperature of 170°C, a blade speed of 50 r/min, and a kneading time of 10 minutes to prepare a resin composition. The torque value and internal temperature during melt kneading were evaluated. The results are shown in Table 4. Furthermore, the torque value and internal temperature are the values read from the mixer after 8 minutes of mixing.

[Table 4] Embodiment 19 Comparative Example 9 Comparative Example 10 blend[g] talc 10.8 10.8 10.8 Polypropylene 36 36 36 Viscosity Reducing Agent A 0.72 Dispersing Stabilizer A 0.72 Torque value [N・m] 7.0 8.0 7.7 Internal temperature [℃] 173 174 174

From the evaluation results of Example 19 and Comparative Examples 9-10, it can be seen that the resin composition containing the inorganic filler dispersant stabilizer of the present invention reduces the torque value, suppresses the temperature rise, and the resin composition is detackified by the inorganic filler dispersant stabilizer of the present invention.

(Example 20: Synthesis of Dispersing Stabilizer G) In a 5-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux cooler, 1,634 g of 1,3-butanediol, 210 g of neopentyl glycol, 2,338 g of adipic acid, and 0.125 g of tetraisopropyl titanium as an esterification catalyst were supplied, and the temperature was gradually raised to 220°C while stirring under a nitrogen flow, so as to carry out a condensation reaction for a total of 16 hours. After the reaction, 373 g of maleic anhydride was supplied at 125°C to terminate the reaction, and a dispersing stabilizer G (acid value 55, hydroxyl value 53, number average molecular weight 1190) containing a polyester having carboxyl groups at both ends was obtained.

(Example 21: Synthesis of Dispersing Stabilizer H) In a 5-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux cooler, 1,394 g of 1,3-butanediol, 179 g of neopentyl glycol, 2,629 g of sebacic acid, and 0.126 g of tetraisopropyl titanium ester as an esterification catalyst were supplied, and the temperature was gradually raised to 220°C while stirring under a nitrogen flow, so as to carry out a condensation reaction for a total of 17 hours. After the reaction, 387 g of maleic anhydride was supplied at 125°C to terminate the reaction, and a dispersing stabilizer H (acid value 56, hydroxyl value 43, number average molecular weight 1550) containing a polyester having carboxyl groups at both ends was obtained.

(Example 22: Synthesis of Dispersing Stabilizer I) In a 3-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux cooler, 1214 g of 3-methyl-1,5-pentanediol, 966 g of sebacic acid, and 0.07 g of tetraisopropyl titanium as an esterification catalyst were supplied, and the temperature was gradually raised to 220°C while stirring under a nitrogen flow, so as to carry out a condensation reaction for a total of 12 hours. After the reaction, 271 g of maleic anhydride was supplied at 125°C to terminate the reaction, thereby obtaining a dispersing stabilizer I (acid value 65, hydroxyl value 35, number average molecular weight 1,540) containing a polyester having carboxyl groups at both ends.

(Example 23: Synthesis of Dispersing Stabilizer J) In a 3-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux cooler, 473 g of 3-methyl-1,5-pentanediol, 850 g of sebacic acid, and 0.04 g of tetraisopropyl titanium ester as an esterification catalyst were supplied. The mixture was stirred under a nitrogen flow while the temperature was gradually raised to 220°C. The condensation reaction lasted for a total of 13 hours to obtain a dispersing stabilizer J (acid value 22, hydroxyl value 1, number average molecular weight 4320) containing a polyester having carboxyl groups at both ends.

(Examples 24-27: Preparation and evaluation of a composition containing calcium carbonate) Calcium carbonate (heavy calcium carbonate, "SUPER S" manufactured by Maruo Calcium Co., Ltd.) as an inorganic filler, DINP (diisononyl phthalate) as a plasticizer, DETDA (diethyltoluenediamine) as an active hydrogen compound, a dispersing stabilizer and a viscosity reducing agent were mixed in the proportions shown in Table 5, and stirred for 2 minutes at 1000 rpm and 0.2 Pa using a planetary stirring device (THINKY ARV-310) to obtain a paste-like composition containing an inorganic filler. The viscosity and storage stability of the obtained paste were evaluated using the same method as above. The results are shown in Table 5.

