Inorganic filler flow modifier, inorganic filler-containing resin composition, and molded article of said resin composition

Abstract

The present invention provides an inorganic filler fluidity modifier that improves the fluidity of an inorganic filler. Specifically, the inorganic filler fluidity modifier is an ester resin represented by the following general formula (1) (M is an aliphatic monoalcohol residue having 3 to 18 carbon atoms, L is an aliphatic hydroxycarboxylic acid residue having 2 to 23 carbon atoms, A is an aliphatic dicarboxylic acid residue having 1 to 8 carbon atoms or an aromatic dicarboxylic acid residue having 6 to 18 carbon atoms).

Description

Technology Field

[0001] The present invention relates to an inorganic filler fluidity modifier, an inorganic filler-containing resin composition, and a molded article of said resin composition. Background Technology

[0002] Building materials, automotive components, sanitary absorbent articles, stone paper, heat dissipation materials, etc. are molded from a resin composition containing an inorganic filler, and various functions such as impact resistance, flexural resistance, dimensional stability, moisture permeability, and heat dissipation are imparted by the inorganic filler.

[0003] In order to enhance the functionality of the above-mentioned molded article and / or to achieve cost reduction through increased volume, it is required to further increase the amount of inorganic filler. However, when the amount of inorganic filler in the resin composition is increased, the fluidity of the inorganic filler decreases, and along with this, the fluidity of the resin composition also decreases, which has the problem of significantly impairing the moldability of the resin composition.

[0004] For example, in the application of urethane waterproofing flooring materials, calcium carbonate is generally used as an inorganic filler; however, increasing the amount of calcium carbonate filler leads to an increase in viscosity, which causes problems with poor moldability and handling properties.

[0005] As a means to solve the problem of the moldability of a composition being compromised by the formulation of fillers, a method of adding a viscosity-reducing agent has been proposed (e.g., Patent Document 1). In addition, a method of improving the fluidity of a composition by adding a fluidity modifier that improves the fluidity of the filler has also been proposed (e.g., Patent Document 2). However, even with the above viscosity-reducing agent and the above fluidity modifier, the effect of improving the fluidity of the resin composition was not sufficient. Prior art literature

[0006] Japanese Patent Publication No. 2011-79935 and Japanese Patent Publication No. 2018-181959 The problem to be solved

[0007] The problem that the present invention aims to solve is to provide an inorganic filler fluidity modifier that improves the fluidity of inorganic fillers. means of solving the problem

[0008] The inventors, having conducted a thorough investigation to solve the above problem, discovered that an ester resin having a specific structure exhibits an excellent fluidity modification effect for inorganic fillers, thereby completing the present invention.

[0009] That is, the present invention relates to an inorganic filler fluidity modifier which is an ester resin represented by the following general formula (1).

[0010]

[0011] (Among the above general formula (1),

[0012] M is an aliphatic monoalcohol residue having 3 to 18 carbon atoms, and

[0013] L is an aliphatic hydroxycarboxylic acid residue having 2 to 23 carbon atoms, and

[0014] A is an aliphatic dicarboxylic acid residue having 1 to 8 carbon atoms or an aromatic dicarboxylic acid residue having 6 to 18 carbon atoms, and n represents the number of repetitions. Effects of the invention

[0015] The present invention provides an inorganic filler fluidity modifier that improves the fluidity of the inorganic filler. Specific details for implementing the invention

[0016] Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within a range that does not impair the effects of the present invention.

[0017] [Inorganic Filler Flow Modifier]

[0018] The inorganic filler fluidity modifier of the present invention is an ester resin represented by the following general formula (1).

[0019] Hereinafter, the ester resin that is an inorganic filler fluidity modifier of the present invention may be referred to as the “ester resin of the present invention.”

[0020]

[0021] (Among the above formula (1),

[0022] M is an aliphatic monoalcohol residue having 3 to 18 carbon atoms, and

[0023] L is an aliphatic hydroxycarboxylic acid residue having 2 to 23 carbon atoms, and

[0024] A is an aliphatic dicarboxylic acid residue having 1 to 8 carbon atoms or an aromatic dicarboxylic acid residue having 6 to 18 carbon atoms, and

[0025] n represents the number of repetitions)

[0026] The ester resin of the present invention is thought to modify the fluidity of an inorganic filler by ensuring compatibility with the base resin in the resin composition, wherein a carboxyl group at one end is adsorbed to the inorganic filler and a polyhydroxycarboxylic acid chain containing an aliphatic monoalcohol residue at the other end.

[0027] In the present invention, "alcohol residue" refers to an organic group remaining after removing the hydroxyl group from the alcohol.

[0028] In the present invention, "hydroxycarboxylic acid residue" refers to the organic group remaining after subtracting the hydroxyl group and the carboxyl group from the hydroxycarboxylic acid. Regarding the number of carbon atoms in the hydroxycarboxylic acid residue, carbon atoms in the carboxyl group are not included.

[0029] In the present invention, a dicarboxylic acid residue refers to an organic group remaining after subtracting two carboxyl groups from a dicarboxylic acid. Regarding the number of carbon atoms in the dicarboxylic acid residue, carbon atoms in the carboxyl groups are not included.

[0030] The lipid chain of the aliphatic monoalcohol residue of M may be straight or branched, and may include an aliphatic structure and / or ether bond. Additionally, the lipid chain of the aliphatic monoalcohol residue of M may be an unsaturated lipid chain having carbon-carbon unsaturated bonds.

[0031] Examples of aliphatic monoalcohol residues of M having 3 to 18 carbon atoms include propanol residues, butanol residues, pentanol residues, hexanol residues, cyclohexanol residues, heptanol residues, octanol residues, nonanol residues, decanol residues, undecanol residues, cetanol residues, stearyl alcohol residues, etc.

[0032] The aliphatic monoalcohol residue of M having 3 to 18 carbon atoms is preferably an aliphatic monoalcohol residue having 5 to 18 carbon atoms, more preferably an aliphatic monoalcohol residue having a branched structure having 5 to 18 carbon atoms, and even more preferably an aliphatic monoalcohol residue having a branched structure having 7 to 18 carbon atoms.

[0033] For example, by making M an aliphatic monoalcohol residue that becomes a branched alkyl group having 5 to 18 carbon atoms, compatibility with the base resin in the resin composition can be further increased.

[0034] The lipid chain of the aliphatic hydroxycarboxylic acid residue of L may be straight or branched, and may include an aliphatic structure and / or ether bond. Additionally, the lipid chain of the aliphatic hydroxycarboxylic acid residue of L may be an unsaturated lipid chain having carbon-carbon unsaturated bonds.

[0035] Examples of aliphatic hydroxycarboxylic acid residues having 2 to 23 carbon atoms of L include hydroxycarboxylic acid residues in which one hydroxyl group is substituted on the lipid chain of an aliphatic carboxylic acid having 2 to 23 carbon atoms, such as propionic acid, butyric acid, valeric acid, caproic acid, enantic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, and stearic acid; specific examples include lactic acid residues, 9-hydroxystearic acid residues, 12-hydroxystearic acid residues, 6-hydroxycaproic acid residues, ricinoleic acid residues, etc.

[0036] The aliphatic hydroxycarboxylic acid residue of L having 2 to 23 carbon atoms is preferably an aliphatic hydroxycarboxylic acid residue having a branched structure having 2 to 23 carbon atoms, and more preferably an aliphatic hydroxycarboxylic acid residue having a branched structure having 12 to 23 carbon atoms.

[0037] For example, by making L a hydroxycarboxylic acid residue that becomes an alkylene group having 2 to 23 carbon atoms, compatibility with the base resin in the resin composition can be further increased.

[0038] n Ls may be of type 1 alone or of type 2 or more.

[0039] L may be, for example, a combination of an aliphatic hydroxycarboxylic acid residue having a branched structure with 12 to 23 carbon atoms and an aliphatic hydroxycarboxylic acid residue having 2 to 6 carbon atoms.

[0040] When L is a combination of L1, an aliphatic hydroxycarboxylic acid residue having a branched structure with 12 to 23 carbon atoms, and L2, an aliphatic hydroxycarboxylic acid residue having 2 to 6 carbon atoms, the abundance ratio (molar ratio) of L1 and L2 is, for example, L1:L2=60~95:40~5.

