Thermoplastic resin composite material and molded article composed of same

Abstract

The present invention addresses the problem of providing a thermoplastic resin composite material that is unlikely to generate a volatile organic compound (VOC) and unlikely to develop scorching (discoloration). The problem is solved by a thermoplastic resin composite material containing a thermoplastic resin, a filler, an organic compound having an amino group and / or an amide group, and a basic inorganic compound. The filler content is 10-70 mass%, the organic compound content is 0.1-5.0 mass%, and the ratio of the organic compound content to the inorganic compound content (compound content / inorganic compound content) is 0.1-1.0.

Description

Thermoplastic resin composite material and molded article formed therefrom

[0001] The present disclosure relates to a thermoplastic resin composite material and a molded article formed therefrom.

[0002] Conventionally, several resin compositions have been proposed. For example, Patent Document 1 describes a polypropylene resin composition characterized by comprising 5 to 85% by mass of a polypropylene resin (A) having a melting point of 150°C or higher, 5 to 85% by mass of a polypropylene resin (B) having a melting point of 110°C or higher and lower than 150°C, and 10 to 80% by mass of a biomass material (C) (provided that the total mass of (A), (B) and (C) is 100% by mass). It is described that such a resin composition is excellent in environmental protection performance and can suppress odor and plastic feel.

[0003] Japanese Patent Application Laid-Open No. 2021-50270

[0004] It is preferable that a thermoplastic resin composite material and a molded article formed therefrom hardly generate volatile organic compounds (VOC) during the production process, and also hardly cause burning (coloring).

[0005] The present disclosure provides a thermoplastic resin composite material and a molded article formed therefrom, in which volatile organic compounds (VOC) are less likely to be generated even when heated in the production stage, and burning (coloring) is also less likely to occur.

[0006] The present disclosure includes a thermoplastic resin composite material comprising: a thermoplastic resin; a filler; an organic compound having an amino group and / or an amide group; and a basic inorganic compound, wherein the content of the filler is 10 to 70% by mass, the content of the organic compound is 0.1 to 5.0% by mass, and the ratio of the content of the organic compound to the content of the inorganic compound (content of organic compound / content of inorganic compound) is 0.1 to 1.0.

[0007] Hereinafter, such a thermoplastic resin composite material is also referred to as "the composite material of the present disclosure".

[0008] According to this disclosure, it is possible to provide a thermoplastic resin composite material and a molded product made therefrom that are less likely to generate volatile organic compounds (VOCs) and less likely to burn (discolor) even when heated during the manufacturing process.

[0009] The composite materials of this disclosure are described below. The composite materials of this disclosure include thermoplastic resins, fillers, organic compounds having amino and / or amide groups, and basic inorganic compounds.

[0010] <Thermoplastic Resin> The thermoplastic resin contained in the composite material of this disclosure will be described. The thermoplastic resin content in the composite material of this disclosure is preferably 5 to 89.9% by mass, more preferably 12 to 80% by mass, and even more preferably 16 to 76% by mass.

[0011] The thermoplastic resin included in the composite material of this disclosure is not particularly limited and may be, for example, a conventionally known thermoplastic resin. Examples include polyethylene resin, polypropylene resin, vinyl chloride resin, methacrylic resin, polystyrene resin, ABS resin, polycarbonate resin, polyacetal resin, polyamide resin, polysulfone resin, modified PPO resin, and polyester resin. From the viewpoint of obtaining a composite material of this disclosure that has excellent flowability when melted and thus superior moldability, and which can be obtained in terms of mechanical properties such as strength and elastic modulus, polyethylene resin and / or polypropylene resin are preferred, polypropylene-polyethylene copolymer is more preferred, and polypropylene resin is even more preferred. When a polypropylene-polyethylene copolymer is used as the thermoplastic resin, the composite material of this disclosure has high impact strength and superior mechanical strength.

[0012] The thermoplastic resin is preferably a random copolymer. When the thermoplastic resin is a random copolymer, the composite material of this disclosure has high impact strength and superior mechanical strength.

[0013] In the composite material of this disclosure, the thermoplastic resin may be of one type or may contain multiple types of thermoplastic resins.

[0014] The thermoplastic resin contained in the composite material of this disclosure preferably has an average weight molecular weight of 200,000 g / mol or less, more preferably 150,000 g / mol or less, and even more preferably 100,000 g / mol or less. In this case, the composite material of this disclosure has high fluidity and excellent moldability when molded.

