TWI689541B - Resin composition and synthetic wood using the same - Google Patents

Abstract

An object of the present invention is to provide a synthetic wood in which resin and natural fibers are uniformly dispersed and excellent in balance of workability, appearance, tensile strength, bending strength, impact resistance, thermal stability, and the like. In order to solve the above problem, a resin composition containing at least one resin (A) selected from thermoplastic resins and thermosetting resins, a compatibilizer (B), and natural fibers (C) is used, and when When the total of the resin (A) and the natural fiber (C) is 100 parts by weight, the resin (A) is contained at a ratio of 1 part by mass to 90 parts by mass, and at 10 parts by mass to 99 parts by mass The natural fiber (C) is contained in a ratio, and the compatibilizer (B) is contained in a ratio of 0.1 to 50 parts by mass.

Description

Resin composition and synthetic wood using the same

The present invention relates to a resin composition having a specific composition and synthetic wood obtained from the resin composition.

Previously, as a composition for synthetic wood, a composition containing wood powder and thermoplastic resins such as polyethylene and polypropylene has been known. The composition for synthetic wood is formed into a target shape by a molding method such as extrusion molding or injection molding to obtain synthetic wood.

However, when the synthetic wood composition is molded to produce synthetic wood, wood powder may be burnt due to heat during molding, resulting in a poor appearance of the synthetic wood. In addition, if a fluidity-improving material such as wax is added to a composition for synthetic wood, the fluidity of the composition is improved, and the molding temperature can be lowered. Therefore, the occurrence of scorch as described above can be prevented. On the other hand, synthetic wood exists The surface is sticky, etc. On the other hand, Patent Document 1 discloses that by using a specific wax, a composition for synthetic wood that obtains a synthetic wood with good appearance and little stickiness on the surface. However, there are higher requirements in terms of the uniform dispersion of resin and wood flour, the appearance and mechanical strength of the obtained synthetic wood.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-026886

[Patent Document 2] Japanese Patent Laid-Open No. 2002-138202

In view of the aforementioned prior art, an object of the present invention is to provide a synthetic wood for obtaining a resin and natural fibers uniformly dispersed, and having excellent balance of workability, appearance, tensile strength, bending strength, impact resistance, thermal stability, etc. Resin composition.

The inventors of the present invention have made intensive studies to solve the above-mentioned problems. As a result, they discovered that by using a resin composition having a specific composition, the above-mentioned problems can be solved, and the present invention has been completed.

That is, the present invention relates to the following [1] to [22].

[1] A resin composition comprising: at least one resin (A) selected from a thermoplastic resin and a thermosetting resin, a compatibilizer (B), and a natural fiber (C), and when the resin ( A) When the total amount with the natural fiber (C) is 100 parts by weight, the resin (A) is contained in a ratio of 1 part by mass to 90 parts by mass, and the resin is contained in a ratio of 10 parts by mass to 99 parts by mass. Natural fiber (C), and the compatibilizer (B) is contained in a ratio of 0.1 to 50 parts by mass.

[2] The resin composition according to [1], wherein the compatibilizer (B) is a polyolefin wax (B1) or a petroleum resin (B2) that satisfies the following (i) to (iv).

(i) The polystyrene-converted number-average molecular weight (Mn) measured by Gel Permeation Chromatography (GPC) is in the range of 300 to 20,000

(ii) The softening point measured according to JIS K2207 is in the range of 70℃~170℃

(iii) The density measured by the density gradient tube method is in the range of 830kg/m ³ ~1200kg/m ³

(iv) The ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) measured by gel permeation chromatography (GPC) is 7.0 or less

[3] The resin composition according to [1] or [2], wherein the compatibilizer (B) is a polyolefin wax (B1).

[4] The resin composition according to [2] or [3], wherein the polyolefin wax (B1) is selected from the group consisting of ethylene homopolymer, propylene homopolymer, ethylene, and alpha 3 to 12 carbon atoms -Modification of unsaturated carboxylic acid derivative monomers of at least one polymer in the group consisting of copolymers of olefins and copolymers of propylene and α-olefins having 4 to 12 carbon atoms, Modified styrene or air oxide of the copolymer.

[5] The resin composition according to [4], wherein the polyolefin wax (B1) is an unsaturated carboxylic acid derivative monomer modification of the polymer or an air oxide of the polymer, and The acid value is 1mgKOH/g~100mgKOH/g.

[6] The resin composition according to [4], wherein the polyolefin wax (B1) is an unsaturated carboxylic acid derivative monomer modification of the polymer or an air oxide of the polymer, and The acid value is 30mgKOH/g~87mgKOH/g.

[7] The resin composition according to [4], wherein the polyolefin wax (B1) is an unsaturated carboxylic acid derivative monomer modification of the polymer or an air oxide of the polymer, and The acid value is 40mgKOH/g~100mgKOH/g.

[8] The resin composition according to [1] or [2], wherein the compatibilizer (B) contains two or more compounds, and among the two or more compounds, the highest softening point is compatible The difference between the softening point of the agent (BH) and the compatibilizer (BL) with the lowest softening point is 5°C or higher.

[9] The resin composition as described in [1] or [2], wherein the compatibilizer (B) contains two or more compounds, and among the two or more compounds, the highest softening point is compatible The difference between the softening point of the agent (BH) and the compatibilizer (BL) with the lowest softening point is 20°C or higher.

[10] The resin composition according to [8] or [9], wherein the compatibilizer (BH) and the compatibilizer (BL) are polyolefin wax (B1).

[11] The resin composition according to [8] or [9], wherein the compatibilizer (BH) is an unsaturated carboxylic acid derivative monomer modification of the polymer or air of the polymer Oxide, and the acid value is 60mgKOH/g~90mgKOH/g.

[12] The resin composition according to any one of [2] to [11], wherein the polyolefin wax (B1) is converted to polystyrene measured by gel permeation chromatography (GPC) The number average molecular weight (Mn) is in the range of 6000-12000.

[13] The resin composition according to any one of [2] to [12], wherein the Mw/Mn of the polyolefin wax (B1) is 5.0 or less.

[14] The resin composition according to any one of [1] to [13], wherein the melting point (Tm) of the resin (A) measured using a differential scanning calorimeter (DSC) is Below 250°C or not observed.

[15] The resin composition according to any one of [1] to [14], wherein the density of the resin (A) measured according to the density gradient tube method is between 830 kg/m ³ and 1800 kg/m ³ Within range.

[16] The resin composition according to any one of [1] to [15], wherein the resin (A) has a bending elastic coefficient of 1 MPa to 10000 MPa.

[17] The resin composition according to any one of [1] to [16], wherein the resin (A) is selected from an olefin-based polymer, polystyrene, and acrylonitrile. Butadiene. At least one resin in the group consisting of acrylonitrile butadiene styrene resin (ABS resin) and polyvinyl chloride.

[18] The resin composition according to any one of [1] to [17], wherein the natural fiber (C) is selected from the group consisting of wood flour, wood fiber, bamboo, cotton, cellulose and nanocellulose At least one fiber in the group consisting of fibers.

[19] The resin composition according to any one of [1] to [18], wherein the melt flow rate (MFR) measured at 230°C and a test load of 10 kgf according to JIS K7210 is 0.01 g/10min~100g/10min.

[20] The resin composition according to any one of [1] to [19], wherein the resin (A) and the resin are used in a batch-plastomill The maximum torque performance time when the compatibilizer (B) and the natural fiber (C) are kneaded is set to T2, and only the resin (A) and the natural fiber will be made using a batch Plastow mill (C) When the maximum torque expression time during kneading is T1, the ratio of T1 to T2 (T1/T2) is 0.5 or more.

[21] A synthetic wood obtained by molding the resin composition according to any one of [1] to [20].

[22] The synthetic wood according to [21], which is a wooden deck or floor board.

In the resin composition of the present invention, the resin and natural fibers are uniformly dispersed. Therefore, according to the resin composition, a synthetic wood excellent in balance of workability, appearance, tensile strength, bending strength, impact resistance, thermal stability, etc. is provided. In addition, since the processability of the resin composition is high, the resin composition can be efficiently formed, or the synthetic wood can be efficiently processed. Furthermore, it is possible to improve the low-temperature formability of synthetic wood, reduce the defect rate due to scorching, and the like. In addition, since the resin composition has high mechanical properties, it is also possible to reduce the weight of the molded article, improve the workability, improve the designability, and suppress the deterioration of water resistance.

FIG. 1 is a photograph of the appearance of strands produced in Examples and Comparative Examples.

Hereinafter, the resin composition of the present invention and the synthetic wood obtained therefrom will be described in detail.

A. Resin composition

The resin composition of the present invention contains at least one resin (A) selected from thermoplastic resins and thermosetting resins, a compatibilizer (B), and natural fibers (C).

When the total of the resin (A) and the natural fiber (C) is 100 parts by weight, the amount of the resin (A) is 1 part by mass to 90 parts by mass, preferably 10 Mass parts to 80 parts by mass, more preferably 25 parts to 75 parts by mass. When tensile strength, bending strength, and heat resistance are required for the molded product of the resin composition, the upper limit is preferably 70 parts by mass, more preferably 60 parts by mass, and particularly preferably 55 parts by mass. In addition, when impact resistance, flexibility, grip, and impact absorption are required for the molded product of the resin composition, the lower limit is preferably 30 parts by mass, more preferably 55 parts by mass, and particularly preferably 60 parts by mass Copies.

When the total of the resin (A) and the natural fiber (C) is 100 parts by weight, the amount of the natural fiber (C) is 10 parts by mass to 99 parts by mass, preferably 20 parts by mass. 90 parts by mass, more preferably 25 parts by mass to 75 parts by mass. When the molded product of the resin composition requires tensile strength, bending strength, and heat resistance, the lower limit is preferably 30 parts by mass, more preferably 40 parts by mass, and particularly preferably 45 parts by mass. In addition, when impact resistance, flexibility, grip, and impact absorption are required for the molded product of the resin composition, the upper limit is preferably 70 parts by mass, more preferably 45 parts by mass, and particularly preferably 40 parts by mass Copies.

In addition, when the total of the resin (A) and the natural fiber (C) is 100 parts by weight, the amount of the compatibilizer (B) is 0.1 to 50 parts by mass, preferably 0.1 Mass parts to 20 parts by mass, more preferably 0.2 parts by mass to 9 parts by mass, particularly preferably 0.3 parts by mass to 7 parts by mass, particularly preferably 0.4 parts by mass to 5 parts by mass, most preferably 1 parts by mass to 3 parts by mass .

In addition, when the total of the resin (A) and the compatibilizer (B) is 100 parts by weight, the amount of the resin (A) is preferably 50 parts by mass to 99.9 parts by mass, more preferably 80 parts by mass to 99.9 parts by mass, particularly preferably 91 parts by mass to 99.8 parts Mass parts, particularly preferably from 93 parts by mass to 99.7 parts by mass, best from 95 parts by mass to 99.6 parts by mass. On the other hand, when the total amount of the resin (A) and the compatibilizer (B) is 100 parts by weight, the amount of the compatibilizer (B) is preferably 0.1 to 50 parts by mass It is more preferably 0.1 to 20 parts by mass, particularly preferably 0.2 to 9 parts by mass, particularly preferably 0.3 to 7 parts by mass, and most preferably 0.4 to 5 parts by mass. In addition, when the total of the resin (A) and the compatibilizer (B) is 100 parts by weight, the amount of the natural fiber (C) is preferably 1 part by mass to 300 parts by mass, more preferably It is 1 part by mass to 150 parts by mass, particularly preferably 50 parts by mass to 150 parts by mass, and particularly preferably 70 parts by mass to 120 parts by mass.

Generally, when the amount of the compatibilizing agent (B) is increased, the processability of the resin composition is improved, but if the amount is excessive, there is a tendency that kneadability or heat resistance stability deteriorates. On the other hand, if the compatibilizer (B) is contained in the above ratio, the balance between the kneadability and processability of the resin (A) and the natural fiber (C) becomes good. Specifically, not only the mixing or processing of the resin composition becomes easy, but also the influence of fumes or odor generated during the molding process on the molding working environment is small, and the eye mucus (adhesion with the molding time elapses There is also little generation of burnt resin (burnt resin, low-molecular-weight substances, additives, etc.) accumulated near the exit of the forming machine such as a die lip, or thermal deterioration such as burnt. Furthermore, since the dispersibility of the natural fiber (C) is improved, it is preferable in that it has little influence on appearance and the balance between mechanical strength and heat resistance becomes good.

In addition, if the amount of the natural fiber (C) is in a relatively small range, it is difficult for sludge to remain after combustion. In addition, in the above case, the natural fiber (C) functions as a modifier or a reinforcing agent for the resin (A) and the compatibilizer (B). another On the one hand, by setting the natural fiber (C) to 10 parts by mass or more with respect to the total of 100 parts by mass of the resin (A) and the natural fiber (C), a resin composition excellent in balance between mechanical strength and heat resistance can be obtained .

Hereinafter, each component and each requirement will be described.

1. Resin (A)

The resin (A) is at least one resin selected from thermoplastic resins and thermosetting resins. These resins may be used alone or in combination of two or more. The definitions and manufacturing methods of thermoplastic resins or thermosetting resins are well known, and are described in publications such as "Practical Plastic Encyclopedia" (edited by the Editorial Committee of Practical Plastic Encyclopedia, issued by the Industrial Survey Association). In the present invention, the resin (A) is more preferably a thermoplastic resin.

1-1. Thermosetting resin

Examples of thermosetting resins include polyurethanes, epoxy resins, thermosetting unsaturated polyester resins, urea resins, melamine resins and phenol resins, and mixed resins of these. Among these resins, (1) epoxy resin, (2) thermosetting unsaturated polyester resin, and (3) phenol resin are preferable. Preferred examples of these resins are shown below. In the following description, the thermosetting resin before thermosetting is described.

(1) Epoxy resin

The epoxy resin is typically a resin obtained by reacting an aromatic diol (for example, bisphenol A) and epichlorohydrin in the presence of a base. In the present invention, bisphenol A type epoxy resin, bisphenol F type epoxy resin, or bisphenol S type epoxy resin having an epoxy equivalent of 170 to 5000 is preferred. Such epoxy resins are already commercially available, for example Product names Epomik (Mitsui Chemical Co., Ltd.), Epiclon (Dainippon Ink Chemical Industry Co., Ltd.), Sumiepoxy (Sumitomo Chemical Co., Ltd.), etc., These commercial products can be preferably used in the present invention.

(2) Thermosetting unsaturated polyester resin

The thermosetting unsaturated polyester resin is typically a resin obtained by esterifying an aliphatic unsaturated dicarboxylic acid and an aliphatic diol. In the present invention, a resin obtained by esterifying an unsaturated dicarboxylic acid such as maleic acid or fumaric acid with a glycol such as ethylene glycol or diethylene glycol is preferred. Such thermosetting unsaturated polyester resins are commercially available, and for example, trade names such as Rigolac (Showa Polymer Co., Ltd.), Sumicon (Sumitomo Bakelite) (Sumitomo Bakelite) ( Shares)) etc., these commodities can be preferably used in the resin composition of the present invention.