[0041] The lipid chain of the aliphatic dicarboxylic acid residue of A may be straight or branched, and may include a ring structure and / or ether bonds. Additionally, the lipid chain of the aliphatic dicarboxylic acid residue of A may be a saturated lipid chain or an unsaturated lipid chain having carbon-carbon unsaturated bonds.

[0042] Examples of aliphatic dicarboxylic acid residues having 1 to 8 carbon atoms of A include malonic acid residues, succinic acid residues, glutaric acid residues, adipic acid residues, pimelic acid residues, souveric acid residues, azelaic acid residues, sebacic acid residues, maleic acid residues, fumaric acid residues, 1,2-dicarboxycyclohexane residues, 1,2-dicarboxycyclohexene residues, etc.

[0043] Examples of aromatic dicarboxylic acid residues having 6 to 18 carbon atoms in A include phthalic acid residues, isophthalic acid residues, terephthalic acid residues, etc.

[0044] A is preferably an aliphatic dicarboxylic acid residue having 1 to 8 carbon atoms, and more preferably an aliphatic dicarboxylic acid residue having 2 to 4 carbon atoms.

[0045] n represents the number of repetitions, and the average value of the number of repetitions is preferably in the range of 2 to 20.

[0046] In addition, the average value of n can be confirmed from the number-average molecular weight of the polyester.

[0047] The number average molecular weight (Mn) of the polyester of the present invention is, for example, in the range of 500 to 5,000, preferably in the range of 500 to 4,000, more preferably in the range of 500 to 3,000, and even more preferably in the range of 700 to 3,000.

[0048] The number average molecular weight (Mn) above is a value converted to polystyrene based on gel permeation chromatography (GPC) measurement, and is measured by the method described in the example.

[0049] The acid value of the polyester of the present invention is preferably in the range of 5 to 120, more preferably in the range of 7 to 80, and even more preferably in the range of 7 to 50.

[0050] The acid value of the above polyester is confirmed by the method described in the example.

[0051] The properties of the polyester of the present invention vary depending on the number average molecular weight or composition, but are preferably liquid at room temperature.

[0052] Here, "liquid at room temperature" means that the polyester of the present invention exhibits fluidity at room temperature of 25°C.

[0053] The polyester of the present invention is obtained using a reaction raw material comprising an aliphatic monoalcohol, an aliphatic hydroxycarboxylic acid, an aliphatic dicarboxylic acid, or an aromatic dicarboxylic acid. Here, the term "reaction raw material" means a raw material constituting the polyester of the present invention, and means not including a solvent or catalyst that does not constitute the polyester.

[0054] The method for manufacturing the polyester of the present invention is not particularly limited and can be manufactured by known methods and by the manufacturing method described below.

[0055] The reaction raw material of the polyester of the present invention may include an aliphatic monoalcohol, a hydroxycarboxylic acid, an aliphatic dicarboxylic acid, or an aromatic dicarboxylic acid, and may include other raw materials.

[0056] The reaction raw material of the polyester of the present invention preferably comprises at least 90 mass% of an aliphatic monoalcohol, an aliphatic hydroxycarboxylic acid, an aliphatic dicarboxylic acid, or an aromatic dicarboxylic acid with respect to the total amount of the reaction raw material, and more preferably comprises only an aliphatic monoalcohol, an aliphatic hydroxycarboxylic acid, an aliphatic dicarboxylic acid, or an aromatic dicarboxylic acid.

[0057] The aliphatic monoalcohol used in the manufacture of the polyester of the present invention is an aliphatic monoalcohol corresponding to an aliphatic monoalcohol residue having 3 to 18 carbon atoms of M, and the aliphatic monoalcohol used may be used alone or in combination of two or more types.

[0058] The aliphatic hydroxycarboxylic acid used in the manufacture of the polyester of the present invention is an aliphatic hydroxycarboxylic acid corresponding to an aliphatic hydroxycarboxylic acid residue having 2 to 23 carbon atoms in L, and the aliphatic hydroxycarboxylic acid used may be used alone or two or more types may be used in combination.

[0059] The aliphatic dicarboxylic acid used in the manufacture of the polyester of the present invention is an aliphatic dicarboxylic acid corresponding to an aliphatic dicarboxylic acid residue having 1 to 8 carbon atoms of A, and the aliphatic dicarboxylic acid used may be used as a single type or two or more types may be used in combination.

[0060] The aromatic dicarboxylic acid used in the manufacture of the polyester of the present invention is an aromatic dicarboxylic acid corresponding to an aromatic dicarboxylic acid residue having 6 to 18 carbon atoms of A, and the aromatic dicarboxylic acid used may be used as a single type or two or more types may be used in combination.

[0061] The reaction raw materials used include derivatives of the above-mentioned esters, above-mentioned acid chlorides, and above-mentioned acid anhydrides, and for example, if they are hydroxycarboxylic acids, they also include compounds having a lactone structure such as ε-caprolactone.

[0062] Any of the aliphatic monoalcohols, aliphatic hydroxycarboxylic acids, aliphatic dicarboxylic acids, and aromatic dicarboxylic acids used in the manufacture of the polyester of the present invention may be derivatives thereof.

[0063] Examples of derivatives include esters, acid chlorides, cyclic esters, etc.

[0064] When using two types of aliphatic hydroxycarboxylic acids in combination, for example, it is preferable to use an aliphatic hydroxycarboxylic acid having a branched structure with 13 to 24 carbon atoms and an aliphatic hydroxycarboxylic acid having 3 to 7 carbon atoms in combination.

[0065] At this time, the molar ratio of an aliphatic hydroxycarboxylic acid having a branched structure with 13 to 24 carbon atoms and an aliphatic hydroxycarboxylic acid having 3 to 7 carbon atoms can be, for example, (aliphatic hydroxycarboxylic acid having a branched structure with 13 to 24 carbon atoms):(aliphatic hydroxycarboxylic acid having 3 to 7 carbon atoms) = 60 to 95:40 to 5.

[0066] The polyester represented by the above general formula (1) can be prepared, for example, by reacting an aliphatic hydroxycarboxylic acid and an aliphatic monoalcohol under conditions where the equivalent amount of a hydroxyl group is greater than the equivalent amount of a carboxyl group to obtain a polyester having a hydroxyl group only at one end of the main chain, and then further reacting the obtained polyester with an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid.

[0067] In the manufacture of the polyester of the present invention, the reaction of the reaction raw materials may be carried out, if necessary, in the presence of an esterification catalyst, for example, within a temperature range of 170 to 250°C for 10 to 25 hours.

[0068] In addition, conditions such as temperature and time for the esterification reaction are not particularly limited and may be set appropriately.

[0069] Examples of the above ester catalysts include titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; zinc-based catalysts such as zinc acetate; tin-based catalysts such as tin octylate and dibutyl tin oxide; and organic sulfonic acid-based catalysts such as p-toluenesulfonic acid.

[0070] The amount of the above esterification catalyst used can be set appropriately, but typically, it is used in the range of 0.001 to 0.1 parts by mass per 100 parts by mass of the total amount of reaction raw materials.

[0071] [Inorganic Filler-Containing Resin Composition]

[0072] The inorganic filler flow modifier of the present invention can function as a flow modifier for the inorganic filler in a resin composition (inorganic filler-containing resin composition) comprising an inorganic filler and a resin. By including the inorganic filler flow modifier of the present invention, the amount of inorganic filler in the resin composition can be increased, and handling properties, moldability, etc., can also be improved.

[0073] Hereinafter, each component included in the inorganic filler-containing resin composition of the present invention will be described.

[0074] (Weapon Filler)

[0075] The inorganic filler contained in the inorganic filler-containing resin composition of the present invention is not particularly limited, and examples include calcium carbonate, talc, silica, clay, antimony oxide, alumina, aluminum hydroxide, magnesium hydroxide, hydrotalcite, calcium silicate, magnesium oxide, potassium titanate, barium titanate, titanium oxide, calcium oxide, manganese dioxide, boron nitride, aluminum nitride, etc.