[0015] The average weight molecular weight of the thermoplastic resin contained in the composite material of this disclosure shall be the value obtained by the following measurement. The average weight molecular weight of the thermoplastic resin shall be measured using an HCL-8321GPC / HT type high-temperature gel permeation chromatograph (Tosoh). The sample shall be weighed to a thermoplastic resin component of 20 mg, 20 mL of mobile phase for GPC measurement shall be added, and the sample shall be shaken at 145°C to dissolve it. The solution shall be thermally filtered through a 0.5 μm PTFE membrane filter to separate cellulose fibers, etc., and the filtrate shall be used for GPC measurement. The conditions for the high-temperature gel permeation chromatograph shall be set as follows. Temperature: 140°C; Mobile phase: o-dichlorobenzene (containing 0.025 wt% BHT); Flow rate: 1.0 mL / min; Injection volume: 0.4 mL; Detector: Differential refractometer (RI); Column calibration: Monodisperse PS (TSKgel standard polystyrene: Tosoh); Molecular weight calibration: Relative calibration method (PS conversion); Analysis software: Empower3 (Waters Japan)

[0016] <Fillers> The fillers contained in the composite material of this disclosure will be described. The filler content in the composite material of this disclosure is 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass. When the filler content in the composite material of this disclosure is 10% by mass or more, the strength of the molded article made from the composite material of this disclosure tends to increase. When the filler content in the composite material of this disclosure is 70% by mass or less, the moldability of the composite material of this disclosure is easily ensured.

[0017] The filler contains cellulose fibers and / or plant-derived materials. The filler may be cellulose fibers and / or plant-derived materials. Cellulose fibers are preferred as the filler because they have a low environmental impact.

[0018] Raw materials for cellulose fibers and plant-derived materials include wood, herbaceous plants, seed hairs, bamboo, and sugarcane. Wood includes coniferous trees such as pine, fir, spruce, hemlock, and cedar, and broad-leaved trees such as beech, birch, poplar, and maple. Herbaceous plants include hemp, flax, Manila hemp, ramie, straw, bagasse, and mitsumata. Seed hairs include cotton linters, bombax cotton, and kapok.

[0019] The cellulose fibers preferably have an average fiber diameter of 10 to 70 μm, more preferably 20 to 60 μm, and even more preferably 30 to 50 μm. In this case, the composite material of this disclosure has superior fluidity during melting, resulting in excellent moldability, and a molded product with excellent mechanical properties such as strength and elastic modulus can be obtained.

[0020] Preferably, all cellulose fibers contained in the filler have a fiber diameter of 10 to 70 μm, more preferably 20 to 60 μm, and even more preferably 30 to 50 μm. Furthermore, if, when the fiber diameter of the cellulose fibers contained in the composite material of this disclosure is measured by the method described later, no cellulose fibers of any other fiber diameter are detected, then all cellulose fibers contained in the filler are considered to be of that fiber diameter.

[0021] The cellulose fibers preferably have an average fiber length of 10 to 400 μm, more preferably 10 to 300 μm, and even more preferably 100 to 300 μm. In this case, the composite material of this disclosure has superior fluidity during melting, resulting in excellent moldability, and a molded product with excellent mechanical properties such as strength and elastic modulus can be obtained.

[0022] Preferably, all cellulose fibers contained in the filler have a fiber length of 10 to 400 μm, more preferably 10 to 300 μm, and even more preferably 100 to 300 μm. Furthermore, if, when the fiber length of the cellulose fibers contained in the filler is measured by the method described below, no cellulose fibers of other fiber diameters are detected, then all cellulose fibers contained in the filler are considered to be of that fiber length.

[0023] This document describes a method for measuring the average fiber diameter and average fiber length of cellulose fibers. First, the composite material of this disclosure is imaged using an X-ray CT analyzer, and the fiber diameter and fiber length of all cellulose fibers in the obtained image are measured. Then, the obtained fiber diameter and fiber length values ​​are simply averaged to obtain the average fiber diameter and average fiber length. The X-ray CT analyzer is used under the following observation conditions: Analyzer: Rigaku high-resolution 3DX X-ray microscope nano3DX Measurement conditions: X-ray source Cu (40kV, 30mA) Analysis software: Dragonfly Object Research Systems Image size: 347.7 × 763.2 μm Thickness: 654 μm

[0024] The fiber diameter and fiber length of the cellulose fibers can be adjusted not only by appropriately selecting the fiber diameter and fiber length of the cellulose fibers used as raw materials, but also by changing the rotation speed of the mixing means when mixing the filler and thermoplastic resin described later, the load applied by the screw pattern, or the blending ratio of the cellulose fibers.

[0025] <Organic Compounds Having Amino and / or Amide Groups> The organic compounds having amino and / or amide groups contained in the composite material of this disclosure will be described. The content of organic compounds having amino and / or amide groups in the composite material of this disclosure is 0.1 to 5.0% by mass, preferably 0.2 to 3.0% by mass, and more preferably 0.3 to 1.0% by mass. When the content of organic compounds having amino and / or amide groups in the composite material of this disclosure is 0.1% by mass or more, volatile organic compounds (VOCs) are easily captured. When the content of organic compounds having amino and / or amide groups in the composite material of this disclosure is 5.0% by mass or less, the strength of the molded article made from the composite material of this disclosure tends to increase.

[0026] Examples of organic compounds having an amino group include alkylamines, tetramethylenediamine, ethanolamine, piperidine, and methylamine. Examples of compounds having an amide group include 2-acrylamido-2-methylpropanesulfonic acid and adipic acid dihydrazide.