(3) Phenolic resin

In the present invention, the phenol resin includes any of the so-called novolak type and the novolak type, but the phenol resin used in the resin composition of the present invention is preferably a novolak hardened with hexamethylenetetramine. Type resin or solid phenolic resin with dimethylene ether bond as the main body. Such phenol resins are already commercially available, for example, the trade name Sumicon PM (Sumitomo Bakelite (share)), Nikkaline (Japan Synthetic Chemical Industry (share)), etc. These products can be used in the present invention.

1-2. Thermoplastic resin

Representatives of thermoplastic resins include the following (1) to (16). These resins may be used alone or in combination of two or more.

(1) Olefin polymer

(2) Polyamide

(3) Polyester

(4) Polyacetal

(5) Polystyrene, acrylonitrile-butadiene-styrene resin, acrylonitrile-acrylic rubber-styrene resin, acrylonitrile-ethylene rubber-styrene resin, (meth)acrylate-styrene resin, benzene Styrene-based resins such as ethylene-butadiene-styrene resin

(6) Acrylic resins such as polymethyl methacrylate or polyethyl methacrylate

(7) Polycarbonate

(8) Polyphenylene oxide

(9) Chlorine resins such as polyvinyl chloride and polyvinylidene chloride

(10) Vinyl acetate resins such as polyvinyl acetate and ethylene-vinyl acetate resin

(11) Ethylene-(meth)acrylate copolymer

(12) Ethylene-acrylic resin, ethylene-methacrylic resin, or these ionomer resins

(13) Vinyl alcohol resins such as polyvinyl alcohol and ethylene-vinyl alcohol resin

(14) Cellulose resin

(15) Thermoplastic elastomers such as vinyl chloride-based elastomers, urethane-based elastomers, polyester-based elastomers

(16) Various copolymer rubbers

Next, specific examples are given for various thermoplastic resins.

(1) Olefin polymer

Examples of olefin-based polymers include homopolymers of olefins such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and polymethylbutene; ethylene-α-olefin random copolymerization Materials, propylene-ethylene random copolymers, ethylene. α-olefin. Non-conjugated polyene copolymer, 4-methyl-1-pentene. Olefin copolymers such as α-olefin copolymers.

The olefin-based polymer can be, for example, an ethylene (co)polymer. The ethylene (co)polymer is preferably an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms. Specific examples of the ethylene homopolymer include ultrahigh molecular weight polyethylene, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, and the like.

On the other hand, when the ethylene (co)polymer is a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, the amount of the structural unit (a) derived from ethylene is preferably 91.0 mol% ~99.9 mol%, more preferably 93.0 mol% to 99.9 mol%, particularly preferably 95.0 mol% to 99.9 mol%, and particularly preferably 95.0 mol% to 99.0 mol%. On the other hand, the amount of the structural unit (b) derived from an α-olefin having 3 or more carbon atoms is preferably 0.1 mol% to 9.0 mol%, more preferably 0.1 mol% to 7.0 mol%, Particularly preferred is 0.1 mol% to 5.0 mol%, and particularly preferred is 1.0 mol% to 5.0 mol%. Among them, (a)+(b)=100 mol%. The content ratio of the structural unit of the olefin-based polymer can be obtained by analysis of ¹³ C-nuclear magnetic resonance (NMR) spectrum.

Here, examples of the α-olefins having 3 to 12 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, and 4-methyl-1. -Pentene, 3-methyl-1- Straight-chain or branched α-olefins such as pentene, 1-octene, 1-decene, 1-dodecene. Preferred are propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, particularly preferred is an α-olefin having 3 to 8 carbon atoms, and particularly preferred is propylene, 1-butene. When ethylene is copolymerized with propylene or 1-butene, the balance of processability, appearance, and mechanical strength of the resin composition becomes good. Furthermore, one kind of α-olefin may be used alone, or two or more kinds may be used in combination.

In addition, the olefin-based polymer may be a propylene homopolymer (polypropylene) or a propylene (co)polymer of propylene and ethylene or an α-olefin having 4 to 12 carbon atoms. When the propylene (co)polymer is a copolymer of propylene and ethylene, the amount of structural units derived from propylene may be 60 mol% to 99.5 mol%. The amount of structural units derived from propylene in this case is preferably 80 mol% to 99 mol%, more preferably 90 mol% to 98.5 mol%, and particularly preferably 95 mol% to 98 mol %. Among them, the total amount of structural units derived from propylene and the amount of structural units derived from ethylene was 100 mol%. If a propylene (co)polymer having a large amount of constituent units derived from propylene is used, a resin composition with a good balance of appearance, mechanical strength, and heat resistance can be obtained.

When the propylene (co)polymer is a copolymer of propylene and an α-olefin having 4 to 12 carbon atoms, examples of the α-olefin having 4 to 12 carbon atoms include 1-butene, 1- Pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1- Linear or branched α-olefins such as dodecene. Among them, particularly preferred is 1-butene. In addition, propylene. The α-olefin copolymer may contain an olefin other than 4 to 12 carbon atoms, and for example, contains a small amount, for example, 10 mol% or less of structural units derived from ethylene or the like. On the other hand, it improves the resistance of the resin composition From the viewpoint of the balance between thermal properties and mechanical strength, a case where a structural unit derived from ethylene is not included is also one of the preferred forms. One type of α-olefin may be used alone, or two or more types may be used in combination.

The propylene (co)polymer is propylene. In the case of an α-olefin copolymer, the amount of the constituent unit (a′) derived from propylene is preferably 60 mol% to 90 mol%, more preferably 65 mol% to 88 mol%, particularly preferably It is 70 mol% to 85 mol%, and especially good is 75 mol% to 82 mol%. On the other hand, the amount of the structural unit (b') derived from an α-olefin having 4 or more carbon atoms is preferably 10 mol% to 40 mol%, more preferably 12 mol% to 35 mol% , Youjia is 15 mol% ~ 30 mol%, particularly good is 18 mol% ~ 25 mol%. Among them, (a')+(b')=100 mol%.

If propylene. When the composition of the α-olefin copolymer is within the above range, a resin composition excellent in appearance can be obtained. The reason is not clear, but because the crystallization rate is slow, the time that the resin composition can flow on the mold or in the cooling step becomes longer. In addition, as a result, it is considered that the surface property becomes good. In addition, when the composition is within the above range, the mechanical strength and heat resistance become good. According to propylene. The melting point Tm obtained from the DSC results of the α-olefin copolymer is usually 60°C to 120°C, preferably 65°C to 100°C, and particularly preferably 70°C to 90°C.

In addition, further, the olefin-based polymer may be ethylene. α-olefin. Non-conjugated polyene copolymer. In this case, a copolymer of ethylene [A] and a C 3-12 alpha-olefin [B] and a non-conjugated polyene [C] is preferred, and it is more preferred that these are randomly copolymerized and The polymer. Examples of α-olefins include α-olefins having 3 to 12 carbon atoms. For example, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, and 4-methyl Yl-1-pentene, Linear or branched α-olefins with 3 to 12 carbon atoms, such as 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, etc. In addition, as the non-conjugated polyene, a cyclic or chain non-conjugated polyene can be used. Examples of cyclic non-conjugated polyenes include cyclopentene, cycloheptene, norbornene, 5-ethylene-2-norbornene, dicyclopentadiene, and 5-vinyl-2-norbornene. Norbornene, norbornadiene (norbornadiene), methyltetrahydroindene, tetracyclododecene, etc. Examples of the chain-like non-conjugated polyene include 1,4-hexadiene, 7-methyl-1,6-octadiene, 4-ethylene-8-methyl-1,7-nonadiene Ene and 4-ethylene-1,7-undecadiene, etc. Among them, 5-ethylene-2-norbornene, dicyclopentadiene and 5-vinyl-2-norbornene are preferred. These cyclic or chain non-conjugated polyenes may be used alone or in combination of two or more.

The ethylene. α-olefin. Examples of non-conjugated polyene random copolymers include ethylene propylene. Diene terpolymer (ethylene propylene diene monomer, EPDM), etc.

In addition, as an olefin polymer, propylene can also be used. α-olefin. Non-conjugated polyene copolymer, or 1-butene. α-olefin. Non-conjugated polyene copolymers, etc.

Furthermore, as an olefin polymer, 4-methyl-1-pentene can also be used. α-olefin copolymer. As 4-methyl-1-pentene. Specific examples of the α-olefin copolymer include, for example, the polymers disclosed in International Publication No. 2011/055803. 4-methyl-1-pentene. The amount of structural units derived from 4-methyl-1-pentene in the α-olefin copolymer is preferably 5 mol% to 95 mol%, and is selected from the group consisting of 4-methyl-1-pentane The amount of structural units derived from at least one or more α-olefins having 2 to 20 carbon atoms other than olefins is preferably 5 mol% to 95 mol%. In addition, 4-methyl-1-pentene. α- A part of the olefin copolymer may contain non-conjugated polyene, and the amount of structural units derived from the non-conjugated polyene is preferably 0 mol% to 10 mol%. The total amount of these constituent units is 100 mol%.

In addition, the stereoregularity of the olefin-based polymer is not particularly limited. When the olefin-based polymer is a propylene-based (co)polymer, it is preferable that the propylene-based (co)polymer has substantially opposite rows ( syndiotactic) structure. For example, if the propylene-based (co)polymer has a substantially aligned structure, the molecular weight (Me) between the complexing points in the same molecular weight becomes smaller and the molecular complexation becomes more, so the melt tension becomes larger and it is difficult to cause sagging. . In addition, when a resin composition containing a propylene-based (co)polymer is used to produce a molded body, it is easy to moderately adhere to a mold or roll for molding. In addition, the propylene-based (co)polymer with a counter-row structure has a slow crystallization rate compared to a common polypropylene-based (co)polymer in the same row, so the cooling on the mold or roller becomes stable and the adhesion improve. As a result, it is presumed that the glossiness of the surface of the molded product is improved, or the abrasion resistance, scratch resistance, impact resistance, etc. are improved. Further, the fact that the propylene-based (co)polymer has a substantially aligned structure means that the peak area corresponding to 19.5 ppm to 20.3 ppm in the ¹³ C-NMR spectrum is relatively 0.5 or more. If the alignment degree is within the above range, the crystallization speed becomes slow to the extent that it can be formed, and the workability becomes very good. In addition, the structural units derived from propylene have substantially the wear resistance of the propylene-based (co)polymer having a row structure compared to polyethylene, block polypropylene, and polypropylene in the same row as general-purpose polyolefin resins. Consumption and damage resistance become very good. In addition, the propylene-based (co)polymer having a counter-row structure can be produced by various well-known production methods.

<graft modification>

When the resin (A) is the olefin-based polymer, the olefin-based polymer may be unmodified, but as described below, the olefin-based polymer may be graft-modified using a polar compound containing a double bond. When the olefin polymer is graft-modified, the compatibility of the resin (A) and the natural fiber (C) is improved, and a resin composition having excellent heat resistance and mechanical strength is obtained.

The graft modification of the olefin polymer can be carried out by a known method. For example, the following method may be exemplified: a olefin polymer is dissolved in an organic solvent, and then a polar compound containing a double bond such as an unsaturated carboxylic acid and a radical initiator, etc. are added to the obtained solution, usually at 60°C to 350°C The reaction is carried out at a temperature of 0° C., preferably 80° C. to 190° C. for 0.5 hours to 15 hours, preferably 1 hour to 10 hours.

If the organic solvent is an organic solvent that can dissolve an olefin-based polymer, it can be used without particular limitation. Examples of such organic solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane.

In addition, another graft modification method may include a method of using an extruder or the like, preferably without using a solvent, and reacting an olefin polymer with a polar compound containing a double bond such as an unsaturated carboxylic acid. The reaction temperature of the reaction conditions in this case can be generally set to be equal to or higher than the melting point of the olefin-based polymer, and specifically set to 100°C to 350°C. The reaction time can usually be set from 0.5 minutes to 10 minutes.

In order to efficiently carry out graft copolymerization of a polar compound containing a double bond, it is preferable to carry out the reaction in the presence of a radical initiator.

Free radical initiators can be used: organic peroxides or organic peroxide esters (for example: benzoyl peroxide, dichlorobenzyl peroxide, dicumyl peroxide, di-third butyl Base peroxide, 2,5-dimethyl-2,5-bis(peroxide benzoate) hexyne-3,1,4-bis(third butyl isopropyl peroxide)benzene, Lauryl peroxide, tert-butyl peroxyacetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl -2,5-di(tert-butylperoxy)hexane, tert-butylperoxybenzoate, tert-butylperoxyphenyl acetate, tert-butylperoxyisobutyrate , Third butyl peroxy-second octanoate, third butyl peroxy trimethyl acetate, cumyl peroxy trimethyl acetate, third butyl peroxy diethyl acetate , Third butyl isopropyl peroxide monocarbonate and third butyl peroxide 2-ethylhexyl monocarbonate), azo compounds (for example: azobisisobutyronitrile, dimethylazoisocarbonate) Butyrate) etc. Among these compounds, dicumyl peroxide, di-third butyl peroxide, 2,5-dimethyl-2,5-di(third butyl peroxide) hexyne- Dialkyl peroxides such as 3,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,4-bis(tert-butylperoxyisopropyl)benzene . The radical initiator is usually used in a ratio of 0.001 part by weight to 1 part by weight with respect to 100 parts by weight of the olefin polymer before modification.

In addition, the shape of the graft-modified olefin-based polymer is not particularly limited, and it may be in the form of particles, for example. An example of a preferable method for obtaining a particulate graft-modified olefin-based polymer includes the following method: one or more kinds of α-olefins selected from α-olefins having 2 to 18 carbon atoms, and Particles having a melting point of 50°C or more and less than 250°C undergo a graft reaction with a single mass having an ethylenically unsaturated group and a polar functional group in the same molecule. The grafting reaction can use the free radical initiator described in polyene It is performed at a temperature below the melting point (Tm) of the hydrocarbon particles. The average particle diameter of the particles of the graft-modified olefin-based polymer can be, for example, 0.2 mm to 2.5 mm, but it is not limited thereto. In addition, in one of the exemplary forms of the present invention, the melting point of the polyolefin particles used in the preparation of the particulate graft-modified olefin polymer is 50° C. or higher and less than 250° C., but is not limited thereto. The grafting reaction can also be carried out without solvent, but it is preferably carried out in the presence of an organic solvent.

(2) Polyamide

Polyamides can be exemplified by nylon-6, nylon-66, nylon-10, nylon-11, nylon-12, nylon-46, nylon-610, nylon-612 and other aliphatic polyamides, consisting of aromatic dicarboxylic acids Aromatic polyamide produced with aliphatic diamine, etc.; preferably nylon-6.

(3) Polyester

Examples of polyesters include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polycaprolactone, polyhydroxybutyrate, and polyester It is an elastomer or the like; preferably polyethylene terephthalate.

(4) Polyacetal

Examples of polyacetals include polyoxymethylene (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, and polybutyraldehyde, and polyacetal is particularly preferred.