[0076] The above-mentioned inorganic filler may be used as a single type or in combination with two or more types.

[0077] The above inorganic filler is preferably one or more selected from the group consisting of calcium carbonate, silica, alumina, aluminum hydroxide, barium titanate, talc, boron nitride, and aluminum nitride, and more preferably one or more selected from the group consisting of calcium carbonate, alumina, aluminum hydroxide, and talc.

[0078] The shape of the above-mentioned inorganic filler, such as particle size, fiber length, and fiber diameter, is not particularly limited and may be adjusted appropriately according to the intended application. Furthermore, the surface treatment state of the above-mentioned inorganic filler is not particularly limited and may be surface modified, for example, with saturated fatty acids, depending on the intended application.

[0079] The content of the inorganic filler fluidity modifier of the present invention is not particularly limited, but for example, is in the range of 0.01 to 30 parts by mass of the inorganic filler fluidity modifier of the present invention per 100 parts by mass of inorganic filler, preferably in the range of 0.05 to 10 parts by mass of the inorganic filler fluidity modifier of the present invention per 100 parts by mass of inorganic filler, and more preferably in the range of 0.1 to 5.0 parts by mass of the inorganic filler fluidity modifier of the present invention per 100 parts by mass of inorganic filler.

[0080] (Plasticizer)

[0081] The inorganic filler-containing resin composition of the present invention preferably includes a plasticizer.

[0082] As the above 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), diundecyl phthalate (DUP), and ditridecyl phthalate (DTDP); terephthalic acid esters such as bis(2-ethylhexyl) terephthalate (DOTP); isophthalic acid esters such as bis(2-ethylhexyl) isophthalate (DOIP); and pyromellitic acid esters such as tetra-2-ethylhexyl pyromellitic acid (TOPM). Aliphatic dibasic acid esters such as di-2-ethylhexyl adipoate (DOA), diisononyl adipoate (DINA), diisodecyl adipoate (DIDA), di-2-ethylhexyl sebacate (DOS), and diisononyl sebacate (DINS); phosphate esters such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP); alkyl esters of polyhydric alcohols such as pentaerythritol; polyesters with a molecular weight of 800 to 4,000 synthesized by the polyesterization of dibasic acids such as adipic acid and glycols; epoxidized esters such as epoxidized soybean oil and epoxidized linseed oil; alicyclic dibasic acids such as diisononyl hexahydrophthalate esters; fatty acid glycol esters such as dicapric acid 1,4-butanediol; and tributyl acetyl citrate (ATBC). Examples include chlorinated paraffin obtained by chlorinating paraffin wax or n-paraffin; chlorinated fatty acid esters such as chlorinated stearic acid esters; and higher fatty acid esters such as butyl oleate.

[0083] The plasticizer to be used may be determined according to the intended use, and the above plasticizer may be used alone or in combination of two or more types.

[0084] The content of the above plasticizer is not particularly limited, but, for example, is in the range of 5 to 300 parts by mass of plasticizer per 100 parts by mass of inorganic filler, and preferably in the range of 10 to 200 parts by mass of plasticizer per 100 parts by mass of inorganic filler.

[0085] The additives contained in the inorganic filler-containing resin composition of the present invention are not limited to the inorganic filler fluidity modifier of the present invention and the plasticizer, and may include other additives other than these.

[0086] Examples of the above other additives include, for instance, degrading agents, flame retardants, stabilizers, stabilizing agents, coloring agents, processing agents, fillers, antioxidants (anti-aging agents), ultraviolet absorbers, light stabilizers, lubricants, antistatic agents, crosslinking agents, etc.

[0087] (profit)

[0088] The resins contained in the inorganic filler-containing resin composition of the present invention are not particularly limited and may 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.

[0089] The resin to be used may be determined according to the intended use, and the above resin may be used as a single type or two or more types may be used in combination.

[0090] The inorganic filler-containing resin composition of the present invention contains resin, but the inorganic filler fluidity modifier of the present invention can also be suitably used in compositions containing viscous compounds such as asphalt instead of resin.

[0091] The inorganic filler-containing resin composition of the present invention can be suitably used as a paste-like resin composition that requires fluidity during use.

[0092] The inorganic filler fluidity modifier of the present invention can be applied to paints, adhesives, structural materials, etc., in that it can reduce the viscosity of the composition and also increase the amount of inorganic filler, and is suitable for structural materials (construction materials) where an increase in filler content is desired, or polysulfide-based sealing materials with a particularly high filler content.

[0093] Hereinafter, compositional examples according to application when the inorganic filler-containing resin composition of the present invention is used as a paste-type resin composition will be described.

[0094] (Structural material)

[0095] Examples of resins contained in the inorganic filler-containing resin composition used in the above structural material include polyolefin, polyurethane, unsaturated polyester, etc.

[0096] The resins used in structural materials (construction materials) vary depending on the application; for example, polyurethane is mainly used as the resin component for waterproofing materials, while unsaturated polyester is mainly used for artificial marble.

[0097] When the structural material is a waterproofing material, the inorganic filler-containing resin composition used for the waterproofing material (hereinafter referred to simply as "resin composition for waterproofing material") is preferably a polyurethane composition containing, for example, a main component containing an isocyanate group-containing compound and a curing agent component containing one or more selected from the group consisting of aromatic polyamines, polyols, water, and moisture.

[0098] As an isocyanate group-containing compound included in the main component, an isocyanate-terminated polyurethane prepolymer obtained by reacting a polyisocyanate having a diphenylmethane diisocyanate structure with a polyol is preferred.

[0099] Examples of the above polyisocyanates include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 2,2'-diphenylmethane diisocyanate. Among these, an isocyanate mixture consisting of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate and / or 2,2'-diphenylmethane diisocyanate is preferred.

[0100] As the above polyol, polyoxypropylene polyol is preferred, and polyoxypolypropylene diol alone or a mixture of polyoxypropylene diol and polyoxypropylene triol is more preferred.

[0101] In the above isocyanate-terminated urethane prepolymer, the ratio of polyisocyanate to polyol is preferably in the range of 1.8 to 2.5 as the molar ratio of isocyanate groups to hydroxyl groups (NCO / OH). In addition, in the isocyanate-terminated urethane prepolymer, the isocyanate group content (NCO group content) is preferably in the range of 2 to 5 mass%.

[0102] Examples of aromatic polyamines included in curing agent components include 4,4'-methylenebis(2-chloroaniline), dimethylthiotoluenediamine, and diethyltoluenediamine. Among these, 4,4'-methylenebis(2-chloroaniline) is known as "MOCA" and is widely used.

[0103] As for the polyol containing the curing agent component, polyether polyol is preferred, and polyoxypropylene polyol is particularly preferred. The number of functional groups of this polyol is preferably in the range of 2 to 4, and more preferably in the range of 2 to 3.

[0104] When the polyurethane is a two-component curing type, the mixing ratio of the main component and the curing agent is such that the molar ratio (NCO / (NH2+OH)) of the isocyanate groups contained in the main component and the active hydrogen-containing groups contained in the curing agent 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.

[0105] The curing agent component may include an inorganic filler, and examples of such inorganic fillers include calcium carbonate, talc, clay, silica, carbon, etc.

[0106] The content of the inorganic filler in the polyurethane composition is preferably in the range of 10 to 60 parts by mass, for example, with respect to 100 parts by mass of the resin component, and preferably in the range of 20 to 50 parts by mass. By setting the content of the inorganic filler to this range, a good balance between the curability of the composition and the performance of the resulting waterproofing material can be achieved.

[0107] In the case of two-component curing polyurethane, the viscosity of both the main component and the curing agent is typically high (main component: range of 7 to 10 Pa·s, curing agent: range of 10 to 30 Pa·s), and the viscosity increases further in winter when the temperature drops. Therefore, the inorganic filler fluidity modifier of the present invention, which can improve the dispersibility of the inorganic filler and increase its content, is useful.

[0108] The inorganic filler flow modifier of the present invention may be included in a resin composition for waterproofing materials. For example, in the case of the two-component curing polyurethane, the inorganic filler flow modifier of the present invention may be included in at least one of the main component and the curing agent component.