[0027] The organic compound having an amino group and / or an amide group is preferably an adipic acid dihydrazide, because it readily adsorbs volatile organic compounds (VOCs), particularly acetaldehyde.

[0028] <Basic Inorganic Compounds> The basic inorganic compounds contained in the composite material of this disclosure will be described. The content of basic inorganic compounds in the composite material of this disclosure is 0.1 to 15% by mass, more preferably 0.1 to 8.0% by mass, and even more preferably 0.2 to 4.0% by mass.

[0029] Examples of basic inorganic compounds include the following (a), (b), and (c): (a) hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide, magnesium hydroxide, and iron hydroxide; (b) basic oxides such as sodium oxide, magnesium oxide, and calcium oxide; (c) carbonates or bicarbonates such as sodium carbonate, sodium bicarbonate, and calcium carbonate.

[0030] The basic inorganic compound preferably contains magnesium hydroxide and / or a silicate compound. This is because, when the basic inorganic compound is a silicate compound, it acts as a catalyst, making it easier for organic compounds having amino and / or amide groups to adsorb volatile organic compounds (VOCs). It may be a silicate compound, and may be an aluminosilicate or a borosilicate.

[0031] In the composite material of this disclosure, the ratio of the content of an organic compound having an amino group and / or an amide group to the content of a basic inorganic compound (content of organic compound / content of inorganic compound) is 0.1 to 1.0, preferably 0.2 to 0.8, and more preferably 0.3 to 0.5. This is because when the value of this ratio is 0.1 or higher, the organic compound having an amino group and / or an amide group readily adsorbs volatile organic compounds (VOCs). When the value of this ratio is 1.0 or lower, the composite material of this disclosure is less likely to burn (discolor).

[0032] In the composite material of this disclosure, the ratio of the filler content to the content of the organic compound having an amino group and / or amide group (filler content / organic compound content) is preferably 10 to 680.

[0033] <Compatibilizer> The composite material of this disclosure may contain a compatibilizer. The compatibilizer content in the composite material of this disclosure is preferably 15% by mass or less, more preferably 0.5 to 6% by mass, and even more preferably 1 to 3% by mass.

[0034] When the composite material of this disclosure contains a compatible additive, it exhibits superior fluidity during melting, resulting in superior moldability and allowing for the production of molded products with superior mechanical properties such as strength and modulus of elasticity. Furthermore, when kneading the cellulose fibers with the thermoplastic resin, the cellulose fibers disperse easily within the thermoplastic resin, thus simplifying the manufacturing process.

[0035] The compatibilizer plays the role of dispersing relatively hydrophilic cellulose fibers within a relatively hydrophobic thermosetting resin. Therefore, the compatibilizer is preferably a block copolymer having nonpolar segments and polar segments.

[0036] The nonpolar segment is preferably an olefin-based segment. The olefin-based segment is a segment obtained by polymerization of an olefin monomer or copolymerization of an olefin monomer and a styrene monomer. Examples of olefin monomers include ethylene, propylene, methylpentene, butadiene, and norbornene derivatives. Only one type of olefin monomer may be used, or two or more types may be used.

[0037] The polar segment is preferably an ester-based segment or a styrene-based segment. The ester-based segment is a segment formed by the condensation polymerization of an alcohol-based monomer and an acid-based monomer.

[0038] Examples of alcohol-based monomers include α,ω-alkylenediols (C2-C12) such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol; polyalkylene glycols such as diethylene glycol, triethylene glycol, and dipropylene glycol; aliphatic dihydric alcohols such as 1,2-propanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol; glycerin, 1,1,1-tris(4-hydroxyphenyl)ethane, trimethylolethane, trimethylolpropane; monosaccharides, disaccharides, ring-opened sugars, and modified sugars. Polyhydric alcohols, bisphenols such as 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, and bis(4-hydroxyphenyl)diphenylmethane, as well as bisphenols whose hydroxyl groups have been modified with alkylene glycols such as polyethylene glycol and polypropylene glycol, and bisphenols whose aromatic rings have been hydrogenated, are used.

[0039] Examples of acidic monomers include saturated aliphatic carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and octyl succinic acid; unsaturated aliphatic carboxylic acids such as maleic acid, fumaric acid, and maleic anhydride; cyclic aliphatic carboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 2,3-bicyclo[2,2,1]dicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid; trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid anhydride, 1,2,4-butanetricarboxylic acid, 1,2,4-butanetricarboxylic acid anhydride, 2,5,7-naphthalentricarboxylic acid, 1,2,4-naphthalentricarboxylic acid, and 1,2,4-naphthalentricarboxylic acid anhydride; and polycarboxylic acids with a valency of three or more. Here, the carboxylic acid may be an acid halide, ester, or acid anhydride. Among these, maleic anhydride-modified polypropylene, which has been successfully modified while maintaining a high molecular weight, exhibits improved adhesion to fillers and, due to molecular-level entanglement, can enhance the strength of polyolefin-based composite materials.

[0040] Styrene-based segments are segments formed by the polymerization of styrene monomers or copolymerization of styrene monomers and acrylic monomers.