[Table 5] Embodiment 24 Embodiment 25 Embodiment 26 Embodiment 27 blend[g] Calcium carbonate 60 60 60 60 DINP 33 33 33 33 DETDA 7 7 7 7 Viscosity reducer n-Hexyl ether Mineral Oil Viscosity Reducing Agent A Dispersing Stabilizer G 0.3 Dispersing stabilizer H 0.3 Dispersing stabilizer I 0.3 Dispersing stabilizer J 0.3 Viscosity [mPa・s] 2,300 1,220 840 2,400 Storage stability ○ ○ ○ ○

(Example 28-30 and Comparative Example 11-16: Preparation and evaluation of alumina-containing compositions) Alumina (high purity alumina, "AKP-3000" manufactured by Sumitomo Chemical Co., Ltd.) as an inorganic filler, alicyclic epoxy resin ("CELLOXIDE 2021P" manufactured by DAICEL Co., Ltd.) or bisphenol A epoxy resin ("EPICLON 850-S" manufactured by DIC Co., Ltd.) as an adhesive resin, a dispersing stabilizer and a viscosity reducing agent were mixed in the proportions shown in Table 6, and stirred for 2 minutes at 1000 rpm and 0.2 Pa using a planetary stirring device (THINKY ARV-310) to obtain a composition containing an inorganic filler. The fluidity and complex viscosity of the obtained composition were evaluated by the following method, and the storage stability was evaluated by the same method as above. The results are shown in Tables 6 and 7.

[Complex viscosity] The obtained composition was subjected to frequency-dependent measurement using the dynamic viscoelasticity measurement method using MCR-302 (manufactured by Anton Paar Co., Ltd.). Specifically, a parallel plate (diameter: 20 mm) was used, the measurement temperature was set to 25°C, the shear strain was set to 0.01%, and the angular frequency was set to the range of 0.1 to 100 rad/s, and the complex viscosity at an angular frequency of 1 rad/s was calculated.

[Evaluation of fluidity] About 0.2 g of the obtained composition was dripped onto a horizontal glass substrate with a dropper. After dripping, the glass substrate was tilted at an angle of 80° relative to the horizontal. The composition on the glass substrate was evaluated as "○" if it flowed down from the glass substrate, and "×" if it did not flow down from the glass substrate and stayed. The evaluation was performed at 25°C.

[Table 6] Embodiment 28 Embodiment 29 Comparative Example 11 Comparative Example 12 Comparative Example 13 blend[g] Alumina 60 60 60 60 60 Cycloepoxy 40 40 40 40 40 Viscosity reducer n-Hexyl ether 1 Viscosity Reducing Agent A 1 Dispersing stabilizer F 1 Dispersing stabilizer H 1 Liquidity ○ ○ × × × Complex viscosity [Pa・s] 420 30 5214000 2683800 77630 Storage stability ○ ○ ○ ○ ○

[Table 7] Embodiment 30 Comparative Example 14 Comparative Example 15 Comparative Example 16 blend[g] Alumina 60 60 60 60 Bisphenol A epoxy resin 40 40 40 40 Viscosity reducer n-Hexyl ether 1 Viscosity Reducing Agent A 1 Dispersing stabilizer F 1 Liquidity ○ × × × Complex viscosity [Pa・s] 80 546300 1550 680940 Storage stability ○ ○ ○ ○

From the results in Tables 6 and 7, it can be seen that viscosity reducer A cannot show viscosity reducing effect in the composition containing epoxy resin.

(Example 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.) as an inorganic filler, acetone, a dispersing stabilizer and a viscosity reducer were mixed in the proportions shown in Table 8, and a planetary stirring device (THINKY ARV-310) was used to stir at 1000 rpm and 0.2 Pa for 2 minutes to obtain a composition containing an inorganic filler. The fluidity and storage stability of the obtained composition were evaluated by the method shown below. The results are shown in Table 8.