[0109] To promote the urethane reaction, the curing agent component may include a known curing catalyst. Examples of such curing catalysts include lead organic acid, tin organic acid, tertiary amine compounds, etc.

[0110] In addition to the inorganic filler and curing catalyst, the curing agent component may include the above-mentioned pigments such as the depigmenting agent, the above-mentioned plasticizer, chromium oxide, titanium oxide, and phthalocyanine; and stabilizers such as antioxidants, ultraviolet absorbers, and dehydrating agents.

[0111] Examples of waterproofing materials obtained by molding a composition for waterproofing materials include roofing materials.

[0112] The above-mentioned rooftop waterproofing material is obtained, for example, by applying a composition in which a main component and a hardener component are mixed to a desired location to form a film, and then curing it by reaction.

[0113] (Sealing material)

[0114] The polysulfide resin used in the above-mentioned polysulfide-based sealing material is not particularly limited as long as it is a resin having sulfide bonds within the molecule, and for example, a hydrocarbon group such as an alkyl group is bonded to the sulfide bond. The polysulfide resin may have, for example, ether bonds, ester bonds, amide bonds, or imide groups in its backbone.

[0115] When a polysulfide resin has ether bonds within its backbone, it becomes a polysulfide-polyether resin. The polysulfide resin may have functional groups, such as thiol groups, hydroxyl groups, and amino groups, at one or both ends.

[0116] As for polysulfide resins, for example, they contain a structural unit represented as -(C2H4OCH2OC2H4-Sx)- (where x is an integer from 1 to 5) in the main chain and also have a thiol group represented as -C2H4OCH2OC2H4-SH at the end.

[0117] It is desirable for the polysulfide resin to have fluidity at room temperature, specifically at 25°C. The number average molecular weight (Mn) of the polysulfide resin is typically 100 to 200,000, and preferably 400 to 50,000 or less.

[0118] In addition, polysulfide-polyether resins may be cited as the above-mentioned polysulfide-based resins. Specifically, thiol group-containing polysulfide-polyether resins may be cited as polysulfide-polyether resins, and for example, in the main chain, (1) "-(R 1 O) n 」(R 1Examples include a polyether portion represented by (2) an alkylene group having 2 to 4 carbon atoms and n being an integer from 6 to 200, and a structural unit represented by (2) "-C2H4OCH2OC2H4-Sx-" and (3) "-CH2CH(OH)CH2-Sx-" (where x is an integer from 1 to 5), and also having a thiol group represented by (4) "-C2H4OCH2OC2H4-SH" or "-CH2CH(OH)CH2-SH" at the end.

[0119] The number average molecular weight of the above polysulfide polyether resin is typically 600 to 200,000, and preferably 800 to 50,000.

[0120] There are no restrictions on the manufacturing method of the above polysulfide resin, and one manufactured by various known methods may be used. In addition, commercially available polysulfide resins may be used. Examples of commercially available polysulfide resins include "Thiokol LP-23, LP-32" (manufactured by Tore Fine Chemical Co., Ltd.) and "THIOPLAST Polymer" (manufactured by AKZO NOBEL). Polysulfide resins may be used alone or in combination of two or more types.

[0121] Various other additives may be used in combination with the polysulfide-based sealing material containing the inorganic filler fluidity modifier of the present invention. Examples of additives include the above-mentioned viscosity modifier, the above-mentioned plasticizer, adhesion modifier, pigment, dye, anti-aging agent, antioxidant, antistatic agent, flame retardant, tackifying resin, stabilizer, dispersant, etc.

[0122] As for the above adhesive imparting agent, for example, silane coupling agents such as aminosilane are particularly effective in improving adhesion to glass surfaces and are also suitable in that they are general-purpose compounds.

[0123] Examples of the above aminosilanes include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxydimethoxysilylpropylamine, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylethyldiethoxysilane, etc.

[0124] Examples of the above pigments include organic pigments such as azo pigments and copper phthalocyanine pigments.

[0125] Examples of the above dyes include black dye, yellow dye, red dye, blue dye, brown dye, etc.

[0126] Examples of the above anti-aging agents include hindered phenol compounds and hindered amine compounds.

[0127] Examples of the above antioxidants include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

[0128] Examples of the above antistatic agents include quaternary ammonium salts; hydrophilic compounds such as polyglycol and ethylene oxide derivatives.

[0129] Examples of the above flame retardants include chloroalkyl phosphate, dimethyl methylphosphonate, bromine-phosphorus compounds, ammonium polyphosphate, neopentyl bromide-polyether, brominated polyether, etc.

[0130] Examples of the above adhesive resins include terpene resin, phenol resin, terpene-phenol resin, rosin resin, xylene resin, epoxy resin, alkyl titanates, organic polyisocyanates, etc.

[0131] Examples of the above stabilizers include fatty acid silyl esters, fatty acid amide trimethylsilyl compounds, etc.

[0132] Dispersants are substances that disperse solids into fine particles in a liquid, and examples include sodium hexametaphosphate, sodium condensed naphthalenesulfonate, and surfactants.

[0133] The above-mentioned polysulfide-based sealing material is typically mixed with a curing agent immediately before use. As the curing agent, for example, a curing agent generally used in polysulfide resin-based sealing materials, such as a metal oxide, a metal peroxide, an organic or inorganic oxidizing agent, an epoxy compound, or an isocyanate compound, may be used. Among these, metal peroxides such as lead dioxide or manganese dioxide are preferred, and manganese dioxide is more preferred. It is preferable to use the fluidity modifier of the present invention mixed into this curing agent.

[0134] When manganese dioxide is used as the curing agent, the amount used is preferably in the range of 2.5 to 25 parts by mass and more preferably in the range of 3 to 20 parts by mass, in order to ensure sufficient curing and obtain a cured product having appropriate elasticity with respect to 100 parts by mass of the polysulfide resin used as the main component.

[0135] The above curing agent may also contain other fillers, plasticizers, curing accelerators, and silane coupling agents.

[0136] When used as a sealing material, the curing conditions are typically 20 to 25°C after mixing the main component and the hardener. In addition, the curing time is typically in the range of 24 to 168 hours.

[0137] The inorganic filler-containing resin composition of the present invention is not limited to the paste-type resin composition and can also be suitably used as a molding resin composition for injection molding, extrusion molding, etc.

[0138] The properties of resin compositions for molding vary, and they may be in a liquid state at the pre-molding stage (room temperature) or become liquid upon heating during molding. However, the inorganic filler fluidity modifier of the present invention can improve the fluidity of the inorganic filler, thereby suppressing the excessive increase in viscosity caused by including the inorganic filler, and thus allowing for smooth melt mixing.

[0139] The inorganic filler fluidity modifier of the present invention can be suitably used in molding resin compositions such as automotive components, sanitary absorbent articles, building materials, stone paper, and heat dissipation members, where it is desired to improve physical properties by increasing the amount of inorganic filler, in that it can increase the amount of inorganic filler.

[0140] Hereinafter, compositional examples according to application when the inorganic filler-containing resin composition of the present invention is used as a molding resin composition will be described.

[0141] (Automotive components)

[0142] As a resin component included in a molding resin composition used for automotive parts (hereinafter referred to simply as "resin composition for automotive parts"), for example, a thermoplastic resin, and among said thermoplastic resins, a polypropylene resin having characteristics such as excellent moldability, high mechanical strength, and cost-effectiveness is preferred.

[0143] The above polypropylene is not particularly limited, but is preferably a polypropylene resin with an MFR (230°C, 2.16 kg) of 60 to 120 g / 10 min.

[0144] The resin composition for automotive parts may further include an olefin-based thermoplastic elastomer as a resin component. The olefin-based thermoplastic elastomer is not particularly limited, but it is preferable to include an ethylene-α-olefin copolymer.

[0145] Examples of inorganic fillers included in a resin composition for automotive parts include talc, calcium carbonate, whiskers (materials of the whiskers include graphite, potassium titanate, alumina, silicon carbide, silicon nitride, mullite, magnesia, magnesium borate, aluminum borate, magnesium sulfate, zinc oxide, titanium boride, etc.), carbon nanofiber, carbon nanotube, kaolin, clay, mica, etc.