[0041] Examples of styrene monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylsterene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene.

[0042] Examples of acrylic monomers include n-butyl methacrylate, isobutyl methacrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diethylaminopropyl acrylate, 2-ethylhexyl acrylate, butyl acrylate-N-(ethoxymethyl)acrylamide, ethylene glycol methacrylate, 4-hexafluorobutyl methacrylate, and the like. These acrylic monomers may be used alone or in combination of two or more thereof. Further, these monomers may be modified.

[0043] Other monomers may be polymerized in the compatibilizer. Examples of the other monomers include vinyl monomers. For example, examples of vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl butyrate; examples of vinyl ether monomers include vinyl methyl ether, vinyl ethyl ether, and vinyl butyl ether; examples of vinyl ketone monomers include vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropenyl ketone; and examples of diene monomers include diene monomers such as isoprene and 2-chlorobutadiene.

[0044] The compatibilizer is preferably an acid-modified polyolefin resin modified with an unsaturated dicarboxylic acid, an acid-modified polyolefin resin modified with an acid anhydride of an unsaturated dicarboxylic acid, or a resin mixture containing both of these. This is because such a compatibilizer not only has good compatibility with the thermoplastic resin, but also improves the affinity (adhesion) between the thermoplastic resin and the cellulose fibers because the carboxylic acid groups of the compatibilizer bond with the OH groups of the cellulose fibers.

[0045] The compatibilizer is preferably selected according to the combination of the cellulose fibers and the thermoplastic resin.

[0046] <Other Components> The composite material of the present disclosure includes the above-mentioned thermoplastic resin, filler, organic compound having an amino group and / or an amide group, and a basic inorganic compound, may include a compatibilizer, and may further include components other than these (hereinafter also referred to as "other components").

[0047] Other components include organic components. These organic components can be anionic or nonionic surfactants and mixtures thereof that are soluble in water and water-soluble alcohols such as ethanol and methanol. Specifically, examples include stearic acid, oleic acid, glycerin, and their compounds. Stearic acid is the most abundant saturated fatty acid in animal and vegetable fats and is widely distributed naturally as a component of oils and fats. Specifically, examples of stearic acid include stearic acid, stearic acid amide, stearic acid ester, aluminum stearate, magnesium stearate, sodium stearate, calcium stearate, barium stearate, PEG stearate, PEG-glyceryl stearate, PG stearate, ascorbyl stearate, isocetyl stearate, glycol stearate, glyceride stearate, glyceryl stearate, cholesteryl stearate, diethanolamide stearate, and diethylaminoethyl stearate. Examples include amides, ethyl stearate, vinyl stearate, sucrose stearate, sorbitan stearate, sodium stearate, batyl stearate, butyl stearate, cetyl stearate, methyl stearate, hexyldecyl stearate, stearyl stearate, glycerol distearate, isohexadecyl stearate, glycerol monostearate, 12-hydroxystearic acid, 2-ethylhexyl stearate, glycerol monoisostearate, and N,N'-ethylenebisstearate amide.Specifically, examples of oleic acid include oleic acid, oleic anhydride, ethyl oleate, oleic acid esters, butyl oleate, methyl oleate, oleyl oleate, sodium oleate, glycidyl oleate, copper(II) oleate, cholesteryl oleate, glycerol dioleate, glyceryl monooleate, butyl oleate ester, propyl oleate ester, dibutylammonium oleate, potassium oleate, ethyl oleate ester, N,N-diethanololeamide, N,N-diethanololeamide, 4-methylumbelliferyl oleate, trimethylolpropane trioleate, sodium sulfosuccinimidyloleate, N,N'-ethylenebisoleamide, and 5-bromo-4-chloro-3-indoxyl oleate.Glycerin specifically refers to glycerin, diglycerin, PPG-9 diglyceryl, PPG-14 polyglyceryl-2 ether, diglycerin monocaprylate, POP(9) polyglyceryl ether, POP(14) polyglyceryl ether, POP(24) polyglyceryl ether, POE(13) polyglyceryl ether, POE(20) polyglyceryl ether, POE(30) polyglyceryl ether, POE(40) polyglyceryl ether, polyglycerin, glycerin fatty acid ester, polyglyceryl monoisostearate, polyglyceryl diisostearate, polyglyceryl monolaurate, decaglyceryl monomyristate, polyglyceryl monooleate, polyglyceryl monostearate, polyglyceryl distearate, and condensed polyglyceryl ricinoleate. Examples include diglyceryl tetraisostearate, polyglyceryl pentaisostearate, adipic acid, diethylene glycol, ethylhexylglycerin, octoxyglycerin, ozonated glycerin, cyclohexylglycerin, thioglycerin, disodium bisdioleoylglycerophosphoglycerin, hexylglycerin, polyglycerin-4, polyglycerin-6, polyglycerin-10, polyglycerin-20, polyglycerin fatty acid esters, diglycerin fatty acid esters, polyoxyethylene polyglyceryl ether, glycerin fatty acid esters, monoglycerides, acetylated monoglycerides, organic acid monoglycerides, medium-chain fatty acid monoglycerides, polyglycerin fatty acid esters, sorbitanic acid fatty acid esters, and propylene glycolic acid fatty acid esters.