(5) Styrene resin

The styrene-based resin may be a homopolymer of styrene, or a binary copolymer of styrene and acrylonitrile, methyl methacrylate, α-methylstyrene, etc., such as an acrylonitrile-styrene copolymer. In addition, acrylonitrile-butadiene-styrene resin, acrylonitrile-acrylic rubber-styrene resin, acrylonitrile-ethylene rubber-styrene resin, (A Base) acrylate-styrene resin, or various styrene elastomers. As the acrylonitrile-butadiene-styrene (ABS) resin, it is preferable to use a structural unit derived from acrylonitrile in an amount of 20 mol% to 35 mol%, and a content of 20 mol% to 30 mol. The amount of mol% contains the structural unit derived from butadiene, and the resin containing the structural unit derived from styrene in an amount of 40 mol% to 60 mol%. The total of these constituent units is 100 mol%.

In addition, as the styrene-based elastomer, a known styrene-based elastomer having a polystyrene phase as a hard segment can also be used. Specific examples include: styrene. Butadiene copolymer (styrene butadiene rubber, SBR), styrene. Isoprene. Styrene copolymer (styrene isoprene styrene, SIS), styrene. Butadiene. Styrene copolymer (styrene butadiene styrene, SBS), styrene. Ethylene. Butadiene. Styrene copolymer (styrene ethylene butadiene styrene, SEBS), and hydrides of these copolymers, styrene. Isobutene. Styrene triblock copolymer (styrene isobutylene styrene, SIBS), styrene. Styrene isobutylene (SIB). Preferably styrene. Isobutene. Styrene triblock copolymer (SIBS), styrene. Isobutylene diblock copolymer (SIB).

(6) Acrylic resin

The acrylic resin may include polymethacrylate or polyethylmethacrylate, preferably polymethyl methacrylate (PMMA).

(7) Polycarbonate

Polycarbonate can be exemplified by bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis (4-hydroxyphenyl) butane etc. It is preferably polycarbonate obtained from 2,2-bis(4-hydroxyphenyl)propane.

(8) Polyphenylene oxide

The polyphenylene ether is preferably poly(2,6-dimethyl-1,4-phenylene ether).

(9) Chlorine resins such as polyvinyl chloride and polyvinylidene chloride

Polyvinyl chloride may be a homopolymer of vinyl chloride, or a copolymer of vinyl chloride and vinylidene chloride, acrylate, acrylonitrile, propylene, and the like. On the other hand, polyvinylidene chloride is generally a resin containing more than 85% of vinylidene chloride units. For example, vinylidene chloride and vinyl chloride, acrylonitrile, (meth)acrylate, allyl ester, Copolymer of unsaturated ether, styrene, etc. In addition, there are cases where vinyl chloride-based elastomers are used.

(10) Vinyl acetate resins such as polyvinyl acetate and ethylene-vinyl acetate resin

Polyvinyl acetate may be a homopolymer of vinyl acetate, or a copolymer of vinyl acetate, ethylene, and vinyl chloride. Among these, ethylene-vinyl acetate copolymer is preferred. In addition, modified ethylene-vinyl acetate copolymers such as saponified ethylene-vinyl acetate copolymers and graft-modified ethylene-vinyl acetate copolymers may also be used.

(11) Ethylene-(meth)acrylate copolymer

The ethylene-(meth)acrylate copolymer is preferably: ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer.

(12) Ethylene-acrylic resin, ethylene-methacrylic resin, or these ionomer resins

The ethylene-acrylic acid copolymer and the ethylene-methacrylic acid copolymer may be copolymers of ethylene and various (meth)acrylic acids. These copolymers can be further metal salted to form metal salts (ionic polymers). The metal element of the metal salt is preferably at least one selected from K, Na, Ca, and Zn. If the metal element is K, Na, Ca, or Zn, the modification is easy, so it is better.

(13) Vinyl alcohol resins such as polyvinyl alcohol and ethylene-vinyl alcohol resin

Examples thereof include polyvinyl alcohol and ethylene-vinyl alcohol resin, and ethylene-vinyl alcohol resin is preferred. The ethylene-vinyl alcohol resin is obtained by hydrolysis of a copolymer of ethylene and vinyl acetate. The ethylene-vinyl alcohol resin not only has high gas barrier properties, oil resistance, and transparency of polyvinyl alcohol, but also has characteristics such as moisture resistance and melt extrusion processability of ethylene components. In addition, the ethylene-vinyl alcohol copolymer resin is well bonded to the natural fiber (C), and is excellent in balance of heat resistance and mechanical strength.

(14) Cellulose resin

Representative examples of cellulose resins include acetyl cellulose. By using plasticizers such as dibutyl phthalate together, it has the characteristics of a thermoplastic resin.

(15) Thermoplastic elastomer

The thermoplastic polyurethane materials listed as the thermoplastic urethane elastomer will be described. The structure of the thermoplastic polyurethane material contains a soft segment containing a high molecular polyol (polymeric glycol), a chain extender and a diisocyanate that constitute a hard segment. Here, as the polymer polyol used as a raw material, any of the techniques previously used in thermoplastic polyurethane materials can be used without particular limitation. For example, there are polyester series and polyether series. In terms of synthesizing a thermoplastic polyurethane material having a high coefficient of resilience and excellent low-temperature characteristics, a polyether system is preferable to a polyester system. Examples of polyether polyols include polytetramethylene glycol and polypropylene glycol, and polytetramethylene glycol is particularly preferred in terms of resilience coefficient and low-temperature characteristics. In addition, the average molecular weight of the polymer polyol is preferably 1,000 to 5,000, and particularly for synthesizing a thermoplastic polyurethane material with high resilience, preferably 2,000 to 4,000. The chain extender can be suitably used by users of existing technologies related to thermoplastic polyurethane materials, and examples include 1,4-butanediol, 1,2-ethylene glycol, and 1,3- Butylene glycol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, etc., but not limited to these. The average molecular weight of these chain extenders is preferably 20 to 15,000. The diisocyanate can be suitably used by users of existing technologies related to thermoplastic polyurethane materials, for example: 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2 , Aromatic diisocyanates such as 6-toluene diisocyanate, or aliphatic diisocyanates such as hexamethylene diisocyanate, etc., but not limited to these compounds. In the present invention, particularly preferred is 4,4′-diphenylmethane diisocyanate which is an aromatic diisocyanate. As the thermoplastic polyurethane material containing the material, a commercially available product can be suitably used, and examples include Pandex T-8290 and T manufactured by DIC Bayer Polymer (share) -8295, T8260, or Resin 2593, 2597, etc. manufactured by Dairi Refinery Industry Co., Ltd.

(16) Various copolymer rubbers

Examples of the rubber other than the elastomer include polybutadiene rubber, polyisoprene rubber, chloroprene rubber, nitrile rubber, butyl rubber, halogenated butyl rubber, and polyisobutylene Butene rubber, natural rubber, silicone rubber, etc. These rubbers may be used alone or in combination of two or more.

1-3. Better resin (A)

In the above example, the resin (A) is preferably selected from an olefin-based polymer, an acid-grafted modified body of an olefin-based polymer, a styrene resin, a chlorine resin, an ethylene-acrylic resin, an ethylene-methacrylic resin, or the Some ionic polymer resins, thermoplastic elastomers, and at least one resin in the group consisting of various copolymerized rubbers are more preferably selected from olefin-based polymers, polystyrene, and acrylonitrile. Butadiene. At least one resin in the group consisting of styrene copolymer resin (ABS resin) and polyvinyl chloride, particularly preferably selected from polyethylene, polypropylene, poly-1-butene, poly 4-methyl-1 -Pentene, polyvinyl chloride, polystyrene, acrylonitrile. Butadiene. Styrene copolymer. In addition, particularly preferred is an ethylene (co)polymer or propylene (co)polymer. When an ethylene (co)polymer or a propylene (co)polymer is used as the resin (A), it is preferable to form a resin composition with less odor, fumes, etc. and a good working environment. In addition, a molded product with little scorch and good quality can be obtained. In addition, ethylene (co)polymers are excellent in low-temperature characteristics and processability, and propylene (co)polymers are excellent in heat resistance and rigidity.

1-4. Properties of resin (A)

The resin (A) preferably has a melting point (Tm) measured by a differential scanning calorimeter (DSC) of 250° C. or lower or is not observed. When the melting point is observed, the upper limit of the melting point is more preferably 230°C, particularly preferably 200°C, and particularly preferably 170°C. In addition, the lower limit of the melting point is preferably 50°C, more preferably 70°C, particularly preferably 90°C, particularly preferably 130°C, and most preferably 150°C. If the melting point is within the range of the upper limit and the lower limit, the When making resin composition or synthetic wood by melt molding, the influence of smoke and odor on the forming environment is small, and the scorching trouble of natural fiber (C), especially wood flour is reduced, so Better. In addition, a resin composition with little stickiness and excellent balance of heat resistance, mechanical strength, impact strength, and impact absorption can be obtained.

The resin (A) is preferably a glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) in the range of -140°C to 50°C, more preferably in the range of -120°C to 40°C, particularly preferably -50℃~-10℃. If the glass transition temperature is within the above range, the resin composition tends to be excellent in the balance of long-term stability, heat resistance, impact resistance, and mechanical strength.

Determined according to the method of the density gradient tube density of the resin (A) is preferably in the range of ^{3 800kg / m 3 ~ 1800kg / m} . The lower limit of the density of the resin (A) is more preferably 810kg / m ^3, particularly preferably 830kg / m ^3, particularly preferably 860kg / m ^3, most preferably 900kg / m ^3. Further, the upper limit of the density of the resin (A) is more preferably 1300kg / m ^3, particularly preferably 1100kg / m ^3, particularly preferably 1000kg / m ^3, particularly preferably 940kg / m ^3, most preferably 905kg / m ^3.

When the density of the resin (A) is within the above range, dimensional stability and mechanical strength are excellent. It is considered that the mechanism is that the resin of the above density tends to have excellent water resistance due to relatively few polar groups, and can suppress water absorption of the natural fiber (C). Therefore, it is considered that the load at the interface between the natural fiber (C) and the resin (A) becomes small, and as a result, not only is the dimensional stability excellent, but also the mechanical strength is improved. In addition, a lighter weight resin composition can be used to obtain the same mechanical strength as before. Furthermore, a resin composition excellent in antifouling properties can be obtained. In addition, processability, heat resistance, mechanical strength, A resin composition with a good balance of impact strength and impact absorption.

The bending modulus of elasticity of the resin (A) measured according to JIS K7171:94 is preferably 1 MPa to 10000 MPa. Here, when the bending elastic coefficient is 500 MPa or more, the bending elastic coefficient is preferably 500 MPa to 7000 MPa, more preferably 700 MPa to 5000 MPa, particularly preferably 900 MPa to 3000 MPa, and particularly preferably 1000 MPa to 2000 MPa. When the bending elastic coefficient is within the above range, it is possible to obtain a resin composition that is not only excellent in workability, but also excellent in balance of scratch resistance, heat resistance, and mechanical strength. In addition, when the bending elastic coefficient is less than 500 MPa, it is preferably less than 300 MPa, more preferably less than 100 MPa, and particularly preferably less than 50 MPa. When the bending elastic coefficient is within the above range, a resin composition that is not only excellent in flexibility but also excellent in impact absorption, light weight, vibration resistance, damping property, and sound insulation property can be obtained. Furthermore, a resin composition excellent in design properties such as mold transferability and wrinkle transferability, and surface gripping properties can be obtained.

2. Compatibilizer (B)

The compatibilizer (B) is a resin different from the resin (A), and is a compound used to make the resin (A) and the natural fiber (C) compatible. The compatibilizer (B) is preferably a polyolefin wax (B1) or petroleum resin (B2) described later.

If the natural fiber (C) is blended with the resin (A) that forms the basis of the resin composition, the compatibility of the resin (A) and the natural fiber (C) is poor, and there may be cases where uniform kneading cannot be achieved. In particular, if the blending amount of the natural fiber (C) with respect to the resin (A) is high, or the surface area of the natural fiber (C) is large (natural fiber is fine), it is often difficult to be compatible. Therefore, when the resin group containing resin (A) and natural fiber (C) When the product and its molded product are molded, the workability deteriorates, or the uniformity of the molded product is insufficient, so that the appearance deteriorates, the heat resistance or mechanical strength decreases, or the flexibility (elongation) decreases in many cases.

Since the compatibilizer (B) in the resin composition of the present invention improves the compatibility of the resin (A) and the natural fiber (C), not only can the processability of the resin composition be improved, but also the appearance, heat resistance, Balance of mechanical strength.

According to the studies of the present inventors and others, if the compatibilizer (B) has a large-volume skeleton in the molecular chain, there is an effect of improving the balance of appearance, heat resistance, and mechanical strength. In addition, it is known that these effects are particularly high if the compatibilizer (B) is selected from the group consisting of polyolefin wax (B1) and petroleum resin (B2).

The detailed mechanism is not clear, but it is considered that the compatibilizing agent having a bulky skeleton in the molecular chain is easily fused with natural fibers (C) such as cellulose, which usually have a bulky skeleton. Therefore, it is considered that when the resin composition of the present invention is molded, the compatibilizer (B) can be locally present on the surface of the natural fiber (C), and the dispersibility of the natural fiber (C) in the resin composition is improved. On the other hand, in the step of solidifying the resin composition from the molten state, when the compatibility of the compatibilizing agent (B) with the natural fiber (C) is poor, or the amount thereof is excessive, the low molecular weight may sometimes be recognized from the resin composition The material oozes, causing deterioration of the appearance accompanying this. In contrast, in the resin composition of the present invention, since the amount of the compatibilizer (B) is within the above range, it is considered that the compatibilizer (B) added to the resin composition can be uniformly present in the natural fiber (C )surface. Therefore, it is considered that in the resin composition, the compatibilizer (B) and the natural fiber (C) are not biased, and the balance of appearance, heat resistance, processability, and mechanical strength becomes good.

In addition, the compound having a bulky skeleton in the molecular chain includes, for example, petroleum resin (B2) or terpene-based resin to be described later. In addition, even waxes that usually contain polyolefins that do not have a bulky framework can be modified by acid modification or styrene modification described later to introduce large-volume structural units into the molecular chain, thereby forming Large-volume skeleton compounds.

If the compatibilizer (B) is an unsaturated carboxylic acid derivative monomer modified product of polyolefin wax (for example, maleic anhydride modified product) or air oxide (one of polyolefin wax (B1) described later), then The compatibility with the natural fiber (C) is particularly improved, so it is preferable. In addition, it is considered that a styrene-modified product of polyolefin wax (one of polyolefin wax (B1) described later) is also easily fused with natural fibers (C) having a large-volume skeleton such as cellulose, which is preferable. If the unsaturated carboxylic acid derivative modified product, air oxide, and styrene modified product of the polyolefin wax are used as the compatibilizer (B), the balance of appearance, heat resistance, processability, and mechanical strength becomes more good.

2-1. Physical properties of polyolefin wax (B1) and petroleum resin (B2)

The polyolefin wax (B1) and the petroleum resin (B2) described later as the compatibilizer (B) preferably satisfy the following requirements (i) to (iv).