[0146] The resin composition for automotive components may include various additives other than the inorganic filler fluidity modifier and inorganic filler of the present invention, and examples of said additives include the above-mentioned viscosity modifier, above-mentioned plasticizer, antioxidant, ultraviolet absorber, light stabilizer, flame retardant, colorant, etc.

[0147] The compositional ratios of the resin components, inorganic fillers, and inorganic filler flow modifiers included in the resin composition for automotive parts are not particularly limited, but it is preferable to adjust the composition to satisfy one or more of the following properties.

[0148] The MFR (230℃, 2.16kg, JIS-K7210-1) of the resin composition for automotive parts is preferably 20g / 10 min or more, and more preferably in the range of 20 to 30g / 10 min.

[0149] The coefficient of linear expansion of the resin composition for automotive parts (JIS-K7197) is 5.0×10⁻⁶ -5 It is desirable that / K or less, and 4.0~5.0×10 -5 It is more desirable to be / K.

[0150] The tensile modulus (JIS-K7161) of the resin composition for automotive parts is preferably 2.5 GPa or higher, and more preferably in the range of 2.5 to 3.0 GPa.

[0151] The Charpy impact value (JIS-K7111) of the resin composition for automotive parts is preferably 30 kJ / m² or higher, and more preferably in the range of 30 to 40 kJ / m².

[0152] Examples of automotive parts obtained by molding a resin composition for automotive parts include a hood, fender, bumper, door, trunk lid, roof, radiator grille, wheel cap, instrument panel, pillar garnish, etc.

[0153] These automotive components can be manufactured by injection molding a resin composition for automotive components.

[0154] (Hygienic absorbent items)

[0155] As for the resin component included in the molding resin composition used for hygienic absorbent articles (hereinafter referred to simply as "resin composition for hygienic absorbent articles"), for example, it is a polyolefin, and among the polyolefins, one or more selected from the group consisting of polyethylene and polypropylene are preferred, and polyethylene is more preferred.

[0156] When using polyethylene as a resin component, for example, two or more types of polyethylene with different densities may be used.

[0157] The polyolefin, which is the resin component of the resin composition for hygienic absorbent articles, is not particularly limited, but preferably has an MFR (190°C, 2.16 kgf) in the range of 0.1 to 20 g / 10 min, and more preferably in the range of 0.5 to 5 g / 10 min.

[0158] By making the MFR 0.1 g / 10 min or higher, sufficient formability of the thin film can be maintained, and by making it 20 g / 10 min or lower, sufficient strength can be achieved.

[0159] The resin composition for hygienic absorbent articles may further include a polystyrene-based elastomer as a resin component.

[0160] Examples of the above-mentioned polystyrene-based elastomers include elastomers containing styrene blocks of styrene-olefin-based (SEP, SEBC, etc.), styrene-olefin-styrene-based (SEPS, SEBS, etc.), styrene-diene-based (SIS, SBS, etc.), and hydrogenated styrene-diene-based (HSIS, HSBR, etc.).

[0161] The styrene component in these polystyrene-based elastomers is preferably in the range of 10 to 40 mass%, and more preferably in the range of 20 to 40 mass%.

[0162] Examples of inorganic fillers included in a resin composition for hygienic absorbent articles include calcium carbonate, calcium sulfate, barium carbonate, titanium oxide, etc., and it is preferable to have one or more selected from the group consisting of calcium carbonate and barium sulfate.

[0163] The shape of these inorganic fillers is not particularly limited, but it is preferable if they are particulate, more preferable if they are fine particles with an average particle size in the range of 0.1 to 10 μm, more preferable if they are fine particles with an average particle size in the range of 0.3 to 5 μm, and particularly preferable if they are fine particles with an average particle size in the range of 0.5 to 3 μm.

[0164] The content of the inorganic filler in the resin composition for hygienic absorbent articles is, for example, preferably polyolefin:inorganic filler = 60 to 20 parts by mass: 40 to 80 parts by mass, more preferably polyolefin:inorganic filler = 55 to 25 parts by mass: 45 to 75 parts by mass, and even more preferably polyolefin:inorganic filler = 50 to 30 parts by mass: 50 to 70 parts by mass.

[0165] If the content of the inorganic filler is within the above range, the moisture permeability, breathability, and liquid impermeability of the resulting hygienic absorbent article can all be sufficiently guaranteed.

[0166] The resin composition for hygienic absorbent articles may include various additives other than the inorganic filler fluidity modifier and inorganic filler of the present invention, and such additives may include the above-mentioned plasticizer, viscosity modifier, compatibilizer, processing aid, antioxidant, heat stabilizer, light stabilizer, ultraviolet absorber, anti-blocking agent, antifog agent, matting agent, surfactant, antibacterial agent, deodorizer, antistatic agent, water repellent, oil repellent, radiation shielding agent, coloring agent, pigment, etc.

[0167] A molded product obtained by molding a resin composition for hygienic absorbent articles can be suitably used as a back sheet (a sheet that has breathability and moisture permeability but does not allow liquid to pass through) used in hygienic absorbent articles such as paper diapers and sanitary napkins.

[0168] The above back sheet can be manufactured, for example, by melt-kneading a resin composition for sanitary absorbent articles, forming it into a sheet by the T-die method or the inflation method, and then uniaxially or biaxially stretching the obtained sheet.

[0169] (Stone Paper)

[0170] Stone paper is a sheet made of calcium carbonate derived from limestone and polyolefins (polyethylene, polypropylene, etc.). It is a sheet with excellent sustainability because it does not require water or wood for molding and the raw material, limestone, exists almost inexhaustibly on Earth.

[0171] Stone paper contains a large amount of calcium carbonate, but the fluidity of calcium carbonate can be increased by the inorganic filler fluidity modifier of the present invention, so the sheet properties can be improved.

[0172] Stone paper can be manufactured, for example, by melt-kneading a stone paper composition comprising calcium carbonate, polyolefin, and the inorganic filler fluidity modifier of the present invention, and then by inflation molding or extrusion molding.

[0173] In the stone paper composition, the calcium carbonate content is, for example, 85:15 to 20:80 in the mass ratio of polyolefin to calcium carbonate (polyolefin:calcium carbonate), preferably 85:15 to 30:70, more preferably 85:15 to 35:65, and even more preferably 80:20 to 40:60.

[0174] The stone paper composition may further include the above-mentioned plasticizer, adhesive agent, foaming agent, colorant, lubricant, coupling agent, stabilizer (antioxidant, UV absorber, etc.), antistatic agent, etc. as auxiliary agents.

[0175] Examples of the above blowing agents include aliphatic hydrocarbon compounds such as propane, normal butane, isobutane, normal pentane, isopentane, and hexane; alicyclic hydrocarbon compounds such as cyclohexane, cyclopentane, and cyclobutane; and halogenated hydrocarbon compounds such as trifluoromonochloroethane and difluorodichloromethane.

[0176] Examples of the above-mentioned lubricants include fatty acid-based lubricants such as stearic acid, hydroxystearic acid, complex stearic acid, and oleic acid; aliphatic amide-based lubricants such as aliphatic alcohol-based lubricants, stearoamide, oxystearoamide, oleylamide, erucylamide, ricinolamide, behenamide, methylolamide, methylenebistearoamide, methylenebistearobehenamide, bisamic acid of a higher fatty acid, and complex amide; aliphatic ester-based lubricants such as stearate-n-butyl, methyl hydroxystearic acid, polyhydric alcohol fatty acid esters, saturated fatty acid esters, and ester-based waxes; and fatty acid metal soap-based lubricants.

[0177] As the above antioxidant, phosphorus-based antioxidants, phenol-based antioxidants, pentaerythritol-based antioxidants, etc. may be used.

[0178] Examples of phosphorus-based antioxidants include phosphoric acid esters such as triesters, diesters, and monoesters of phosphoric acid such as triphenyl phosphite, trisnonylphenyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite; and phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl)phosphate, and 2-ethylphenyl diphenyl phosphate.

[0179] Examples of phenolic antioxidants include α-tocopherol, butylhydroxytoluene, cinnafil alcohol, vitamin E, n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane.