[0048] The content of other components that the composite material of this disclosure may contain is preferably 10% by mass or less, and more preferably 5% by mass or less. The content of other components can be determined as the remainder after measuring the cellulose fibers, thermoplastic resin, and compatibilizer contained in the composite material of this disclosure as described above.

[0049] When heat is applied during the manufacturing of the composite material of this disclosure, acetaldehyde is generated from the filler (cellulose fibers, etc.). The generated acetaldehyde then reacts with an organic compound having an amino group and / or an amide group. As a result, a carbonyl derivative is generated. Therefore, the composite material of this disclosure contains a carbonyl derivative.

[0050] The carbonyl derivative content in the composite material of this disclosure is 1 to 15% by mass. The carbonyl derivative content in the composite material of this disclosure is determined by FT-IR analysis and the resulting IR spectrum. Further details will be explained later when describing the examples.

[0051] <Manufacturing Method> The manufacturing method of the composite material of this disclosure is not particularly limited, and it can be obtained by mixing the above-mentioned thermoplastic resin, filler, organic compound having an amino group and / or amide group, and basic inorganic compound, and optionally a compatibilizer and other components.

[0052] The composite material of this disclosure is preferably manufactured by the manufacturing method described below (hereinafter also referred to as the "manufacturing method of this disclosure"). The inventors believe that the composite material of this disclosure obtained by the manufacturing method of this disclosure has high moldability and mechanical strength due to its special structure.

[0053] The manufacturing method of the present disclosure is a method for obtaining a composite material of the present disclosure by kneading cellulose fibers as a filler, a thermoplastic resin, an organic compound having an amino group and / or an amide group, a basic inorganic compound, and optionally a compatibilizer and other components, wherein the kneading is such that, if only a thermoplastic resin is used, the average weight molecular weight of the thermoplastic resin before kneading is A (g / mol) and the average weight molecular weight of the thermoplastic resin after kneading is B (g / mol), then B / A is 0.28 to 0.68, and such kneading is applied to the kneading of cellulose fibers as a filler, a thermoplastic resin, an organic compound having an amino group and / or an amide group, a basic inorganic compound, and optionally a compatibilizer and other components to obtain a composite material of the present disclosure.

[0054] The manufacturing method of the present disclosure described above involves spraying water onto cellulose fibers, then crushing them, and contacting them with a molten compatibilizer to adhere the compatibilizer to the small pieces of cellulose fibers. Subsequently, these are kneaded together with a thermoplastic resin, an organic compound having amino and / or amide groups, a basic inorganic compound, and other components as needed to obtain the composite material of the present disclosure. The kneading is such that, if only the thermoplastic resin is used for kneading, the average weight molecular weight of the thermoplastic resin before kneading is A (g / mol) and the average weight molecular weight of the thermoplastic resin after kneading is B (g / mol), then B / A is 0.28 to 0.68. Preferably, such kneading is applied to the kneading of cellulose fibers as fillers, a thermoplastic resin, an organic compound having amino and / or amide groups, a basic inorganic compound, and, as needed, a compatibilizer and other components to obtain the composite material of the present disclosure.

[0055] In the manufacturing method disclosed herein, the average gravimetric molecular weights A and B of the thermoplastic resin before and after kneading are determined by measuring the average gravimetric molecular weight of the thermoplastic resin using an HCL-8321GPC / HT type high-temperature gel permeation chromatograph (Tosoh). The sample was weighed to a total of 20 mg of thermoplastic resin (PP) component, 20 mL of mobile phase for GPC measurement was added, and the mixture was shaken at 145°C to dissolve it. The solution was thermally filtered through a 0.5 μm PTFE membrane filter, and the filtrate was used for GPC measurement. The conditions for the high-temperature gel permeation chromatograph were set as follows. Temperature: 140°C; Mobile phase: o-dichlorobenzene (containing 0.025 wt% BHT); Flow rate: 1.0 mL / min; Injection volume: 0.4 mL; Detector: Differential refractometer (RI); Column calibration: Monodisperse PS (TSKgel standard polystyrene: Tosoh); Molecular weight calibration: Relative calibration method (PS conversion); Analysis software: Empower3 (Waters Japan)

[0056] The manufacturing method described above in this disclosure may specifically be the following manufacturing method X. In other words, the manufacturing method X described below may be the manufacturing method described in this disclosure.

[0057] In manufacturing method X, it is preferable to crush (including disintegration; the same applies hereinafter) the pulp to obtain pulp fragments. These pulp fragments then become cellulose fibers. In other words, the cellulose fiber content in the resulting composite material of this disclosure is equal to the amount of pulp added.

[0058] The method for crushing pulp into pulp fragments is not particularly limited. Examples include crushing methods using grinders such as hammer mills, cutter mills, or jet mills, and methods using mixers such as Henschel mixers, super mixers, or ribbon mixers.