(i) The polystyrene-converted number average molecular weight (Mn) of polyolefin wax (B1) and petroleum resin (B2) measured by gel permeation chromatography (GPC) is preferably in the range of 300 to 20,000 . More preferably, it is 500 to 18000, especially, 1000 to 12000, especially 1500 to 12000, especially 3700 to 12000, especially 6000 to 12000, and most preferably 8000 to 10000. If the number average molecular weight is within the above range, the dispersibility of the natural fiber (C) in the resin composition is improved, and the appearance, heat resistance, Excellent mechanical strength. In addition, the processability and kneadability of the resin composition tend to be good.

(ii) The softening point of polyolefin wax (B1) and petroleum resin (B2) measured according to JIS K2207 is preferably in the range of 70°C to 170°C. The upper limit of the softening point is more preferably 160°C, particularly preferably 150°C, and particularly preferably 145°C. In addition, the lower limit is more preferably 80°C, particularly preferably 90°C, particularly preferably 95°C, and most preferably 105°C. When the softening point is within the above range, the resin composition is excellent in appearance, processability, heat resistance, and mechanical strength.

Density (iii) polyolefin waxes (B1) and petroleum resin (B2) by using a density gradient tube method is preferably determined in the range ^{830kg / m 3 ~ 1200kg / m} 3 in. More preferably, it is 860kg/m ³ ~1100kg/m ³ , especially 890kg/m ³ ~1000kg/m ³ , especially 895kg/m ³ ~960kg/m ³ , especially 895kg/m ³ ~935kg/m ³ . When the density is within the above range, not only the dispersibility of the natural fiber is improved, but also the appearance, heat resistance, and mechanical strength of the resin composition are excellent. In addition, there is a tendency that the workability and kneadability are also good. The reason for this is not clear, but it is considered as follows: Usually, the density of the natural fiber (C) is 1000 kg/m ³ or more. On the other hand, if a compatibilizer (B) with a density lower than that of the natural fiber (C) is used, when the compatibilizer (B) is localized on the surface of the natural fiber (C), the natural fiber (C) is reduced. As a result of the surface tension effect of the surface, the cohesion of the natural fiber (C) can be reduced. In addition, the natural fibers can be uniformly dispersed, thereby being excellent in workability or kneadability, and excellent in appearance, heat resistance, and mechanical strength of the resin composition.

Furthermore, the difference between the density of the resin (A) and the density of the compatibilizer (B) is preferably less than 50 kg/m ³ , particularly preferably less than 30 kg/m ³ , and particularly preferably less than 15 kg/m ³ . If the density difference is within the above range, the processability, appearance, heat resistance, and mechanical strength are excellent. The reason is considered to be that substances with similar densities tend to mix with each other. That is, since the compatibility between the resin (A) and the compatibilizer (B) is high, it is considered that as a result, the dispersibility of the natural fiber (C) coated with the compatibilizer (B) is improved, so the processability is improved. In addition, bleeding from the resin (A) caused by the compatibilizer (B) is suppressed, and therefore, it is considered that the appearance, heat resistance, and mechanical strength can be balanced.

(iv) The ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) of polyolefin wax (B1) and petroleum resin (B2) measured by gel permeation chromatography (GPC) is preferably 7.0 or less. It is more preferably 5.0 or less, and particularly preferably 3.0 or less. When Mw/Mn is included in the above range, there are few low-molecular-weight components that cause a drop in physical properties, and therefore the appearance, heat resistance, and mechanical strength are excellent.

Here, as the compatibilizing agent (B), any two or more compatibilizing agents can be selected from polyolefin wax (B1), petroleum resin (B2), and other compatibilizing agents (B) described below, and These compatibilizers are used in combination. At this time, if the melting point or softening point of the compatibilizer used in combination is different from each other, it is particularly easy to balance the processability and mechanical strength of the resin composition.

When two or more compatibilizers (B) are used together, the difference between the softening point of the compatibilizer (BH) with the highest softening point and the compatibilizer (BL) with the lowest softening point is preferably 5 Above ℃, more preferably above 10 ℃, particularly preferably above 20 ℃, particularly preferably above 30 ℃, particularly preferably above 40 ℃.

If the difference between the softening point of the compatibilizer (BH) and the softening point of the compatibilizer (BL) is within the above range, the processability and mechanical strength of the obtained resin composition Excellent, so better. In addition, it can particularly reduce the torque of the extruder or suppress shear heating. The reason is not clear. For example, when acid-modified polypropylene wax (BH) with a high softening point and polyethylene wax (BL) with a low softening point are used as a compatibilizer (B), it is considered that Polyethylene wax (BL) with a lower softening point melts in the system at an earlier time, the dispersibility of the natural fiber (C) in the resin (A) is improved, and the torque of the extruder is effectively reduced. Furthermore, it is believed that the melted polyethylene wax (BL) suppresses shear heat generation in the system, and as a result, the scorching of natural fibers is suppressed. That is, it is considered that the compatibilizer (BL) having a low softening point exhibits excellent processability. On the other hand, after the dispersibility of the natural fiber (C) is improved, the acid-modified polypropylene wax (BH) with a high softening point melts, whereby the contact efficiency of the acid-modified polypropylene wax (BH) with the natural fiber (C) It becomes good, and the modification effect of the acid-modified polypropylene wax (BH) of the natural fiber (C) is improved. Therefore, it is considered that not only the processability of the resin composition can be improved, but also the mechanical properties can be effectively improved.

The softening point of the compatibilizer (BH) with the highest softening point is preferably in the range of 100°C to 180°C, and more preferably in the range of 110°C to 175°C. In addition, the softening point of the compatibilizer (BL) having the lowest softening point is preferably in the range of 80°C to 150°C, and more preferably in the range of 90°C to 145°C.

When the compatibilizer (BH) with the highest softening point and the compatibilizer (BL) with the lowest softening point are selected from olefin wax (B1), the melting point of the compatibilizer (BH) with the highest softening point is It is preferably in the range of 90°C to 170°C, and more preferably in the range of 100°C to 165°C. In addition, the melting point of the compatibilizer (BL) having the lowest softening point is preferably in the range of 70°C to 140°C, and more preferably in the range of 80°C to 135°C.

In addition, the greater the added amount of the compatibilizer (BL) with the lowest softening point, the easier the dispersibility of the natural fiber (C) is. Specifically, the mass ratio of (BH) to (BL) (BH)/(BL) is preferably in the range of 1/200 to 1/1, more preferably 1/50 to 1/1.1, and particularly preferably 1/20~1/1.3, the best is 1/10~1/1.5. In addition, when any two or more compatibilizers are selected from the group consisting of polyolefin wax (B1), and these compatibilizers are used in combination, especially the balance between processability and mechanical strength tends to change Well.

The compatibilizer (BH) with the highest softening point is preferably a modified polyolefin wax (B1) described later, preferably the compatibilizer (BH) with the highest softening point and the compatibilizer (BL) with the lowest softening point It is selected from polyolefin wax (B1). In addition, it is particularly preferred that the polyolefin wax (B1) is an unsaturated carboxylic acid derivative monomer modified product of an olefin wax.

The compatibilizer (BH) at the highest softening point is an unsaturated carboxylic acid derivative monomer modified product of polyolefin wax described later (for example, maleic anhydride modified product) or an air oxide (polyolefin wax described later ( In the case of one of B1), the acid value range of the compatibilizer (BH) with the highest softening point is preferably 40 mgKOH/g to 100 mgKOH/g, more preferably 50 mgKOH/g to 100 mgKOH/g, and particularly preferably 60 mgKOH /g~100mgKOH/g, particularly preferably 60mgKOH/g~95mgKOH/g, particularly preferably 60mgKOH/g~90mgKOH/g, particularly preferably 80mgKOH/g~90mgKOH/g. If the acid value of the compatibilizer (BH) having the highest softening point is within the above range, a resin composition excellent in heat resistance and mechanical strength can be obtained.

Here, the compatibilizer (BL) at the lowest softening point is an unsaturated carboxylic acid derivative monomer modified product of polyolefin wax described later (for example, maleic anhydride modified product) In the case of air oxide (one of polyolefin wax (B1) described later), the acid value is preferably 90 mgKOH/g or less, and more preferably 65 mgKOH/g or less. In this case, the lower limit is preferably 15 mgKOH/g or more. If the compatibilizer (BL) with the lowest softening point has an acid value in the above range, not only the processability is maintained, but also the load deformation temperature and softening point as the resin composition are improved, and a resin composition with excellent heat resistance can be formed . The reason is not clear, but it is considered as follows: even if a temperature above the softening point is applied to the resin composition, since the acid value is in the above range, the compatibilizer (BL) with the lowest softening point is easier than the natural fiber (C) The surface is localized and fixed. As a result, even at high temperatures, the molecular mobility is not improved, and the heat resistance of the resin composition is improved.

On the other hand, if the acid value of the compatibilizer (BL) having the lowest softening point is low, the processability of the resin composition becomes particularly good. Specifically, the acid value is preferably 3 mgKOH/g or less, and more preferably the acid value is 1 mgKOH/g or less. The compatibilizer (BL) with the lowest softening point is particularly preferably an unmodified polyolefin wax (B1). It is considered that the lower the acid value of the polyolefin wax (B1), which is the compatibilizer (BL) with the lowest softening point, the polyolefin wax (B1) and the natural fiber (C) are at the extrusion processing temperature of the resin composition The interaction becomes smaller and the processability becomes superior.

In addition, it is also preferable to use polyolefin wax (B1) and petroleum resin (B2) together. In this case, the greater the ratio of polyolefin wax (B1), the dispersibility, appearance, and mechanical properties of natural fiber (C) , Workability and heat resistance are more likely to be superior. On the other hand, the greater the ratio of petroleum resin (B2), the easier the kneadability of resin (A) and natural fiber (C) can be significantly improved.

2-2. Polyolefin wax (B1)

In the present invention, the concept of "polyolefin wax" includes not only general polyolefin wax (hereinafter also referred to as "unmodified polyolefin wax") but also modified products thereof (hereinafter also referred to as "modified polyolefin") wax"). The preferred polyolefin wax (B1) as the compatibilizer (B) of the resin composition of the present invention is a homopolymer or copolymer of ethylene or at least one selected from α-olefins having 3 to 12 carbon atoms. Substance, or its unsaturated carboxylic acid derivative monomer modified substance (for example, maleic anhydride modified substance), air oxide, or styrene modified substance. More preferably, it is a copolymer selected from the group consisting of ethylene homopolymer, propylene homopolymer, ethylene and at least one α-olefin selected from α-olefins having 3 to 12 carbon atoms, and propylene and 4 to 4 carbon atoms. 12. A polymer in the group consisting of a copolymer of at least one α-olefin in the α-olefin, or an unsaturated carboxylic acid derivative monomer modified product of the polymer (for example, maleic anhydride modified product) Or modified styrene, air oxide. In addition, polyolefin wax (B1) can also be used as an additive for toner, an additive for hot melt, a pigment dispersant, a processing aid, an additive for electric cable compound, and three-dimensional (three) -dimensional, 3D) resin formulations for printers, etc.

Here, examples of the α-olefin having 3 to 12 carbon atoms (or 4 to 12 carbon atoms) which are polymerized with ethylene or propylene include propylene having 3 carbon atoms, 1-butene having 4 carbon atoms, and carbon 1-pentene having 5 atoms, 1-hexene having 6 carbon atoms, 4-methyl-1-pentene, 1-octene having 8 carbon atoms, etc., preferably propylene, 1-butene, 1-hexene, 4-methyl-1-pentene.

In the following, the unmodified polyolefin wax and its manufacturing method will be described first. Next, the modified polyolefin wax obtained by modifying these will be described.

(Unmodified polyolefin wax)

As described above, unmodified polyolefin wax can be used as polyolefin wax (B1). Hereinafter, as specific examples of the unmodified polyolefin wax, polyethylene wax, polypropylene wax, and 4-methyl-1-pentene wax will be described, but the unmodified polyolefin wax is not limited to It should be.

. Polyethylene wax

In the case where the polyolefin wax (B1) is a polyethylene-based wax, examples of preferred polyethylene-based waxes are described in, for example, Japanese Patent Laid-Open No. 2009-144146, etc., and are briefly described below.

When the polyolefin wax (B1) is a polyethylene wax, it is preferably an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms. Specific examples of the ethylene homopolymer include high-density polyethylene wax, medium-density polyethylene wax, low-density polyethylene wax, and linear low-density polyethylene wax.

On the other hand, in the case where the polyethylene-based wax is a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, the amount of the structural unit (a) derived from ethylene is preferably 91.0 mol% to 99.9 mol% Ear %, more preferably 93.0 mol%~99.9 mol%, especially good 95.0 mol%~99.9 mol%, especially good 95.0 mol%~99.0 mol%. On the other hand, the amount of the structural unit (b) derived from an α-olefin having 3 or more carbon atoms is preferably 0.1 mol% to 9.0 mol%, more preferably 0.1 mol% to 7.0 mol%, Particularly preferred is 0.1 mol% to 5.0 mol%, and particularly preferred is 1.0 mol% to 5.0 mol%. Among them, (a)+(b)=100 mol%. The content ratio of the structural unit of the olefin-based polymer can be determined by analysis of ¹³ C-NMR spectrum.

Here, examples of the α-olefins having 3 to 12 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, and 4-methyl- Linear or branched α-olefins such as 1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, preferably propylene, 1-butene Olefins, 1-hexene, 4-methyl-1-pentene, 1-octene, particularly preferably α-olefins having 3 to 8 carbon atoms, particularly preferably propylene and 1-butene, most preferably 1-butene. When ethylene is copolymerized with propylene or 1-butene, the compatibilizer (B) tends to be hard and the stickiness tends to be reduced, so that the surface properties of the molded product become good. In addition, it is also preferable in terms of improving mechanical strength or heat resistance. By combining ethylene with propylene or 1-butene, the reason why the compatibilizer (B) becomes harder and less sticky is not clear. It is presumed that it is because: propylene or 1-butene and other α- Compared with olefins, the melting point is efficiently lowered by a small amount of copolymerization. Therefore, if the melting points are compared with the same melting point, the crystallinity tends to be high. One type of α-olefin may be used alone, or two or more types may be used in combination.

The polyethylene wax is particularly suitable when the resin (A) is a polyethylene resin. When these are combined, the compatibility of the resin (A) and the compatibilizer (B) improves, and the balance of the appearance, processability, mechanical strength, and heat resistance of the obtained molded product becomes good.

. Polypropylene wax

The polyolefin wax (B1) may be a polypropylene wax. The polypropylene wax may be a homopolymer of propylene obtained by copolymerizing propylene and other monomers as needed in the presence of a stereospecific catalyst, or a copolymer mainly composed of propylene, or may be a High molecular weight polypropylene is obtained by thermal decomposition. In addition, polypropylene wax It is purified by a method such as solvent fractionation by fractionating the difference in solubility of the solvent, or molecular distillation by fractionation by the difference in boiling point. The polypropylene wax may be a propylene homopolymer, a polymer of propylene and ethylene, or a copolymer of propylene and an α-olefin having 4 to 12 carbon atoms.