[0180] (Heat dissipation component)

[0181] In electronic devices such as PCs, smartphones, and televisions, heat generation increases alongside performance, so heat dissipation components containing thermally conductive fillers are frequently used to efficiently dissipate the generated heat. Furthermore, automobiles, such as electric and hybrid vehicles, are also equipped with a large number of electronic devices, so heat dissipation components containing thermally conductive fillers are widely used.

[0182] The resin component included in the molding resin composition used for heat dissipation members (hereinafter referred to simply as "resin composition for heat dissipation members") is, for example, a thermosetting resin, an active energy beam curable resin, or a thermoplastic resin.

[0183] As the thermosetting resin of the resin composition for the heat dissipation member, known thermosetting resins may be used, for example, novolak-type phenolic resins such as phenol novolak resin and cresol novolak resin; phenolic resins such as unmodified resol phenolic resin and rheologically modified resol phenolic resin modified with tung oil, linseed oil, walnut oil, etc.; bisphenol-type epoxy resins such as bisphenol A epoxy resin and bisphenol F epoxy resin; novolak-type epoxy resins such as lipid chain modified bisphenol-type epoxy resin, novolak epoxy resin, and cresol novolak epoxy resin; epoxy resins such as biphenyl-type epoxy resin and polyalkylene glycol-type epoxy resin; and resins having a triazine ring such as urea resin and melamine resin. Examples include vinyl resins such as (meth)acrylic resin or vinyl ester resin; unsaturated polyester resin, bismaleimide resin, polyurethane resin, diallyl phthalate resin, silicone resin, resin having a benzoxazine ring, cyanate ester resin, etc.

[0184] The above thermosetting resin is best used together with a curing agent.

[0185] As a curing agent used together with a thermosetting resin, amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, and guanidine derivative; amide compounds such as dicyandiamide and polyamide resins synthesized from a linolenic acid dimer and ethylenediamine; acid anhydride compounds such as phthalic anhydride, trimellitic anhydride, pyrromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride; Examples of phenolic compounds include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadienephenol addition type resin, phenol aralkil resin (xylock resin), resorcin novolak resin, naphtol aralkil resin, trimethylolmethane resin, tetraphenylolethane resin, naphtol novolak resin, naphtol-phenol coaxial novolak resin, naphtol-cresol coaxial novolak resin, biphenyl modified phenol resin, biphenyl modified naphtol resin, aminotriazine modified phenol resin, alkoxy group-containing aromatic ring modified novolak resin, etc.

[0186] As the thermoplastic resin of the resin composition for a heat dissipation member, known thermoplastic resins may be used, for example, polyethylene resin, polypropylene resin, polymethyl methacrylate resin, polyvinyl acetate resin, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride resin, polystyrene resin, polyacrylonitrile resin, polyamide resin, polycarbonate resin, polyacetal resin, polyethylene terephthalate resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyallylsulfone resin, thermoplastic polyimide resin, thermoplastic urethane resin, polyaminobismaleimide resin, polyamideimide resin, polyetherimide resin, bismaleimidetriazine resin, polymethylpentene resin, fluorinated resin, liquid crystal polymer, olefin-vinyl alcohol copolymer, Examples include ionomer resins, polyarylate resins, acrylonitrile-ethylene-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, and acrylonitrile-styrene copolymers.

[0187] Examples of thermally conductive fillers contained in a resin composition for heat dissipation members include alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, calcium oxide, magnesium oxide, zinc oxide, beryllia, aluminum oxide, aluminum nitride, boron nitride, hydrated metal compounds, fused silica, crystalline silica, amorphous silica, silicon carbide, silicon nitride, titanium carbide, diamond, etc.

[0188] The above thermally conductive filler may be used after surface treatment with silane-based, titanate-based, and aluminate-based coupling agents, etc.

[0189] The shape of the thermally conductive filler is not particularly limited and may be any of spherical, needle-shaped, flake-shaped, dendritic, or fibrous.

[0190] The content of the thermally conductive filler in the resin composition for heat dissipation members can be appropriately adjusted according to the application, and it is preferable to have the thermally conductive filler in the range of 30 to 500 parts by mass per 100 parts by mass of the resin component.

[0191] The resin composition for the heat dissipation member may include various additives other than the inorganic filler fluidity modifier and the thermally conductive filler of the present invention, and such additives may include dyes, pigments, antioxidants, polymerization inhibitors, defoaming agents, leveling agents, ion capture agents, humectants, viscosity modifiers, preservatives, antibacterial agents, antistatic agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, etc.

[0192] If the resin composition for the heat dissipation member contains a thermosetting resin, the heat dissipation member can be molded by heating the resin composition. If the resin composition for the heat dissipation member contains an active energy beam curable resin, it can be cured and molded by irradiating active energy beams such as ultraviolet rays or infrared rays. If the resin composition for the heat dissipation member contains a thermoplastic resin, the heat dissipation member can be obtained by known molding methods such as injection molding, extrusion molding, or press molding.

[0193] A heat dissipation member obtained by molding a resin composition for a heat dissipation member can be used as a heat sink. A heat dissipation member obtained by molding a resin composition for a heat dissipation member can also be used as a heat dissipation bonding member for bonding a part to be heat dissipated with a metal heat dissipation member.

[0194] The resin composition for heat dissipation members can also be used as a semiconductor encapsulation material.

[0195] [Example]

[0196] The present invention will be specifically explained below through examples and comparative examples.

[0197] In addition, the present invention is not limited to the following examples.

[0198] In the embodiments of the present invention, the values ​​of acid value and hydroxyl value are values ​​evaluated by the following method.

[0199] [Method for Measuring Acid Value]

[0200] It was measured by the method based on JIS K0070-1992.

[0201] [Method for Measuring Hydroxyl Value]

[0202] It was measured by the method based on JIS K0070-1992.

[0203] In the embodiments of the present invention, the number average molecular weight of the polyester is a value converted to polystyrene based on GPC measurement, and the measurement conditions are as follows.

[0204] [GPC Measurement Conditions]

[0205] Measuring device: High-speed GPC device "HLC-8320GPC" manufactured by Toso Kabushiki Kaisha

[0206] Column: Toso Kabushiki Kaisha "TSK GURDCOLUMN SuperHZ-L" + Toso Kabushiki Kaisha "TSK gel SuperHZM-M" + Toso Kabushiki Kaisha "TSK gel SuperHZM-M" + Toso Kabushiki Kaisha "TSK gel SuperHZ-2000" + Toso Kabushiki Kaisha "TSK gel SuperHZ-2000"

[0207] Detector: RI (Refractor)

[0208] Data Processing: "EcoSEC Data Analysis Version 1.07" manufactured by Doso Kabushiki Kaisha

[0209] Column temperature: 40℃

[0210] Developing solvent: Tetrahydrofuran

[0211] Flow rate: 0.35 mL / min

[0212] Measurement sample: 7.5 mg of the sample was dissolved in 10 ml of tetrahydrofuran, and the resulting solution was filtered through a microfilter and used as the measurement sample.

[0213] Sample injection volume: 20μl

[0214] Standard Sample: Based on the measurement manual of the above "HLC-8320GPC," the following monodisperse polystyrene with a known molecular weight was used.