[0059] It is preferable to spray water onto the pulp before grinding, or to grind the pulp while spraying water onto it. This is because spraying water makes the pulp easier to break down.

[0060] The size of the pulp fragments obtained by crushing the pulp is not particularly limited. To facilitate mixing and shorten the kneading time, it is preferable that the longest diameter of the pulp fragments be 10 to 50 mm.

[0061] In manufacturing method X, it is preferable to knead a thermoplastic resin, an organic compound having an amino group and / or an amide group, a basic inorganic compound, and pulp fragments and / or cellulose fibers obtained by crushing pulp fragments. Further compatibility agents and / or other components may be added and kneaded together.

[0062] Here, pulp may be fed into a crusher or mixer as described above to break it into pulp fragments, then a compatibilizer may be added, the compatibilizer may be melted, and the pulp fragments and compatibilizer may be mixed. After that, a thermoplastic resin, an organic compound having amino and / or amide groups, and a basic inorganic compound may be added and kneaded. If the compatibilizer is added before adding the thermoplastic resin, the organic compound having amino and / or amide groups, and the basic inorganic compound, and the compatibilizer is melted and kneaded with the pulp fragments, the melted compatibilizer will adhere to the cellulose fibers formed from the loosened pulp fragments. As a result, the moldability and mechanical strength of the composite material of the present disclosure obtained by the manufacturing method of the present disclosure tend to be increased.

[0063] Next, the cellulose fibers (or cellulose fibers with a compatibilizer attached), the thermoplastic resin, the organic compound having an amino group and / or an amide group, and the basic inorganic compound are kneaded at a temperature above the melting point of the thermoplastic resin, specifically at a kneading temperature 10 to 50°C higher than the melting point of the thermoplastic resin. Let this kneading time be Y1. Subsequently, the mixture is kneaded at a kneading temperature 50 to 80°C lower than the melting point of the thermoplastic resin. Let this kneading time be Y2. Subsequently, the mixture is kneaded at a kneading temperature of 30°C or lower. Let this kneading time be Y3.

[0064] The ratio of the above-mentioned mixing times Y1, Y2, and Y3 (Y1:Y2:Y3) is preferably 35-40:50-55:5-15. In this case, the composite material of this disclosure has superior fluidity during melting, resulting in better moldability.

[0065] Here, the melting point of the thermoplastic resin is determined by using a differential thermogravimetric thermometer (TG-DSC, manufactured by Hitachi High-Tech Science Corporation) and identifying the endothermic peak. The specific measurement conditions were as follows: First, a sample with a thickness of 0.2 mm was molded; Step 1: The temperature was raised to 240°C at a rate of 30°C / min and held for 10 minutes; Step 2: The temperature was lowered to 30°C at a rate of 10°C / min; Step 3: The temperature was raised to 240°C at a rate of 10°C / min. The endothermic peak at the third step was taken as the melting point.

[0066] The mixing temperature is the value obtained by measuring the temperature of the discharge port of the mixing equipment (mixer) using a temperature sensor.

[0067] The mixing method is not particularly limited, and examples include methods using a twin-screw extruder, a Banbury mixer, or a pressure roller.

[0068] When performing such an operation, namely kneading at a temperature above the melting point of the thermoplastic resin, followed by kneading at a temperature 50 to 80°C below the melting point of the thermoplastic resin, and then kneading at a temperature of 30°C or lower, using only thermoplastic resin, the ratio B / A tends to be between 0.28 and 0.68, where A (g / mol) is the average weight molecular weight of the thermoplastic resin before kneading and B (g / mol) is the average weight molecular weight of the thermoplastic resin after kneading.

[0069] Such a manufacturing method X may fall under the manufacturing method of the present disclosure.

[0070] The composite material of the present disclosure obtained by such a manufacturing method of the present disclosure may be further granulated. The shape of the granulated body (pellets) obtained by granulation is not particularly limited. For example, it may be particulate, cylindrical, polygonal prismatic, etc.

[0071] One granulation method involves extruding the composite material of this disclosure from a die using an extruder and cutting it into pellets with a rotating blade under air cooling. The cutting length of the pellets can be changed by adjusting the rotation speed of the rotating blade.

[0072] The composite material of this disclosure, which is in the form of a granulated body (pellet), can be molded using a mold such as an injection mold.

[0073] <Molded articles> Examples of molded articles made from the composite material of this disclosure include molded parts for vehicles, equipment, and devices having fine or complex structures, industrial materials such as containers, pallets, plastic cores, and building materials, daily necessities, and general merchandise.

[0074] The content of each component in the molded article of this disclosure may be the same as that of the composite material of this disclosure. The method for measuring the content of carbonyl derivatives will be described later when describing the examples.

[0075] When heat is applied during the manufacturing of the composite material of this disclosure, acetaldehyde is generated from the filler (cellulose fibers, etc.). The generated acetaldehyde then reacts with an organic compound having an amino group and / or an amide group. As a result, a carbonyl derivative is generated. Therefore, the composite material of this disclosure contains a carbonyl derivative.