In the case where the polypropylene-based wax is a copolymer of propylene and ethylene, the structural unit derived from propylene can be 60 mol% to 99.5 mol%. The amount of constituent units derived from propylene is preferably 80 mol% to 99 mol%, more preferably 90 mol% to 98.5 mol%, and particularly preferably 95 mol% to 98 mol%. By using the propylene copolymer, a resin composition excellent in balance of appearance, mechanical strength, and heat resistance can be obtained.

In the case where the polypropylene-based wax is a copolymer of propylene and an α-olefin having 4 to 12 carbon atoms, examples of the α-olefin having 4 to 12 carbon atoms include 1-butene, 1-pentene, and 3 -Methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, etc. Straight chain or branched α-olefin. Among them, particularly preferred is 1-butene.

In addition, the polypropylene wax is propylene. In the case of an α-olefin copolymer, the amount of the constituent unit (a′) derived from propylene is preferably 60 mol% to 90 mol%, more preferably 65 mol% to 88 mol%, particularly preferably It is 70 mol% to 85 mol%, and especially good is 75 mol% to 82 mol%. On the other hand, the amount of the structural unit (b') derived from an α-olefin having 4 or more carbon atoms is preferably 10 mol% to 40 mol%, more preferably 12 mol% to 35 mol% , Youjia is 15 mol% ~ 30 mol%, particularly good is 18 mol% ~ 25 mol%. Among them, (a')+(b')=100 mol%.

The polypropylene wax is propylene. In the case of α-olefin copolymer, if its composition Within the above range, a resin composition excellent in appearance can be obtained. As a reason for this, it is considered that since it takes time until the compatibilizer crystallizes, it is possible to ensure that the resin composition can flow for a long time on the mold or in the cooling step. As a result, the surface quality of the obtained molded product becomes good. In addition, there is a tendency that heat resistance and mechanical strength are also excellent.

The polypropylene wax is particularly suitable when the resin (A) is a polypropylene resin. When these are combined, the compatibility of the resin (A) and the compatibilizer (B) improves, and the balance of the appearance, processability, mechanical strength, and heat resistance of the obtained molded product becomes good.

. 4-Methyl-1-pentene wax

Polyolefin wax (B1) may also be 4-methyl-1-pentene disclosed in International Publication No. 2011/055803. An α-olefin copolymer is obtained by thermal decomposition, or a 4-methyl-1-pentene-based polymer as shown in Japanese Patent Laid-Open No. 2015-028187.

(Manufacturing method of unmodified polyolefin wax)

The unmodified polyolefin wax such as polyethylene wax or polypropylene wax may be obtained by directly polymerizing ethylene or α-olefin, or may be obtained by thermally decomposing a high molecular weight copolymer By. In the case of thermal decomposition, it is preferable to perform thermal decomposition at 300°C to 450°C for 5 minutes to 10 hours. In this case, unsaturated ends exist in the unmodified polyolefin wax. Specifically, if the number of vinylidene groups per 1000 carbon atoms measured by ¹ H-NMR is 0.5 to 5, the compatibility effect with respect to the natural fiber (C) is improved, which is particularly preferable. In addition, the unmodified polyolefin wax can also be purified by a method such as solvent fractionation or distillation by fractionating the difference in the solubility of the solvent. In addition, it may be one containing a single polymer, or a mixture of two or more polymers.

In the case of directly polymerizing ethylene or α-olefin, various well-known manufacturing methods can be applied, for example, using a Ziegler/Natta catalyst or a metallocene catalyst to convert ethylene or α-olefin Production method of olefin polymerization.

For example, it can be applied to a suspension polymerization method in which the polymerization monomer or its polymer is present as particles in an inert hydrocarbon medium such as hexane, and the polymerization monomer or its polymer is polymerized; A gas phase polymerization method that uses a solvent to perform polymerization and the like. In addition, a solution polymerization method in which a polymerization monomer or a polymer thereof is polymerized in a state of being melted in an inert hydrocarbon medium can also be applied. Among these methods, the solution polymerization method is particularly preferable in terms of both economy and quality. The polymerization reaction can also be carried out by any method such as batch method or continuous method. In addition, the polymerization can also be carried out in two or more stages with different reaction conditions.

Examples of the inert hydrocarbon medium used in the suspension polymerization method or the solution polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane , Cyclohexane, methylcyclopentane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; vinyl chloride, chlorobenzene, dichloromethane and other halogenated hydrocarbons. One kind of inert hydrocarbon medium may be used alone, or two or more kinds may be used in combination. In addition, a so-called bulk polymerization method using α-olefin itself as a solvent can also be used.

The catalyst is preferably a metallocene-based catalyst. Examples of the metallocene catalyst include catalysts containing the following compounds: (a) transition metals selected from Group 4 of the periodic table Metallocene compounds; (b) selected from (b-1) organoaluminum oxy compounds, (b-2) and metallocene compounds (a) react to form ion-pair compounds (hereinafter, referred to as "ionized ions" At least one compound among organo-aluminum compounds (refer to Japanese Patent Laid-Open No. 08-239414, International Publication No. 2007/114102 manual).

The metallocene compound (a) selected from the transition metals in Group 4 of the periodic table includes the metallocene compounds described in Japanese Patent Laid-Open No. 08-239414 and the International Publication No. 2007/114102 manual, among which the metallocene compounds are particularly suitable Bis(n-butylcyclopentadienyl) zirconium dichloride and bis(n-butylcyclopentadienyl) zirconium dimethyl are used.

As the organoaluminum oxy compound (b-1), conventionally known aluminoxane can be used as it is. For example, the organoaluminum oxy compound described in Japanese Patent Laid-Open No. 08-239414 and International Publication No. 2007/114102 manual can be cited. The organoaluminum oxy compound (b-1) is preferably methyl aluminoxane, which is easily available because it is a commercially available product, and modified methyl aluminoxane (modified) prepared using trimethyl aluminum and triisobutyl aluminum. methyl aluminoxane, MMAO).

Examples of the ionized ionic compound (b-2) include the ionized ionic compounds described in Japanese Patent Laid-Open No. 08-239414 and International Publication No. 2007/114102 manual. The ionized ionic compound (b-2) is easily available as a commercially available product and has a great help in improving the polymerization activity. Therefore, triphenylcarbonium tetrakis(pentafluorophenyl) borate and N,N- Dimethylanilinium tetrakis (pentafluorophenyl) borate.

Examples of organoaluminum compounds (b-3) include International Publication No. 2007/114102 The organoaluminum compound described in the manual. The organoaluminum compound (b-3) is preferably trimethylaluminum, triethylaluminum, and triisobutylaluminum, which are commercially available and easily available. Among them, particularly preferred is triisobutylaluminum which is easy to handle.

When the compound (b) selected from the compounds (b-1) to (b-3) is combined, the polymerization activity is greatly improved, so triisobutylaluminum and triphenylcarbonium are particularly preferred Combination of tetrakis (pentafluorophenyl) borate and triisobutylaluminum with N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

When the metallocene catalyst is used to polymerize the monomer, the content of each component can be set as described below.

(1) The metallocene compound (a) can be used in an amount of 10 ^-9 mol to 10 ^-1 mol, preferably 10 ^-8 mol to 10 ^-2 mol per 1 liter of reaction volume.

(2) In the case of using a catalyst containing a metallocene compound (a) and an organoaluminum oxy-compound (b-1), the compound (b-1) may contain the aluminum atom (Al) in the compound (b-1) and The molar ratio [Al/M] of all transition metal atoms (M) in the metallocene compound (a) is used in an amount of 0.01 to 5000, preferably 0.05 to 2000.

(3) In the case of using a catalyst containing a metallocene compound (a) and an ionic compound (b-2), the compound (b-2) may be one of the compound (b-2) and the metallocene compound (a) The molar ratio [(b-2)/M] of all transition metal atoms (M) is used in an amount of 1 to 10, preferably 1 to 5.

(4) When using a catalyst containing a metallocene compound (a) and an organoaluminum compound (b-3), usually all the transition metal atoms in the compound (b-3) and the metallocene compound (a) The molar ratio of (M) [(b-3)/M] becomes 0.01~50,000, It is preferably used in an amount of 0.05 to 10000.

In addition, the polymerization temperature is usually in the range of 10°C to 200°C, and from the viewpoint of producing the unmodified polyolefin wax having the preferred amount of the constituent units, the polymerization temperature is preferably in the range of 60°C to 180°C, More preferably, it is in the range of 75°C to 170°C. The polymerization pressure can be set to normal pressure to 7.8 MPa-G (G is gauge pressure) or less, more preferably normal pressure to 4.9 MPa-G (G is gauge pressure) or less.

At the time of polymerization, ethylene or α-olefin is supplied to the polymerization system in proportion to the amount of unmodified polyolefin wax having the specific composition. In addition, molecular weight regulators such as hydrogen may be added during polymerization.

An unmodified polyolefin wax is obtained by treating the polymerization solution polymerized in the above-mentioned manner by a conventional method.

In addition, the polymer obtained by the method can be further purified by the following methods: degassing under vacuum at a temperature above the melting point; temporarily dissolved in solvents such as toluene, xylene, hexane, heptane, etc. After the medium, a polar solvent such as methanol or acetone is added, and a method of filtering to remove the low molecular weight portion; or a method of removing the high molecular weight portion or the low molecular weight portion after all dissolved in the solvent and precipitating at a specific temperature.

When the polyolefin wax (B1) is an unmodified polyolefin wax, the number average molecular weight (Mn) and the limiting viscosity [η] may change if the polymerization temperature during polymerization is increased or the hydrogen concentration is increased. The low tendency can be controlled within the range. Or it can be adjusted by the amount of the organoaluminum oxy compound used as the cocatalyst and/or the ionized ionic compound. Furthermore, it can be adjusted by purification after polymerization.

The content of units derived from ethylene or each α-olefin can be controlled by the type of catalyst, polymerization temperature, etc., in addition to adjusting the formulation amount during polymerization.

The Mw/Mn of the polyolefin wax (B1) (unmodified polyolefin wax) can be controlled by the type of catalyst, polymerization temperature, and the like. Chigler is usually used in polymerization. For the nat catalyst or the metallocene catalyst, in order to set the Mw/Mn in a preferable range, it is preferable to use a metallocene catalyst. In addition, it can also be purified by a method such as solvent fractionation or distillation by fractionating the difference in the solubility of the solvent, so as to be within a preferable range.

The softening point of polyolefin wax (B1) (unmodified polyolefin wax) can be adjusted by the composition of ethylene or α-olefin. For example, if it is a copolymer of ethylene and α-olefin, by increasing the amount of α-olefin Content, while obtaining a tendency for the softening point to decrease. In addition, it can also be controlled by the type of catalyst or polymerization temperature. Furthermore, it can be adjusted by purification after polymerization.

The density of the polyolefin wax (B1) (unmodified polyolefin wax) can be adjusted by the composition of ethylene or α-olefin and the polymerization temperature and hydrogen concentration during polymerization.

(Modified polyolefin wax)

As described above, the polyolefin wax (B1) may be a modified polyolefin wax, that is, a graft modified product of the polyolefin wax (for example, an unsaturated carboxylic acid derivative monomer modified product (maleic anhydride modified product, etc. ), or styrene-modified product), may also be the air oxide of the polyolefin wax. As the unmodified polyolefin wax used as these raw materials, the unmodified polyolefin wax having the above physical properties is suitably used.

. Air oxide of polyolefin wax

The air oxide of polyolefin wax is the side of the unmodified polyolefin wax that will be the raw material It is obtained by stirring in a molten state while bringing it into contact with oxygen or an oxygen-containing gas. The unmodified polyolefin wax used as a raw material is usually in a molten state at a temperature of 130°C to 200°C, preferably 140°C to 170°C.

In the case of oxidative modification, the unmodified polyolefin wax is stirred in the molten state while being brought into contact with oxygen or an oxygen-containing gas to perform an oxidation reaction. However, in the description of "oxygen or oxygen-containing gas" in this specification, It contains not only pure oxygen (oxygen obtained by ordinary liquid air fractionation or electrolysis of water, but also other components of the degree of impurities), but also a mixed gas of pure oxygen and other gases, such as air or ozone.

As a method of contacting the unmodified polyolefin wax with oxygen or the like, specifically, a method of continuously supplying an oxygen-containing gas from the lower part of the reactor and bringing it into contact with the unmodified polyolefin wax. In this case, the oxygen-containing gas is preferably supplied so that the amount of oxygen corresponding to 1.0 NL to 8.0 NL per minute per 1 kg of the raw material mixture.

The acid value (JIS K5902) of the air oxide of the polyolefin wax obtained in the above manner is preferably 1 mgKOH/g~100 mgKOH/g, more preferably 20 mgKOH/g~90 mgKOH/g, even more preferably 30 mgKOH/g~87 mgKOH /g. Here, the acid value means the number of mg of potassium hydroxide required for neutralization per 1 g of sample.

When the acid value of the air oxide of the polyolefin wax is within the above range, the appearance, processability, heat resistance, and mechanical strength are particularly excellent. The reason is believed to be that the balance of the compatibilizing effect of the natural fiber (C) and the resin (A) is excellent. The detailed mechanism is not clear, but it is believed that if the acid value is within the range, the affinity of the natural fiber (C) and the compatibilizer (B) is moderately improved, and the fusion with the resin (A) is also maintained, As a result, the uniformity of the entire system is improved, the dispersibility of the natural fiber (C) becomes good, the appearance or processability becomes good, and the appearance is improved. By this, even if a low molecular weight wax is added, the heat resistance or mechanical strength as a resin composition becomes high.

In addition, especially in the case of obtaining a resin composition excellent in workability or appearance, the acid value range of the air oxide of the polyolefin wax is preferably 1 mgKOH/g to 55 mgKOH/g, and the lower limit is more preferably 20 mgKOH/g, Especially good is 30mgKOH/g, and the best is 42mgKOH/g. In addition, the upper limit is more preferably 50 mgKOH/g, particularly preferably 48 mgKOH/g, and most preferably 46 mgKOH/g.

On the other hand, when obtaining a resin composition excellent in heat resistance or mechanical strength, the range of the acid value of the air oxide of the polyolefin wax is preferably 40 mgKOH/g to 100 mgKOH/g, more preferably 50 mgKOH/g~ 100mgKOH/g, particularly preferably 60mgKOH/g~100mgKOH/g, particularly preferably 60mgKOH/g~95mgKOH/g, particularly preferably 60mgKOH/g~90mgKOH/g, and particularly preferably 80mgKOH/g~90mgKOH/g.