[0215] (Monodisperse Polystyrene)

[0216] "A-300" manufactured by Doso Kabushiki Kaisha

[0217] "A-500" manufactured by Toso Kabushiki Kaisha

[0218] "A-1000" manufactured by Doso Kabushiki Kaisha

[0219] "A-2500" manufactured by Dosokabushiki Kaisha

[0220] "A-5000" manufactured by Toso Kabushiki Kaisha

[0221] "F-1" manufactured by Doso Kabushiki Kaisha

[0222] "F-2" manufactured by Doso Kabushiki Kaisha

[0223] "F-4" manufactured by Doso Kabushiki Kaisha

[0224] "F-10" manufactured by Doso Kabushiki Kaisha

[0225] "F-20" manufactured by Toso Kabushiki Kaisha

[0226] "F-40" manufactured by Toso Kabushiki Kaisha

[0227] "F-80" manufactured by Toso Kabushiki Kaisha

[0228] "F-128" manufactured by Toso Kabushiki Kaisha

[0229] "F-288" manufactured by Toso Kabushiki Kaisha

[0230] (Synthesization Example 1: Synthesis of Flow Modifier A)

[0231] In a 3-liter 4-neck flask equipped with a thermometer, a stirrer, and a reflux condenser, 1,859 g of hydrogenated castor oil fatty acid (main component: 12-hydroxystearic acid), 325 g of isononyl alcohol, and 0.064 g of tin octylate (Neostane U28, manufactured by Nitto Kasei Co., Ltd.) as an esterification catalyst were added, and a condensation reaction was carried out for a total of 24 hours by gradually increasing the temperature to 210°C while stirring under a nitrogen stream. After confirming that the acid value was 1 or less, the temperature was lowered to 120°C. 89.0 g of maleic anhydride was added, and the reaction was carried out at 120°C. The loss of maleic anhydride was confirmed by IR, and a fluidity modifier A (acid value 19 mgKOH / g, hydroxyl group 14 mgKOH / g, number average molecular weight 1,620), which is a polyester resin liquid at room temperature, was obtained.

[0232] (Synthesization Example 2-4: Synthesis of Flow Modifiers B, C, and D)

[0233] Flowability modifier B (acid value 34 mgKOH / g, hydroxyl group 20 mgKOH / g, number average molecular weight 1050), flowability modifier C (acid value 16 mgKOH / g, hydroxyl group 10 mgKOH / g, number average molecular weight 2200), and flowability modifier D (acid value 19 mgKOH / g, hydroxyl group 36 mgKOH / g, number average molecular weight 1160) were obtained, respectively, in the same manner as in Synthesis Example 1, except that the amounts of hydrogenated castor oil fatty acid, isononyl alcohol, and maleic anhydride were adjusted.

[0234] None of them were liquid at room temperature.

[0235] (Synthesization Example 5: Synthesis of Flow Modifier E)

[0236] In a 2-liter 4-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 987 g of hydrogenated castor oil fatty acid (main component: 12-hydroxystearic acid), 132 g of isononyl alcohol, and 1.05 g of tin octylate (Neostane U28, manufactured by Nitto Kasei Co., Ltd.) as an esterification catalyst were added, and a condensation reaction was carried out for a total of 34 hours by gradually increasing the temperature to 220°C while stirring under a nitrogen stream. After confirming that the acid value was 1 or less, the temperature was lowered to 150°C. 58.9 g of phthalic anhydride was added, and the reaction was carried out at 150°C. The loss of phthalic anhydride was confirmed by IR, and a fluidity modifier E (acid value 18 mgKOH / g, hydroxyl group 4 mgKOH / g, number average molecular weight 2,560), which is a polyester resin liquid at room temperature, was obtained.

[0237] (Synthesization Example 6: Synthesis of Flow Modifier F)

[0238] In a 3-liter 4-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 1859 g of hydrogenated castor oil fatty acid (main component: 12-hydroxystearic acid), 325 g of isononyl alcohol, and 0.064 g of tin octylate (Neostane U28, manufactured by Nitto Kasei Co., Ltd.) as an esterification catalyst were added, and a condensation reaction was carried out for a total of 24 hours by gradually increasing the temperature to 210°C while stirring under a nitrogen stream. After confirming that the acid value was 1 or less, the temperature was lowered to 150°C. 140 g of phthalic anhydride was added, and the reaction was carried out at 150°C. The loss of phthalic anhydride was confirmed by IR, and a fluidity modifier F (acid value 17 mgKOH / g, hydroxyl group 16 mgKOH / g, number average molecular weight 1,460), which is a polyester resin liquid at room temperature, was obtained.

[0239] (Synthesization Example 7: Synthesis of Flow Modifier G)

[0240] In a 3-liter 4-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 1,302 g of hydrogenated castor oil fatty acid (main component: 12-hydroxystearic acid), 355 g of isononyl alcohol, and 0.10 g of tin octylate (Neostane U28, manufactured by Nitto Kasei Co., Ltd.) as an esterification catalyst were added, and a condensation reaction was carried out for a total of 24 hours by gradually increasing the temperature to 210°C while stirring under a nitrogen stream. After confirming that the acid value was 1 or less, the temperature was lowered to 150°C. 113 g of succinic anhydride was added, and the reaction was carried out at 150°C. The loss of succinic anhydride was confirmed by IR, and a fluidity modifier G (acid value 45 mgKOH / g, hydroxyl group 22 mgKOH / g, number average molecular weight 1,200), which is a polyester resin liquid at room temperature, was obtained.

[0241] (Synthetic Comparative Example 1: Synthesis of Flow Modifier A')

[0242] In a 2-liter 4-neck flask equipped with a thermometer, stirrer, and reflux condenser, 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 titanate as an esterification catalyst were added, and a condensation reaction was carried out for a total of 10 hours by gradually increasing the temperature to 220°C while stirring under a nitrogen stream. 44.2 g of maleic anhydride was added, and the reaction was carried out at 150°C. The disappearance of maleic anhydride was confirmed by IR spectroscopy, and a fluidity modifier A', a polyester resin that is liquid at room temperature, was obtained (acid value 29 mgKOH / g, hydroxyl group 120, number average molecular weight 950).

[0243] (Synthetic Comparative Example 2: Synthesis of Flow Modifier B')

[0244] In a 4-necked flask with a volume of 2 liters equipped with a thermometer, a stirrer, and a reflux condenser, 987 g of hydrogenated castor oil fatty acid (main component: 12-hydroxystearic acid), 132 g of isononyl alcohol, and 1.05 g of tin octylate (Neostane U28, manufactured by Nitto Kasei Co., Ltd.) as an esterification catalyst were added, and a condensation reaction was carried out for a total of 34 hours by gradually increasing the temperature to 220°C while stirring under a nitrogen stream. After confirming that the acid value was 1 or less, a fluidity modifier B', which is a polyester resin liquid at room temperature, was obtained (acid value 0.4 mgKOH / g, hydroxyl group 21 mgKOH / g, number average molecular weight 2,870).

[0245] In addition to flow modifiers A~G, flow modifier A', and flow modifier B', a known n-hexyl ether was also prepared separately as a flow modifier.

[0246] (Examples 1-13 and Comparative Examples 1-6: Preparation and Evaluation of Compositions Containing Heavy Calcium Carbonate)

[0247] 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, and a fluidity modifier 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 rotating / revolutionary stirrer (THINKY ARV-310) to obtain a paste-like inorganic filler-containing composition.

[0248] For the obtained paste, the viscosity was evaluated by the following method. The results are shown in Tables 1 and 2.

[0249] (Method for measuring viscosity)

[0250] The viscosity of the obtained paste was measured using an E-type viscometer (TV-25H manufactured by Toyosan Kyo Co., Ltd.) with a standard rotor (1˚34'×R24, shear speed [1 / S] 3.83×N, N is the rotational speed of the rotor [rpm]). Specifically, the obtained paste was treated at a measurement temperature of 25℃ and a rotational speed of 10 rpm, and the viscosity value of the paste was read after 3 minutes of treatment.

[0251] [Table 1]

[0252]

[0253] [Table 2]

[0254]

[0255] While the calcium carbonate-containing compositions using fluidity modifiers A to F of Examples 1-13 each have low viscosity, the calcium carbonate-containing compositions using n-hexyl ether, a viscosity reducing agent, or fluidity modifiers A' and B' of Comparative Examples 1-6 each have high viscosity.

[0256] (Examples 14 and Comparative Examples 7-10: Preparation and Evaluation of Colloidal Calcium Carbonate-Containing Compositions)

[0257] Calcium carbonate (colloidal calcium carbonate, "Calpine 200" manufactured by Maruo Calcium Co., Ltd.) as an inorganic filler, DINP (diisononyl phthalate) as a plasticizer, and a fluidity modifier were mixed in the proportions shown in Table 3, and stirred for 2 minutes at 1000 rpm and 0.2 Pa using an oily stirring device (THINKY ARV-310) to obtain a paste-like inorganic filler-containing composition.