[0076] A molded article made from the composite material of this disclosure preferably contains 1 to 15% by mass of a carbonyl derivative.

[0077] Using the composite material of this disclosure, a molded article of this disclosure can be obtained, for example, by a conventionally known molding method.

[0078] This disclosure includes the following (1) to (6): (1) A thermoplastic resin composite material comprising a thermoplastic resin, a filler, an organic compound having an amino group and / or an amide group, and a basic inorganic compound, wherein the content of the filler is 10 to 70% by mass, the content of the organic compound is 0.1 to 5.0% by mass, and the ratio of the content of the organic compound to the content of the inorganic compound (content of organic compound / content of inorganic compound) is 0.1 to 1.0. (2) The thermoplastic resin composite material according to (1) above, wherein the ratio of the content of the filler to the content of the organic compound (content of filler / content of organic compound) is 10 to 680. (3) The thermoplastic resin composite material according to (1) or (2) above, wherein the filler comprises cellulose fibers. (4) The thermoplastic resin composite material according to any one of (1) to (3) above, wherein the organic compound comprises adipic acid dihydrazide. (5) The thermoplastic resin composite material according to any one of (1) to (4) above, wherein the inorganic compound comprises magnesium hydroxide and / or a silicate compound. (6) The thermoplastic resin composite material according to any one of (1) to (5) above, comprising 1 to 15% by mass of a carbonyl derivative.

[0079] The present disclosure will be explained below using examples. The present disclosure is not limited to these examples.

[0080] In each of the examples and comparative examples, the thermoplastic resins, fillers, organic compounds having amino and / or amide groups, basic inorganic compounds, and phase solvents shown in Tables 1 and 2 were prepared. Specifically, they were as follows: • Thermoplastic resins: polypropylene, polyethylene, polypropylene-polyethylene copolymer • Fillers: cellulose fibers (average fiber diameter: 200 μm, average fiber diameter: 30 μm), wood flour (average fiber diameter: 200 μm, average fiber diameter: 50 μm) • Organic compounds having amino and / or amide groups: adipic acid dihydrazide, methylamine, 2-acrylamido-2-methylpropanesulfonic acid • Basic inorganic compounds: aluminosilicate, borosilicate, sodium hydroxide, magnesium oxide, calcium carbonate • Compatibilizers: maleic anhydride-modified polypropylene, silane-modified polypropylene

[0081] In the following, "organic compounds having an amino group and / or an amide group" (including in the table) will also be referred to as "organic compounds," and "basic inorganic compounds" will also be referred to as "inorganic compounds."

[0082] Next, water was sprayed onto the filler material, and then it was placed into a Henschel mixer. The filler material was then crushed into small pieces.

[0083] Next, the specified compatibilizer was added to the Henschel mixer, and the filler and compatibilizer were mixed together, with the temperature inside the Henschel mixer set to the temperature at which the compatibilizer melts. The compatibilizer was then thoroughly coated onto the filler.

[0084] Next, the specified thermoplastic resin, organic compound, and inorganic compound were fed into a twin-screw extruder. Then, a mixture of filler and compatibilizer was fed into the twin-screw extruder, and the thermoplastic resin, organic compound, inorganic compound, filler, and compatibilizer were kneaded together.

[0085] Here, first, the temperature inside the twin-screw extruder was adjusted to be 10 to 50°C higher than the melting point of the thermoplastic resin, and mixing was performed. Let this mixing time be y1. Next, the temperature inside the twin-screw extruder was adjusted to be 50 to 80°C lower than the melting point of the thermoplastic resin, and mixing was performed. Let this mixing time be y2. Next, mixing was performed with the temperature inside the twin-screw extruder below 30°C. Let this mixing time be y3. The ratio of the above mixing times y1, y2, and y3 (y1:y2:y3) satisfied the requirements of 35-40:50-55:5-15.

[0086] If such mixing is performed using only thermoplastic resin, and the average weight molecular weight of the thermoplastic resin before mixing is A (g / mol), and the average weight molecular weight of the thermoplastic resin after mixing is B (g / mol), then B / A will be between 0.28 and 0.68.

[0087] By this method, thermoplastic resin composites were obtained in each of the examples and comparative examples. In each of the examples and comparative examples, acetaldehyde is generated from the cellulose fibers during kneading in a twin-screw extruder. The generated acetaldehyde then reacts with the organic compound to produce a carbonyl derivative. Therefore, the thermoplastic resin composites obtained in each of the examples and comparative examples contain a carbonyl derivative in addition to the thermoplastic resin, organic compound, inorganic compound, filler, and compatibilizer.

[0088] In principle, the thermoplastic resin, filler, and compatibilizer in the thermoplastic resin composites obtained in each of the examples and comparative examples do not react with other components. Therefore, the respective content of each component in the thermoplastic resin composite was calculated from the amount added. The content of each component, such as organic compounds, inorganic compounds, and carbonyl derivatives, was determined as follows. Furthermore, the content of each component is almost the same in the composite material and the molded article. The content of each component in the composite material and the molded article is shown in Tables 1 and 2.