. Graft modification of polyolefin wax

The graft-modified polyolefin wax may be, for example, modified polyolefin wax (hereinafter, also referred to as acid-modified polyolefin wax (B1')) obtained by acid-grafting unmodified polyolefin wax. Or styrene-modified polyolefin wax modified by grafting with styrene, polyolefin-wax modified by graft modification with these mixtures, and the like. The graft modified products of these polyolefin waxes can be prepared by a conventionally known method. For example, it can be obtained by (1) unmodified polyolefin wax as raw material and (2) unsaturated carboxylic acid or its derivative, styrene, or sulfonate in (3) organic peroxidation Matter equal Melt-kneading in the presence of a combination initiator, or (1) unmodified polyolefin wax as raw material and (2) unsaturated carboxylic acid or its derivative, styrene or sulfonate dissolved in an organic solvent The solution obtained in the middle is kneaded in the presence of (3) an organic peroxide or other polymerization initiator.

For melt kneading, for example, an autoclave, a Henschel mixer, a V blender, a tumbler blender, and a ribbon blender are used. ), single-shaft extruder, multi-shaft extruder, kneader, Banbury mixer, etc. In these devices, if an batch-type device with excellent melt-kneading performance such as an autoclave is used, the components can be more evenly dispersed. Polyolefin wax from reaction. Compared with the continuous type, the batch type is easier to adjust the residence time. In addition, since the residence time can be extended, it is easier to improve the modification rate and the modification efficiency, which is the best form in the present invention.

In the case where the acid-modified polyolefin wax (B1') is a wax modified by grafting with an unsaturated carboxylic acid derivative-based monomer and a styrene-based monomer, the graft amount ratio is The saturated carboxylic acid derivative monomer)/(styrene monomer)" is preferably 0.01 to 1, more preferably 0.03 to 0.8, and particularly preferably 0.05 to 0.6. When the graft amount ratio is less than 0.01, since the interaction of the unsaturated carboxylic acid derivative-based monomer with the surface of the natural fiber (C) is reduced, it is difficult to improve the impact resistance. In addition, when the graft amount ratio is greater than 1, the melt viscosity of the acid-modified polyolefin wax (B1') becomes high, which makes production difficult.

Examples of unsaturated carboxylic acids or their derivatives used in acid graft modification include methyl acrylate, ethyl acrylate, butyl acrylate, and second-butyl acrylate, Isobutyl acrylate, propyl acrylate, isopropyl acrylate, 2-octyl acrylate, dodecyl acrylate, stearyl acrylate, hexyl acrylate, isohexyl acrylate, phenyl acrylate, 2-chloroacrylate Acrylates such as phenyl ester, diethylaminoethyl acrylate, 3-methoxybutyl acrylate, diethylene glycol ethoxylate acrylate, 2,2,2-trifluoroethyl acrylate; Methyl acrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid-second butyl ester, isobutyl methacrylate, propyl methacrylate, isopropyl methacrylate, methacrylic acid- 2-octyl ester, dodecyl methacrylate, stearyl methacrylate, hexyl methacrylate, decyl methacrylate, phenyl methacrylate, 2-chlorohexyl methacrylate, methyl methacrylate Methacrylates such as diethylaminoethyl acrylate, 2-hexyl ethyl methacrylate, 2,2,2-trifluoroethyl methacrylate; ethyl maleate, cis Maleic acid esters such as propyl crotonate, butyl maleate, diethyl maleate, dipropyl maleate, and dibutyl maleate; Fumaric acid esters such as ethyl fumarate, butyl fumarate, and dibutyl fumarate; maleic acid, fumaric acid, itaconic acid, butylene Dicarboxylic acids such as enoic acid, nadic acid, methylhexahydrophthalic acid; maleic anhydride, itaconic anhydride, citraconic anhydride, allyl succinic anhydride, glutaic anhydride, nadic anhydride, etc. Anhydride etc. Among these compounds, maleic anhydride is preferred. Maleic anhydride has relatively high reactivity with the unmodified polyolefin wax as a raw material, and itself has few large structural changes due to polymerization or the like, and tends to be stable as a basic structure. Therefore, in the case where the compatibilizer (B) is a polyolefin wax modified with maleic anhydride, the polyolefin wax modified with maleic anhydride remains stable under the high-temperature environment in the forming process In a state where it can efficiently act on natural fibers (C) surface. As a result, it is considered that the balance of appearance, heat resistance, processability, and mechanical strength as the resin composition becomes good.

The acid value (JIS K5902) of the acid-modified polyolefin wax (B1') obtained in the above manner is preferably 1 mgKOH/g to 100 mgKOH/g, more preferably 20 mgKOH/g to 90 mgKOH/g, and still more preferably 30 mgKOH/ g~87mgKOH/g. Here, the acid value means the number of mg of potassium hydroxide required for neutralization per 1 g of sample.

If the acid value of the acid-modified polyolefin wax (B1') is within the above range, the appearance, processability, heat resistance, and mechanical strength are particularly excellent. The reason is considered to be that the balance between the compatibilizing effect of the natural fiber (C) and the resin (A) is excellent. The detailed mechanism is not clear, but it is considered that if the acid value is within the range, the affinity of the natural fiber (C) and the compatibilizer (B) is moderately improved, and the fusion with the resin (A) is also maintained, so the result In order to improve the uniformity of the entire system, the dispersibility of the natural fiber (C) becomes good, the appearance or processability becomes good, and the appearance is improved. From this, it is considered that even if a low-molecular-weight wax is added, the heat resistance or mechanical strength of the resin composition is improved.

In addition, especially in the case of obtaining a resin composition having excellent processability or appearance, the acid value of the acid-modified polyolefin wax (B1′) is preferably in the range of 1 mgKOH/g to 55 mgKOH/g, and the lower limit is more preferably 20 mgKOH /g, especially good is 30mgKOH/g, the best is 42mgKOH/g. In addition, the upper limit is more preferably 50 mgKOH/g, particularly preferably 48 mgKOH/g, and most preferably 46 mgKOH/g.

On the other hand, when obtaining a resin composition excellent in heat resistance or mechanical strength, the acid value of the acid-modified polyolefin wax (B1′) is preferably in the range of 40 mgKOH/g to 100 mgKOH/g, more preferably 50 mgKOH /g~100mgKOH/g, Especially preferred is 60mgKOH/g~100mgKOH/g, especially preferred 60mgKOH/g~95mgKOH/g, especially preferred 60mgKOH/g~90mgKOH/g, and especially preferred 80mgKOH/g~90mgKOH/g.

Examples of styrenes in the case where polyolefin wax is graft-modified with styrenes include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methyl Styrene, p-chlorostyrene, m-chlorostyrene and p-chloromethylstyrene, 4-vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5- Vinylpyridine, 2-isopropenylpyridine, 2-vinylquinoline, 3-vinylisoquinoline, N-vinylcarbazole, N-vinylpyrrolidone, etc.

As the content of styrene when the polyolefin wax is graft-modified with styrene, when the polyolefin wax is set to 100 parts by mass, it is preferably 1 part by mass to 500 parts by mass, more preferably 5 Mass parts to 200 parts by mass, more preferably 20 parts by mass to 160 parts by mass, particularly preferably 22 parts by mass to 30 parts by mass. If the styrene content of the modified polyolefin wax is within the above range, the compatibility between the modified polyolefin wax and the natural fiber (C) becomes good, and excessive interactions such as increase in viscosity etc. Since it is suppressed, the balance of workability, appearance, heat resistance, and mechanical strength is excellent.

In addition, the polyolefin wax or the graft-modified polyolefin wax may also be modified with sulfonate. In this case, the modified mass is preferably 0.1 millimole to 100 millimole per 1 g of polymer, and particularly preferably 5 millimole to 50 millimole. When the modified mass of the sulfonate is within the above range, the dispersibility of the natural fiber (C) becomes good, and the mechanical strength of the molded body obtained from the resin composition is improved.

The acid-modified polyolefin wax (B1') may also be a commercially available product. Acid modification of commercial products Examples of high-quality polyolefin wax (B1') include Diacarna-PA30 (Mitsubishi Chemical Corp.), high-quality wax (Hi-Wax) acid treatment type 2203A (Mitsui Chemical Co., Ltd.), and oxidation Paraffin (Japanese fine wax (share)), etc.

2-3. Petroleum resin (B2)

The compatibilizer (B) may be petroleum resin (B2) as described above. Examples of the petroleum resin (B2) include, for example, an aliphatic petroleum resin using the C5 fraction of tar naphtha as the main raw material, an aromatic petroleum resin using the C9 fraction as the main raw material, and these Copolymerized petroleum resin. That is, C5 series petroleum resin (resin obtained by polymerizing the C5 fraction of naphtha decomposing oil), C9 series petroleum resin (resin obtained by polymerizing the C9 fraction of naphtha decomposing oil), C5C9 Copolymerized petroleum resin (resin obtained by copolymerizing the C5 fraction and C9 fraction of naphtha decomposition oil). When the compatibilizer is petroleum resin (B2), the kneadability with other components becomes good.

The petroleum resin (B2) as the compatibilizer (B) is preferably not subjected to hydrogenation treatment (hydrogenation treatment). Petroleum resins that have not been hydrogenated generally have excellent heat resistance. Therefore, even after the thermal step of forming, the function as a compatibilizer will not be impaired.

In addition, examples of the petroleum resin (B2) include styrene, indene, coumarone containing tar naphtha fraction, and coumarone-indene such as dicyclopentadiene. ) Series resins; alkylphenol resins represented by the condensate of tertiary butylphenol and acetylene; xylene series resins obtained by reacting o-xylene, p-xylene or m-xylene with formalin, etc.

Among the petroleum resins (B2), vinyl aromatic petroleum resins are preferred. Examples of vinyl aromatic petroleum resins include: homopolymers of vinyl aromatic hydrocarbons; or vinyl aromatic hydrocarbons and fractions of 4 and 5 carbon atoms by-produced from petroleum purification and petroleum decomposition Copolymerized resin of any fraction in

Vinyl aromatic petroleum resins, examples of vinyl aromatic hydrocarbons include isopropenyl toluene, styrene, vinyl toluene, α-methyl styrene, etc., these compounds may be used alone, or two The above is used in combination, but among these, particularly preferred is isopropenyl toluene. In the vinyl aromatic petroleum resin, when the vinyl aromatic hydrocarbon is isopropenyl toluene, the kneading property of the resin composition becomes particularly good.

C4 and C5 fractions (hereinafter referred to as C4 and C5 fractions) copolymerized with vinyl aromatic hydrocarbons are by-produced during petroleum purification and petroleum decomposition; the boiling point at normal pressure is- 15℃~+45℃, including 1-butene, 2-butene, isobutene, butadiene, 1-pentene, 2-pentene, cyclopentene, 1,3-pentadiene (1,3 -piperylene), isoprene, cyclopentadiene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, etc. .

The fractions of carbon atoms 4 and 5 which are copolymerized with vinyl aromatic hydrocarbons are any fractions selected from C4 fractions and C5 fractions. Of course, the C4 fractions and C5 fractions may be C4 fractions other than butadiene. C5 fractions other than isoprene, C5 fractions other than cyclopentadiene, etc.

The polymerization reaction to obtain the vinyl aromatic petroleum resin may be carried out in the presence of a polymerization catalyst. The polymerization catalyst is, for example, the commonly used Friedel- Friedel-Crafts catalyst, examples of Friedel-Crafts catalyst include aluminum chloride, aluminum bromide, ethyl aluminum dichloride, boron trifluoride, boron trifluoride Various complexes, etc. The polymerization reaction can be carried out in a suitable solvent. Examples of suitable solvents include hydrocarbon solvents such as pentane, hexane, octane, kerosene, cyclopentane, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene and mesitylene. The polymerization temperature is usually -50°C to +80°C. In addition, vinyl aromatic petroleum resins can also be graft-modified with unsaturated carboxylic acid derivative-based monomers in the same manner as polyolefin waxes.

2-4. Other compatibilizers (B)

In addition, as the compatibilizer (B), in addition to the polyolefin wax (B1) and the petroleum resin (B2), the following rosin-based resins and terpene-based resins can also be used. Examples of the rosin-based resin include natural rosin, polymerized rosin, modified rosin modified by maleic acid, fumaric acid, (meth)acrylic acid, and the like, and rosin derivatives. In addition, examples of the rosin derivative include the above-mentioned natural rosin, polymerized rosin, or modified rosin esterified products, phenol-modified products, and esterified products thereof. Furthermore, the rosin derivative may also include these hydrides.

Examples of the terpene-based resin include resins including α-pinene, β-pinene, limonene, dipentene, terpene phenol, terpene alcohol, and terpene aldehyde. Aromatic modified terpene-based resins obtained by polymerizing aromatic monomers such as methylstyrene and isopropenyltoluene with α-pinene, β-pinene, limonene, dipentene, etc. In addition, these hydrides can also be cited.

In addition, from the viewpoint of excellent weather resistance and discoloration resistance, one or more resins selected from the group consisting of rosin-based resins, terpene-based resins, and petroleum resins are Preferably it is a hydrogenated derivative.

In addition, these petroleum resins, rosin-based resins, and terpene-based resins may be acid-grafted and oxidatively modified in the same manner as the polyolefin wax (B1).

2-5. Form of Compatibilizer (B)

When preparing the resin composition, the compatibilizer (B) may be solids such as powder, lozenges, and lumps, or may be dispersed in water or a solvent, or dissolved in water or a solvent. The method of dissolving or dispersing the compatibilizing agent (B) in water or an organic solvent is not particularly limited, and examples include a method of dissolving and dispersing the compatibilizing agent (B) in water or an organic solvent while stirring; or With stirring, the temperature of the mixture of the compatibilizer (B) and water or the organic solvent is increased, and the method is gradually cooled from a completely or incompletely dissolved state to form fine particles. The method of micronization can be exemplified by the following method: the solvent composition is set in advance so as to precipitate at 60°C to 100°C, and the average cooling rate during this period is adjusted to 1°C/hour to 20°C/hour, preferably 2°C /Hour~10℃/hour, cooling and precipitation. Alternatively, after dissolving the compatibilizing agent (B) in the affinity solvent, a lean solvent may be added to the solution to precipitate it. In addition, after the water or the organic solvent is removed from the solution in which the compatibilizer (B) is dispersed in water or a solvent, it can be used by dissolving and dispersing with an arbitrary solvent.

3. Natural fiber (C)

Natural fiber (C) is preferably other than wood flour, wood fiber, bamboo, bamboo fiber, cotton, cellulose, nanocellulose, wool, or agricultural product fiber (wheat straw, hemp, flax, kenaf) , Kapok, jute, ramie, sisal hemp, henequen, corn fiber or coconut palm, or In addition to the wood pulp of tree fruit shells or rice husks, needle-bleached kraft pulp (NBKP), and broad-leaved tree bleached kraft pulp (LBubholz Bleached Kraft Pulp, LBKP), Manila Natural pulp, such as Manila hemp, paper mulberry, paper bush, and goose skin, non-wood pulp, rayon, cotton, etc. More preferably, it is wood flour, wood fiber, bamboo, bamboo fiber, or nanocellulose. If manufacturing cost and performance balance are considered, wood powder, wood fiber, and wood powder are the most preferable.