[0258] For the obtained paste, the viscosity was evaluated by the same method as above. The results are shown in Table 3.

[0259] [Table 3]

[0260]

[0261] (Examples 15-20 and Comparative Examples 11-19: Preparation and Evaluation of Compositions Containing Aluminum-Based Inorganic Fillers)

[0262] High-purity alumina (Sumitomo Chemicals Co., Ltd. “AKP-3000”), spherical alumina (Denka Chemicals Co., Ltd. “DAW-07”), aluminum hydroxide as inorganic fillers, DINP (diisononyl phthalate) as a plasticizer, and a fluidity modifier were mixed in the proportions shown in Tables 4 and 5, and stirred for 2 minutes at 1000 rpm and 0.2 Pa using an oily stirring device (THINKY ARV-310) to obtain a paste-like inorganic filler-containing composition.

[0263] For the obtained paste, the fluidity and viscosity were evaluated by the following method. The results are shown in Tables 4 and 5.

[0264] (Method for evaluating liquidity)

[0265] Approximately 0.4g of the obtained composition was dropped onto a horizontal glass substrate using a dropper. After dropping, the glass substrate was tilted at an angle of 80˚ relative to the horizontal, and the composition on the glass substrate was evaluated as “○” if it flowed down the glass substrate and remained on the glass substrate without flowing down, and as “×” if it did not flow down. The evaluation was performed at 25℃.

[0266] (Method for measuring viscosity)

[0267] The viscosity of the obtained paste was measured using an E-type viscometer (TV-25H manufactured by Toyosan Kyo Co., Ltd.) with a No. 6 rotor (3˚×R9.7, shear speed [1 / S] 2.00×N, N is the rotational speed of the rotor [rpm]). Specifically, the obtained paste was treated at a measurement temperature of 25℃ and a rotational speed of 1 rpm, and the viscosity value of the paste was read after 3 minutes of treatment.

[0268] [Table 4]

[0269]

[0270] [Table 5]

[0271]

[0272] It is read that the aluminum-based inorganic filler-containing composition using fluidity modifier B or fluidity modifier G of Examples 15-20 has good fluidity, whereas in Comparative Examples 11-19, fluidity is not obtained.

[0273] (Examples 21-32 and Comparative Examples 20-22: Preparation and Evaluation of Compositions Containing Heavy Calcium Carbonate)

[0274] Calcium carbonate (heavy calcium carbonate, "Super S" manufactured by Maruo Calcium Co., Ltd.) as an inorganic filler, DINP (diisononyl phthalate), PB-10 (benzoic acid ester-based plasticizer, manufactured by DIC Co., Ltd.), and DINA (diisononyl adipose acid) as plasticizers, silicone oil ("KF-54" manufactured by Shin-Etsu Silicon Co., Ltd.), squalene, paraffin-based process oil ("P100" manufactured by Nihon Sun Sekiyu Co., Ltd.), and a fluidity modifier were mixed in the proportions shown in Tables 6 and 7, and stirred for 2 minutes at 1000 rpm and 0.2 Pa using an oily stirring device (THINKY ARV-310) to obtain a paste-like inorganic filler-containing composition.

[0275] For the obtained paste, the fluidity and viscosity were evaluated by the following method. The results are shown in Tables 6 and 7.

[0276] (Method for evaluating liquidity)

[0277] Approximately 0.4g of the obtained composition was dropped onto a horizontal glass substrate using a dropper. After dropping, the glass substrate was tilted at an angle of 80˚ relative to the horizontal, and the composition on the glass substrate was evaluated as “○” if it flowed down the glass substrate and remained on the glass substrate without flowing down, and as “×” if it did not flow down. The evaluation was performed at 25℃.

[0278] (Method for measuring viscosity)

[0279] The viscosity of the obtained paste was measured using an E-type viscometer (TV-25H manufactured by Toyosan Kyo Co., Ltd.) with a standard rotor (1˚34'×R24, shear speed [1 / S] 3.83×N, N is the rotational speed of the rotor [rpm]). Specifically, the obtained paste was treated at a measurement temperature of 25℃ and a rotational speed of 10 rpm, and the viscosity value of the paste was read after 3 minutes of treatment.

[0280] [Table 6]

[0281]

[0282] [Table 7]

[0283]

[0284] While the inorganic filler-containing compositions using flow modifier A or flow modifier G in Examples 21-32 have good flowability, it is read that flowability is not obtained in Comparative Examples 20-22 using flow modifier A'.

[0285] (Example 33 and Comparative Examples 23-24: Preparation and Evaluation of Compositions Containing Aluminum-Based Inorganic Fillers)

[0286] As an inorganic filler, spherical alumina (Denka Co., Ltd. “DAW-07” and “DAW-45”), bisphenol A type epoxy resin, and a flow modifier were mixed in the proportions shown in Table 8, and stirred for 2 minutes at 1000 rpm and 0.2 Pa using an oily stirring device (THINKY ARV-310) to obtain a paste-like inorganic filler-containing composition.

[0287] The viscosity of the obtained paste was evaluated by the following method. The results are shown in Table 8.

[0288] (Method for measuring viscosity)

[0289] The viscosity of the obtained paste was measured using an E-type viscometer (TV-25H manufactured by Toyosan Kyo Co., Ltd.) with a No. 6 rotor (3˚×R9.7, shear speed [1 / S] 2.00×N, N is the rotational speed of the rotor [rpm]). Specifically, the obtained paste was treated at a measurement temperature of 25℃ and a rotational speed of 2 rpm, and the viscosity value of the paste was read after 3 minutes of treatment.

[0290] [Table 8]

[0291]

[0292] It is read that even if the dispersion medium is a resin such as bisphenol A type epoxy resin, high fluidity is obtained by using fluidity modifier B.

Claims

Claim 1 An inorganic filler fluidity modifier that is an ester resin represented by the following general formula (1), has a number average molecular weight in the range of 500 to 5,000, and is a liquid ester resin at room temperature. (In the above general formula (1), M is an aliphatic monoalcohol residue having 3 to 18 carbon atoms, L is a ricinoleic acid residue or an aliphatic hydroxycarboxylic acid residue in which one hydroxyl group is substituted on the lipid chain of an aliphatic carboxylic acid selected from pentadecylic acid, palmitic acid, margaric acid and stearic acid, A is an aliphatic dicarboxylic acid residue having 1 to 8 carbon atoms or an aromatic dicarboxylic acid residue having 6 to 18 carbon atoms, and n represents the number of repetitions) Claim 2 An inorganic filler fluidity modifier according to claim 1, wherein the aliphatic monoalcohol residue is an aliphatic monoalcohol residue in which M is a branched alkyl group having 5 to 18 carbon atoms. Claim 3 In claim 1, A is an inorganic filler fluidity modifier, which is an aliphatic dicarboxylic acid residue having 2 to 4 carbon atoms. Claim 4 An inorganic filler flow modifier according to any one of claims 1 to 3, wherein the acid value is in the range of 5 to 120 mgKOH / g. Claim 5 In any one of claims 1 to 3, an inorganic filler fluidity modifier selected from the group consisting of calcium carbonate, silica, alumina, aluminum hydroxide, talc, barium titanate, boron nitride, and aluminum nitride. Claim 6 An inorganic filler-containing resin composition comprising a resin, an inorganic filler, and an inorganic filler flow modifier described in any one of claims 1 to 3. Claim 7 A resin composition containing an inorganic filler according to claim 6, wherein the inorganic filler is one or more selected from the group consisting of calcium carbonate, silica, alumina, aluminum hydroxide, talc, and barium titanate. Claim 8 In claim 6, an inorganic filler-containing resin composition further containing a plasticizer. Claim 9 A resin composition containing an inorganic filler according to claim 6, wherein the resin is one or more selected from the group consisting of polyolefin, polyester, polysulfide, polyvinyl chloride, modified polysulfide, silicone resin, modified silicone resin, acrylic urethane resin, epoxy resin, polyurethane, acrylic resin, polyester, and unsaturated polyester. Claim 10 A molded article of a resin composition containing inorganic fillers as described in paragraph 6. Claim 11 delete Claim 12 delete Claim 13 delete Claim 14 delete

Images