[Evaluation of fluidity] About 0.2 g of the obtained composition was dripped onto a horizontal glass substrate with a dropper. After dripping, the glass substrate was tilted at an angle of 80° relative to the horizontal. The composition on the glass substrate was evaluated as "○" if it flowed down from the glass substrate, and "×" if it did not flow down from the glass substrate and stayed. The evaluation was performed at 25°C.

[Evaluation of storage stability] 12 g of the obtained composition was stored in a 50 cc glass bottle and placed in a thermostat at 25°C for 2 weeks. The composition after placement was visually and tactilely confirmed and evaluated according to the following criteria. ○: The presence of inorganic filler aggregates (hard lumps) could not be confirmed ×: The presence of inorganic filler aggregates (hard lumps) could be confirmed

[Table 8] Embodiment 31 Embodiment 32 Comparative Example 17 Comparative Example 18 Comparative Example 19 blend[g] Alumina 60 60 60 60 60 acetone 40 40 40 40 40 Viscosity reducer n-Hexyl ether 1 Viscosity Reducing Agent A 1 Dispersing stabilizer F 1 Dispersing stabilizer H 1 Liquidity ○ ○ × × × Storage stability ○ ○ ○ ○ ○

without.

FIG. 1 is a graph showing the measurement results of the dispersion stabilizer C produced in Example 3 by MALDI-TOFMS (matrix-assisted laser desorption ionization-time of flight mass spectrometry).

Claims (9)

A resin composition containing an inorganic filler comprises a resin, an inorganic filler and an inorganic filler dispersing stabilizer, wherein the inorganic filler dispersing stabilizer is a polyester represented by the following general formula (1) and has an acid value in the range of 20 to 400 mgKOH/g.

(In the above general formula (1), _A1 is an aliphatic dibasic acid residue having 2 to 12 carbon atoms; _A2 and _A3 are each independently an aliphatic polybasic acid residue having 2 to 12 carbon atoms or an aromatic polybasic acid residue having 6 to 15 carbon atoms; _G1 and _G2 are each independently an aliphatic diol residue having 2 to 9 carbon atoms; m represents a repeating number and is an integer in the range of 1 to 20; p is an integer obtained by subtracting 1 from the number of acid functional groups (hydroxy acid functional groups) of the aliphatic polybasic acid or aromatic polybasic acid of _A2 ; q is an integer obtained by subtracting 1 from the number of acid functional groups of the _aliphatic polybasic acid or aromatic polybasic acid of A3; each repeating unit _A1 and _G1 enclosed in parentheses may be the same or different). The resin composition containing inorganic filler as claimed in claim 1, wherein the number average molecular weight of the inorganic filler dispersing stabilizer is in the range of 300 to 5,000. A resin composition containing an inorganic filler as claimed in claim 1, wherein the inorganic filler is one or more selected from the group consisting of calcium carbonate, silicon dioxide, aluminum oxide, aluminum hydroxide, talc, barium titanium oxide, boron nitride and aluminum nitride. The resin composition containing inorganic filler as claimed in claim 1 further contains a viscosity reducing agent. A resin composition containing an inorganic filler as claimed in claim 4, wherein the aforementioned detackifier is one or more selected from the group consisting of polycarboxylic acid alkyl ammonium salts, higher fatty acid amides, polyester acid unsaturated and polyamino amide salts, and polyesters having a carboxyl group only at one end. The resin composition containing inorganic filler as claimed in any one of claims 1 to 5 further contains a plasticizer. A resin composition containing an inorganic filler as claimed in any one of claims 1 to 5, wherein the resin is one or more selected from the group consisting of polyolefins, polyesters, polysulfides, polyvinyl chloride, modified polysulfides, silicone resins, modified silicone resins, acrylic urethane resins, epoxy resins, polyurethanes, acrylic resins, polyesters and unsaturated polyesters. A molded product, which is a molded product of a resin composition containing an inorganic filler as described in any one of claims 1 to 7. A waterproof material comprising a viscosity reducing agent and a resin composition containing an inorganic filler as in claim 1 or 2, wherein the resin is polyurethane and the inorganic filler is calcium carbonate.