Wood flour, wood fiber, etc. are not particularly limited to logs or tree species, and wood materials generated as industrial waste in the wood industry, or wood powder and wood fibers obtained from unused wood materials can be used. The wood powder may be wood powder obtained from one tree species, or may be a mixed powder containing two or more tree species. Since wood flour easily absorbs moisture in the air, it is desirable to heat and dry in advance to reduce the moisture in the wood flour. For example, it is 20% by mass or less, preferably 1% by mass or less. By reducing the water concentration in the wood powder, the mixing property (kneading property) of the wood powder and the resin (A) can be improved, a more uniform resin composition can be obtained, and it can exert good performance as a synthetic wood. The heating and drying condition is preferably a condition using a temperature of 100°C to 130°C for 30 minutes to 4 hours.

4. Other resins

Furthermore, the resin composition of the present invention may include other polymers other than the resin (A) as optional components within a range that does not impair the object of the present invention. The formulation amount is not particularly limited, but it is preferably about 0.1 to 30 parts by mass relative to 100 parts by mass of the resin (A).

5. Foaming agent

The resin composition may contain a foaming agent (D). The foaming agent (D) may be used alone or in combination of two or more. As the foaming agent (D), a foaming agent generally used in foam molding can be widely used, and specific examples include inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, and ammonium nitrite. ; N,N'-dimethyl-N,N'-dinitroso-p-xylylenediamine, N,N'-dinitroso pentamethylenetetramine (N,N'-dinitroso pentamethylene tetramine , DPT) and other nitroso compounds; azodicarbonic acid amide (ADCA), azobisisobutyronitrile (AIBN), azocyclohexanonitrile, azodiaminobenzene, azo Azo compounds such as barium azodicarboxylate; benzenesulfonyl hydrazide, tosyl hydrazide, p,p'-oxybis (benzene sulfonyl hydrazide) (p,p'-oxybis (benzene sulfonyl hydrazide), OBSH), di Sulfonyl hydrazide compounds such as phenylsulfon-3,3'-disulfonylhydrazine; calcium azide, 4,4-diphenyl disulfonyl azide, p-toluenesulfonyl azide and other azide compounds. Among these compounds, nitroso compounds, azo compounds, and azide compounds are preferred.

When the resin composition contains a foaming agent (D), it is 1 to 20 parts by weight, preferably 1 part by weight, relative to 100 parts by weight of the total amount of the thermoplastic resin (A) and the compatibilizer (B). Parts to 15 parts by weight, more preferably 1 part to 10 parts by weight. If the foaming agent (D) is contained in the above ratio, a molded body having a high bubble ratio and good compressive strength is obtained.

6. Filler

The resin composition of the present invention may contain a filler for the purpose of improving the rigidity of the obtained synthetic wood.

Examples of fillers include glass fiber, carbon fiber, silica fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, carbon black, graphite, silica, glass beads, silicate (calcium silicate, talc) , Clay, etc.), metal oxides (iron oxide, titanium oxide, magnesium oxide, aluminum oxide, etc.), metal carbonates (calcium sulfate, barium sulfate), and various metal (magnesium, silicon, aluminum, titanium, copper, etc.) powder , Mica, glass flake, etc. Furthermore, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium titanate, calcium sulfite, asbestos, Montmorillonite, bentonite, molybdenum sulfide, etc.

In addition, it may be an organic filler, and examples of the organic filler include lignin, starch, and products containing the same.

These fillers may be used alone or in combination of two or more. The addition amount of these fillers is not particularly limited, and it is usually 70 parts by mass or less, and more preferably 30 parts by mass or less relative to 100 parts by mass of the total mass of the resin (A) and the compatibilizer (B).

7. Other additives

The resin composition of the present invention may contain additives other than the foaming agent and the filler. Other additives include those known in the field of polyolefins, and examples include: nucleating agents, antiblocking agents, pigments, dyes, lubricants, plasticizers, mold release agents, and anti-blocking agents. Oxidizing agent, flame retardant, ultraviolet absorber, antibacterial agent, surfactant, antistatic agent, weathering stabilizer, heat stabilizer, anti-slip agent, foaming agent, crystallization aid, anti-fogging agent, anti-aging agent, salt Acid absorbers, impact modifiers, crosslinking agents, co-crosslinking agents, crosslinking aids, adhesives, softeners, processing aids, etc.

These additives may be used alone or in combination of two or more. The content of these additives is not particularly limited according to the application within the range not detrimental to the object of the present invention, and the additives to be formulated are preferably respectively 100 parts by mass relative to the total mass of the resin (A) and the compatibilizer (B). It is about 0.05 to 70 parts by mass. The upper limit is more preferably 30 parts by mass.

As the nucleating agent, in the case where the resin (A) is an olefin polymer, in order to further improve the moldability of the olefin polymer, that is, to increase the crystallization temperature and accelerate the crystallization rate, a known nucleating agent can be used. Specific examples include dibenzylidene sorbitol-based nucleating agents, phosphate salt-based nucleating agents, rosin-based nucleating agents, metal benzoate-based nucleating agents, fluorinated polyethylene, 2,2- Sodium methylene bis(4,6-di-tert-butylphenyl) phosphate, pimelic acid or its salt, 2,6-naphthoic acid dicarboxylic acid dicyclohexylamide, etc.

The formulation amount of the nucleating agent is not particularly limited, and is preferably 0.1 to 1 part by mass relative to 100 parts by mass of the total mass of the resin (A) and the compatibilizer (B). The nucleating agent can be added as appropriate during polymerization, after polymerization, or during molding.

As the anti-caking agent, a known anti-caking agent can be used. Specific examples include fine powder silica, fine powder alumina, fine powder clay, powdered or liquid silicone resin, tetrafluoroethylene resin, fine powder cross-linked resin, such as cross-linked acrylic acid, methacrylic acid Resin powder, etc. Among these, fine powder silica and crosslinked acrylic and methacrylic resin powders are preferred.

Pigments may include: inorganic pigments (titanium oxide, iron oxide, chromium oxide, sulfur Cadmium, etc.), organic pigments (azo lake (azo lake) system, thioindigo (thioindigo) system, phthalocyanine (phthalocyanine) system, anthraquinone (anthraquinone) system). Examples of the dye include azo-based, anthraquinone-based, and triphenylmethane-based. The addition amount of these pigments and dyes is not particularly limited. The total amount is generally 5 parts by mass or less relative to 100 parts by mass of the total mass of the resin (A) and the compatibilizer (B), preferably 0.1 parts by mass to 3 parts by mass Copies.

Lubricants, for example, can be used: waxes other than the compatibilizer (vaseline, tall oil, castor oil, rapeseed oil, soybean oil, coconut oil (cocoanut oil), beeswax, paraffin, flowing paraffin, carnauba wax, montanic acid wax, microcrystalline wax, etc.), higher fatty acids (stearic acid, etc.) , And its metal salts (zinc stearate, calcium stearate, etc.), higher alcohols (stearyl alcohol, etc.), its esters (butyl stearate, etc.), higher fatty acid amide (stearate amide, etc.) , Process oil, various lubricants. As the lubricant, for example, Lucant (manufactured by Mitsui Chemicals) is used. Lucant can also be upgraded. The lubricant is preferably used at a ratio of 0.05 parts by mass to 10 parts by mass relative to 100 parts by mass of the total mass of the resin (A) and the compatibilizer (B). More preferably, it is used at a ratio of 0.05 parts by mass to 2 parts by mass, and particularly preferably, it is used at a ratio of 0.05 parts by mass to 1 part by mass.

Examples of plasticizers include aromatic carboxylic acid esters (dibutyl phthalate, etc.), aliphatic carboxylic acid esters (methyl acetyl ricinoleate, etc.), and aliphatic dicarboxylic acid esters (hexane di) Acid-propylene glycol-based polyester, etc.), aliphatic tricarboxylic acid ester (triethyl citrate, etc.), phosphate triester (triphenyl phosphate, etc.), epoxy fatty acid ester (stearic acid epoxy butyl ester) Etc.), petroleum resin.

The antioxidant can use a well-known antioxidant. Specific examples include phenol-based (2,6-di-tert-butyl-4-methylphenol, etc.) and polycyclic phenol-based (2,2'-methylenebis(4-methyl-6- Tertiary butylphenol, etc.), phosphorus series (tetra(2,4-di-tert-butylphenyl)-4,4-biphenylene diphosphate, etc.), sulfur series (thiodipropionate di Lauryl ester, etc.), amine-based (N,N-diisopropyl-p-phenylenediamine, etc.), lactone-based antioxidants, etc.

Examples of the flame retardant include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.), inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus) Wait).

Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, salicylic acid-based, and acrylate-based ultraviolet absorbers.

Examples of antibacterial agents include quaternary ammonium salts, pyridine-based compounds, organic acids, organic acid esters, halogenated phenols, and organic iodine.

The surfactant may include nonionic, anionic, cationic or amphoteric surfactants. Examples of nonionic surfactants include higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts. Non-ionic surfactants such as polyethylene glycol, polyethylene oxide, fatty acid esters of glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbit or sorbitan, polyols Alkyl ethers, alkanolamines, aliphatic amides, and other polyol-type nonionic surfactants. Examples of the anionic surfactant include sulfate ester salts such as alkali metal salts of higher fatty acids, sulfonate salts such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates, and phosphate esters such as higher alcohol phosphate salts. salt. Examples of cationic surfactants include alkyl tris Quaternary ammonium salts such as methyl ammonium salts. Amphoteric surfactants include, for example, amino acid type double-sided surfactants such as higher alkylaminopropionate, and betaine type amphoteric interfaces such as higher alkyl dimethyl betaine and higher alkyl dihydroxyethyl betaine. Active agent.

Examples of the antistatic agent include the aforementioned surfactants, fatty acid esters, and polymer antistatic agents. The polymer antistatic agent may, for example, be polyetheresteramide.

As the crosslinking agent, for example, an organic peroxide can be used.

Examples of organic peroxides include dicumyl organic peroxides, di-third butyl organic peroxides, and 2,5-dimethyl-2,5-di-(third butyl peroxide). Alkanes, 2,5-dimethyl-2,5-di-(third butyl peroxide) hexyne-3, 1,3-bis(third butyl isopropyl peroxide)benzene, 1,1 -Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl organic Peroxide, p-chlorobenzyl peroxide, 2,4-dichlorobenzyl organic peroxide, tert-butyl peroxybenzoate, tert-butyl peroxybenzoate , Third butyl peroxy isopropyl carbonate, diethyl acetyl organic peroxide, lauryl oxy organic peroxide, third butyl cumyl organic peroxide.

Among these compounds, in terms of odor and scorch stability, it is more suitable to use: 2,5-dimethyl-2,5-di-(third butyl peroxy)hexane, 2,5-Dimethyl-2,5-di-(third butyl peroxide) hexyne-3, 1,3-bis(third butyl isopropyl peroxide) benzene, 1,1-bis (Third butyl peroxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(third butyl peroxy) valerate, especially suitable for 1,3- Bis (third butyl isopropyl peroxide) benzene.

100 masses relative to the total mass of the resin (A) and compatibilizer (B) of the present invention Parts, the organic peroxide is preferably used in a ratio of 0.05 parts by mass to 10 parts by mass.

When using organic peroxide for cross-linking treatment, as a cross-linking aid, it can be formulated with sulfur, p-quinone dioxime, p,p'-dibenzoyl quinone dioxime, N-methyl-N-4- Peroxy crosslinking aids such as dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N,N'-m-phenylene di-cis-butadiene diimide, or Divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethyl Multifunctional methacrylate monomers such as acrylate and allyl methacrylate, and multifunctional vinyl monomers such as vinyl butyrate and vinyl stearate.

By using the compound, a uniform and mild cross-linking reaction can be expected. In the present invention, divinylbenzene is particularly suitable. Divinylbenzene is easy to handle, has good compatibility with polymers, and has the function of solubilizing organic peroxides, and functions as a dispersant for organic peroxides. Therefore, a homogeneous cross-linking effect can be obtained, and a dynamically heat-treated product that achieves a balance between fluidity and physical properties can be obtained. The cross-linking aid is preferably used in a ratio of 0.05 parts by mass to 10 parts by mass relative to 100 parts by mass of the total mass of the resin (A) and the compatibilizer (B).

Examples of softeners include coal tar softeners such as coal-tar and coal-tar pitch, synthetic polymer materials such as atactic polypropylene, and dioctyl phthalate. , Dioctyl adipate, dioctyl sebacate and other ester plasticizers, diisododecyl carbonate and other carbonate plasticizers.

The amount of the softener is not particularly limited, and it is preferably an amount of 1 part by mass to 200 parts by mass relative to 100 parts by mass of the total mass of the resin (A) and the compatibilizer (B). The softener not only facilitates processing when preparing the resin composition, but also contributes to the dispersion of carbon black and the like.

8. Preparation method of resin composition

The resin composition of the present invention can be produced by any of various methods by dry blending or melt blending. As a specific method, for example, it is suitable to use the following method: the resin (A), the compatibilizer (B), the natural fiber (C), and other arbitrary components are simultaneously or in any order, using a roller, a V-type blender, The blending is carried out with a Nauta mixer, a Banbury mixer, a kneading roll, a uniaxial or biaxial extruder, etc. Or, by dispersing or dissolving the resin (A), compatibilizer (B), natural fiber (C), and other arbitrary components in any solvent at once, suitable drying methods such as natural drying or forced drying by heating Method for drying to blend.

Generally speaking, melt blending is better in appearance and impact resistance than dry blending. In addition, melt blending also tends to be excellent in appearance and impact resistance by sufficiently kneading. In particular, when two or more compounds are used in combination as a compatibilizer (B), a method of dry blending or melt blending two or more compatibilizers (B) in advance is preferable in terms of operation. For the method of melt blending, the above method or a batch kettle method can be used as appropriate.

The MFR of the resin composition of the present invention measured by JIS K7210: 230°C and a test load of 10 kgf is preferably 0.01 g/10min to 100 g/10min, more preferably 0.1 g/10min to 50 g/10min, and particularly preferably 0.5 g/10min~30g/10min, especially good is 1g/10min~20g/10min, especially good is 3g/10min~15g/10min. If the MFR of the resin composition is within the above range, the processability and heat resistance, The balance of mechanical strength is excellent.

In the resin composition of the present invention, when the resin (A), the compatibilizer (B), and the natural fiber (C) are kneaded using a batch Prasto mill, the maximum torque expression time is T2, and , The maximum torque performance time when mixing resin (A) and natural fiber (C) only with T1, T1 and T2 without using the compatibilizer (B) The ratio (T1/T2) is preferably 0.5 or more, more preferably 0.8 or more, particularly preferably 1.1 or more, and particularly preferably 1.4 or more. The compatibilizer (B) has the effect of improving the dispersibility of natural fibers. However, if it is added in excess, the compatibilizer (B) will be oiled during kneading (compositing), thereby delaying the generation of the maximum torque. The result is T1 /T2 decreases. That is the tendency of kneadability to deteriorate. On the other hand, in the present invention, the resin (A) has good compatibility with the natural fiber (C) and the compatibilizer (B) during compounding, so the increase in the maximum torque is accelerated, and as a result, T1/T2 tends to increase. As a result of this vigorous research, T1/T2 can be set to the above or more by setting the composition ratio as described above.