[0089] <Organic compounds, inorganic compounds, carbonyl derivatives> FT-IR analysis was performed under the following conditions, and the content of each component was measured from the obtained IR spectrum. Instrument: Nicolet iN10 MX (Thermo SCIENTIFIC) Resolution: 4cm -1 Number of measurements: 16 Measurement wavefrequency range: 4000 cm -1 ~650cm -1 Detector: MCT Measurement method: Transmission method

[0090] For each of the thermoplastic resin composite materials obtained in the examples and comparative examples, dumbbell test specimens were prepared, and their odor characteristics, burn (discoloration), and mechanical strength were evaluated using the following method. The results are shown in Tables 1 and 2.

[0091] <Method for preparing dumbbell test specimens> Dumbbell test specimens (Type A1) for bending tests were prepared using an injection molding machine (J80ADS, manufactured by Japan Steel Works, Ltd.). The molding conditions for the test specimens were kept constant at a mold temperature of 25°C, an injection speed of 30 mm / s, and a holding pressure of 35 MPa, but the cylinder temperature setting was changed. Molding was performed at a cylinder temperature of 185°C or higher and less than 195°C. If molding was not possible under these conditions, the overall evaluation of the sample was given a rating of D.

[0092] <Odor Characteristics Evaluation (VOCs)> - VOC Sampling Method: In accordance with the sampling bag method (JASO M 902:2011), two dumbbell test pieces obtained under the above molding conditions were sealed in Smart Bag 2F (capacity 10L) washed with nitrogen gas to collect by solid phase adsorption (DNPH cartridge), and 5 ± 0.2 L of nitrogen gas was filled. Next, this Smart Bag 2F was left in an oven maintained at 65°C for 2 hours, and the gas inside the bag was collected in a DNPH cartridge. DNPH cartridge sampling was performed with a gas suction flow rate of 0.75 L / min, suction time of 4 minutes, and gas collection volume of 3 L.

[0093] Measurement Method: Derivatized components were collected from the DNPH cartridge using the sample ring described above, and solvent desorption was performed with acetonitrile to obtain an extract. This extract was used as the measurement solution, and quantification was performed using a high-performance liquid chromatograph as follows: Analytical instrument: HPLC 1200 Series (Agilent Technologies) Column: ZORBAX Eclipse XDB-C18 5-Micron Solvent: Water, acetonitrile Injection volume: 30 μl Column temperature: 40°C DAD: 360 nm

[0094] • Evaluation Method: The quantitative value of VOC (acetaldehyde) in the sample is expressed in μg / g. A: Less than 0.010 μg / g B: 0.010 μg / g or more and less than 0.015 μg / g C: 0.015 μg / g or more and less than 0.020 μg / g D: 0.02 μg / g or more

[0095] <Evaluation of Burning (Discoloration)> The density of the dumbbell test pieces formed as described above was measured using a spectrophotometer (X-rite). The density values ​​were evaluated as follows: A: Less than 1.00 B: 1.00 or more and less than 1.25 C: 1.25 or more and less than 1.50 D: 1.50 or more

[0096] <Method for Evaluating Mechanical Strength> The flexural modulus was measured in accordance with ISO 178. The flexural modulus of each dumbbell-shaped test specimen obtained above was measured using an Instron-type material testing machine (Shimadzu Corporation: Autograph AG25 TA). The values ​​of the flexural modulus were then evaluated as follows: A: 2500 MPa or more B: 2000 MPa or more and less than 2500 MPa C: 1500 MPa or more and less than 2000 MPa D: Less than 1500 MPa

[0097] <Criteria for Overall Evaluation> Based on the evaluation of odor characteristics, burn (discoloration), and mechanical strength as described above, the overall evaluation was conducted as follows: • If all are A → A • If even one is B → B • If even one is C → C • If even one is D → D

[0098]

[0099]

[0100] This application claims priority based on Japanese Patent Application No. 2025-38621, filed on 11 March 2025, and incorporates all of its disclosures herein.

Claims

1. A thermoplastic resin composite material comprising a thermoplastic resin, a filler, an organic compound having an amino group and / or an amide group, and a basic inorganic compound, wherein the filler content is 10 to 70% by mass, the organic compound content is 0.1 to 5.0% by mass, and the ratio of the organic compound content to the inorganic compound content (organic compound content / inorganic compound content) is 0.1 to 1.

0.

2. The thermoplastic resin composite material according to claim 1, wherein the ratio of the content of the filler to the content of the organic compound (content of filler / content of organic compound) is 10 to 680.

3. The thermoplastic resin composite material according to claim 1 or 2, wherein the filler comprises cellulose fibers.

4. The thermoplastic resin composite material according to any one of claims 1 to 3, wherein the organic compound comprises adipic acid dihydrazide.

5. The thermoplastic resin composite material according to any one of claims 1 to 4, wherein the inorganic compound comprises magnesium hydroxide and / or a silicate compound.

6. A thermoplastic resin composite material according to any one of claims 1 to 5, comprising 1 to 15% by mass of a carbonyl derivative.

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