B. Synthetic wood

The synthetic wood of the present invention can be produced by molding the resin composition into a desired shape by a conventionally known method such as coating, extrusion molding, compression molding, injection molding, and the like. The shape of the synthetic wood is not particularly limited, and is, for example, a film shape, a plate shape, a prism shape, a column shape, or the like.

The synthetic wood as a foam can be produced by melting and heating a resin composition containing a foaming agent (D) (hereinafter also referred to as a “composition for synthetic wood”) and foam molding. Specifically, by supplying the composition for synthetic wood to the melt In the extruder, the foaming agent (D) is thermally decomposed while melting and kneading at an appropriate temperature to generate gas, and the molten composition containing the gas is ejected from the die to form a foam . The melt-kneading temperature and melt-kneading time in this method may be appropriately selected according to the foaming agent and kneading conditions used. Usually, the melt-kneading temperature is 150°C to 230°C, and the melt-kneading time is 1 minute to 60 minutes.

The expansion ratio is not particularly limited, and it is generally 1.3 to 10 times, particularly 1.6 to 6 times, in terms of lightness, cushioning properties from external stress, or appropriate compression strength. In addition, the independent bubble ratio is preferably 50% by volume or more, and particularly preferably 70% by volume or more in terms of good cushioning properties of external force and suitable compression strength.

[Use of synthetic wood]

The synthetic wood of the present invention can be used for the use of existing wood.

For example, it can be used as exterior components of buildings such as outdoor fences, wooden decks, pergola (vine sheds), lattice frames (lattice), interior wall materials, floor boards, ceiling materials, furniture materials, etc. Interior components, other game equipment, etc.

In addition, it can be used as an impact-absorbing member. Specific examples of the impact-absorbing member include health products, nursing care products (eg, anti-falling films, felts and sheets), impact-absorbing pads, and protectors. Protective equipment (e.g. helmet, protection), sporting goods (e.g. sports handle), sports protective gear, brackets, balls, handling equipment (e.g. impact-absorbing handles for transportation, impact-absorbing sheet), industrial Materials (e.g. damping pads, shock-absorbing shock absorbers, shock-absorbing members for footwear, shock-absorbing foams, shock-absorbing films), shock-absorbing members for automobiles (e.g. bumper) Components, buffer components), etc.

Furthermore, it can be suitably used for: instrument panel, console box, meter cover, door lock bezel, steering wheel, power window switch base (power window switch base), center cluster (center cluster), dashboard (dashboard) and other automotive interior components; weather strip, bumper (bumper), bumper guard (bumper guard), side block Side mudguard, body panel, spoiler, front grille, strut mount, wheel cap, center pillar, Door mirrors, center ornaments, body side strips, door strips, window strips, windows, head light covers, tail light covers, windproof parts, etc. Mounting components; various front panels of audio-visual (AV) equipment, etc.; surface decoration materials such as buttons and emblems; housings and display windows of mobile phones, etc. , Buttons and other parts; furniture exterior materials; construction interior materials for walls, ceilings, beds, etc.; exterior walls, fences, roofs, door leaves, eaves, and other construction exterior materials for buildings such as siding ; Surface decoration materials such as window frames, doors, handrails, door sills, door lintels and other furniture; various optical components such as displays, lenses, mirrors, goggles, window glass; various transportation vehicles other than cars such as trams, airplanes, and ships Components for interior and exterior use; and various other uses such as bottles, cosmetic containers, storage boxes and other packaging containers, packaging materials, gifts, small sundries and other groceries.

In addition, it is suitable for electrical insulation materials and industrial Materials, construction materials, etc. Especially suitable for use as: residential components, building skirting boards, surface decorative boards, door materials, outer wall materials, face-washing dressing tables, counter materials, foundation base plates, window frames, wall materials, cornice wood, handrails, handles, structural materials, Civil timber, pillars, alcove pillars, decorative pillars, seismic materials, wallpaper doors and windows ceiling materials, base materials, tatami mats, floors, concrete panels (concrete panels), tread materials, shielding panels, sound insulation panels, furniture box ceilings, Doors, front panel back panel, shelf panels, side drawer panels, curtain panels, decks, back panels, seat panels, kitchen components, waterproof materials, mildew-resistant materials, anti-corrosive materials, sliding window panels, skirt panels, side panels, bathroom units (bath unit), floor pan (floor pan), bathroom ceiling, bathroom wall, bathroom, bucket, sanitary ceramic equipment, toilet seat, toilet lid, home appliances, radio television receiver (radio television receiver), cabinet (cabinet), Stereo cabinet, amp-cabinet, speaker, main board of piano organ, large roof, curved roof, up and down rolling board, etc.

The present invention has the advantage of realizing the effective utilization of wood or unused wood as industrial waste in the wood industry, and is extremely effective in industry.

Furthermore, it can also be used as a member etc. for the following uses. Specific examples include: small mobile mechanisms represented by bicycles and electric assisted bicycles, escalators, elevators, etc., and aviation represented by manned aircraft, drones, ultra-high-speed passenger aircraft, rockets, and satellites. Materials, fuel cell vehicles, fuel cell vehicles, linear motor car and other moving mechanisms, various game equipment, various components of robots, such as signal, electric wire, water pipe, gas pipe ), various infrastructure represented by optical fiber (infrastructure), liquid crystal panels, solar cells, antennas, transistors, office automation (OA) equipment interiors, OA equipment enclosures, bathroom lighting fixtures, umbrellas, raincoats, thermal insulation, paving, paints, barriers , Hydrophilic and hydrophobic control agents, paper materials, tires, shock absorbers, hoses, anti-vibration rubber and other rubber materials, food. Beverage containers, materials for 3D printers, agricultural films, liquid filters, air filters, semiconductor filters, various non-woven materials, musical instruments, speakers, audio materials, wigs, wigs, watches, tombstones, glasses, Sunglasses, wearable terminals, etc.

[Example]

The present invention will be described in detail based on examples, but the present invention is not limited to these examples.

1. Resin (A)

The following (A1) to (A5) are used as the resin (A).

(A1) Using homopolypropylene (the melt flow rate at 230°C and 2.16 kgf is 1.5 g/10 min, the melting point is 165°C, the density is 910 kg/m ³ , and the bending modulus of elasticity is 1200 MPa).

(A2) Using Novatec PP EA6A (made in Japan Polypropylene), the melt flow rate at 230°C and 2.16kgf is 1.9g/10min, the melting point is 165°C, and the density is 900kg/m ³ , The bending modulus of elasticity is 2200MPa).

(A3) Notio SN0285 (manufactured by Mitsui Chemicals Co., Ltd., melt flow rate at 230°C, 2.16kgf is 1.4g/10min, melting point is 154°C, density is 864kg/m ³ , bending elasticity coefficient is 30MPa).

(A4) Using Milastomer 6030NS (manufactured by Mitsui Chemicals Co., Ltd.), the melt flow rate at 230°C and 10kgf is 30g/10min, the melting point is 165°C, the density is 890kg/m ³ , and the bending elastic coefficient is 20MPa).

(A5) Tafmer DF605 (manufactured by Mitsui Chemicals Co., Ltd., melt flow rate at 230°C, 2.16kgf is 0.9g/10min, melting point is <50°C, density is 861kg/m ³ , bending elastic coefficient 20MPa).

In addition, these physical properties were measured under the following conditions, respectively.

<melt flow rate (MFR)>

According to JIS K7210, the measurement was performed under the conditions of 230° C. and 2.16 kgf. Only (A4) Milastomer 6030NS was measured under the conditions of 230°C and 10 kgf in accordance with JIS K7210.

<melting point>

The measurement was performed using DSC-20 (manufactured by Seiko Electronics Co., Ltd.) according to differential scanning calorimetry (DSC). A sample of about 10 mg was sealed in an aluminum pan, and the temperature was increased from -30°C to 200°C at 10°C/min, and the endothermic peak of the obtained curve was determined as the melting point. Prior to this temperature rise measurement, the sample was temporarily heated to about 200°C and held for 5 minutes, and then the temperature was reduced to -30°C at 10°C/min to unify the thermal history of the sample. When there are a plurality of endothermic peaks of the obtained curve, the peak temperature at which the amount of endothermic heat is the largest among the endothermic peaks is taken as the melting point (Tm).

<density>

Measured according to the density gradient tube method of JIS K7112.

<coefficient of bending elasticity>

Measured according to JIS K7171:94.

2. Compatibilizer (B)

As the compatibilizing agent (B), polyolefin wax W1 to polyolefin wax W8 and polyolefin wax W10 to polyolefin wax W15, and the following petroleum resin W9 and calcium stearate W16 shown in Table 1 and Table 2 were used. . The melting point of polyolefin wax W1 is 129°C, and the melting point of polyolefin wax W3 is 136°C. The melting point is measured by the same method as the resin (A). Polyolefin wax W14 is a wax obtained by graft-modifying 20 parts by mass of styrene with respect to 100 parts by mass of polyolefin wax.

The petroleum resin W9 (isopropenyl toluene. C5 fraction copolymer) and polyolefin wax W15 were synthesized by the following method.

In addition, calcium stearate W16 (melting point is 149° C. (the softening point cannot be measured)) does not correspond to the so-called compatibilizer (B) in the present invention.

The composition and physical property value of each compatibilizer (B) are shown in Table 1 and Table 2 together. In addition, the measurement method of the composition and each physical property value is described below.

<Synthesis method of petroleum resin W9>

In an autoclave with an actual capacity of 1270 ml equipped with a stirring wing, a mixture of C5 fraction obtained by thermal decomposition of isopropenyl toluene and naphtha and dehydrated purified toluene (volume ratio: total of monomers) was continuously supplied /Toluene=1/1), and boron trifluoride phenolate complex (10 times equivalent of phenol) diluted to 10-fold with dehydrated purified toluene, polymerized at a reaction temperature of 5℃ 合反应。 He reaction. The weight ratio of isopropenyltoluene to the C5 fraction was set to a 90/10 ratio, the supply amount of the mixture of monomer and toluene was set to 1.0 liter/hour, and the supply amount of the diluted catalyst was set to 80 ml/hour. Then, the reaction mixture was transferred to the second-stage autoclave, and after the polymerization reaction was continued at 5°C, when the total residence time in the first-stage and second-stage autoclaves became 2 hours, continuously The reaction mixture was discharged, and 1 liter of the reaction mixture was collected at a time that was three times the residence time to complete the polymerization reaction. After the polymerization was completed, 1 equivalent of NaOH aqueous solution was added to the collected reaction mixture to deash the catalyst residue. Furthermore, after washing the obtained reaction mixture with a large amount of water 5 times, the solvent and unreacted monomers were distilled off under reduced pressure using an evaporator to obtain isopropenyl toluene. C5 fraction copolymer (petroleum resin W9).

<Synthesis method of polyolefin wax W15>

100 parts by mass of propylene homopolymer particles with an MFR (at 230°C and a load of 2.16 kg) of 0.6 g/10 min, a melting point of 160°C, and an average particle size of 380 μm were added to a planetary mixer with a capacity of 2 liters ) (Manufactured by Inoue Co., Ltd., PLM-2), heating was performed in an oil bath at 125°C while stirring in a nitrogen atmosphere. In this state, a solution prepared by dissolving 15 parts by mass of maleic anhydride in 35 parts by mass of toluene was added dropwise in a planetary mixer over 4 hours. At the same time, it took 2 hours and 40 minutes to dropwise dissolve 12.3 parts by mass of third butyl isopropyl peroxymonocarbonate (Nippon Oil Co., Ltd. Pabuzier (Perbutyl) I) as an organic peroxide. Solution in 3.5 parts by mass of toluene. After the toluene solution of maleic anhydride was added dropwise, the heating was continued for 1 hour. Stir to make the reaction knot bundle. During the reaction, the planetary mixer was always set under a nitrogen atmosphere. After the reaction is completed, cooling is performed to extract the contents of the planetary mixer. Acetone was added thereto, and the total volume was set to 1 liter. After stirring at room temperature for 10 minutes, it was filtered. The same operation was repeated 4 times in total, and vacuum drying was performed at 70°C for 5 hours to obtain polyolefin wax W15.

<Composition of polymer>

The content ratio of the constituent unit derived from ethylene of the compatibilizer (B) and the constituent unit derived from the α-olefin having 3 to 4 carbon atoms is determined by analysis of ¹³ C-NMR spectrum. In addition, in Tables 1 and 2, C3 means propylene, C2 means ethylene, and C4 means 1-butene.

<Mn and Mw/Mn>

The number average molecular weight Mn and molecular weight distribution (Mw/Mn) of polyolefin wax W1 to polyolefin wax W8 and polyolefin wax W10 to polyolefin wax W15 were determined by GPC measurement. The measurement was performed under the following conditions. In addition, the number average molecular weight Mn and the weight average molecular weight Mw were determined using a commercially available monodisperse standard polystyrene to prepare a standard curve.

Apparatus: Gel Permeation Chromatograph Alliance GPC2000 (made by Waters)

Solvent: o-dichlorobenzene

Column: TSKgel GMH6-HT×2, TSKgel GMH6-HTL column×2 (all made by Tosoh)

Flow rate: 1.0ml/min

Sample: 0.15mg/mL o-dichlorobenzene solution

Temperature: 140℃

In addition, the number average molecular weight Mn and molecular weight distribution (Mw/Mn) of petroleum resin W9 were also determined by GPC measurement. The measurement was performed under the following conditions. In addition, the number average molecular weight Mn and the weight average molecular weight Mw were determined by using a commercially available monodisperse standard polystyrene to prepare a standard curve.

Device: GPC HLC-8320 (manufactured by Tosoh Corporation)

Solvent: tetrahydrofuran

Column: TSKgel G7000×1, TSKgel G4000×2, TSKgel G2000×1 (all made by Tosoh)

Flow rate: 1.0ml/min

Sample: 20mg/mL tetrahydrofuran solution

Temperature: room temperature

<softening point>

Measured according to JIS K2207.

<density>

It was measured by the density gradient tube method of JIS K7112.

<acid value>

Measured according to JIS K5902.

3. Natural fiber (C)

As the natural fiber (C), wood powder with an average particle diameter controlled to 300 μm was used.

[Example 1 to Example 2, Comparative Example 1]

(Preparation of resin composition)

Add 50 parts by mass of resin (A) (A1: homopolypropylene), and 50 parts by mass One part of natural fiber (C) (wood flour) and two parts by mass of compatibilizer (B) shown in Table 3 (polyolefin wax W1 or polyolefin wax W2) were dry blended. However, in Comparative Example 1, no compatibilizer (B) was added.

Then, using a co-rotating twin-screw extruder HK25D (φ25 mm, L/D=41) manufactured by Parker Corporation, melt-kneading was performed. The screw speed was 150 rpm, the feed rate was 2 kg/h, the outlet temperature was 210° C., and air cooling was performed on a belt conveyor to form a strand.

(Evaluation of resin composition)

The MFR, torque, resin pressure, mucus, smoke, and flow rate curve (viscosity) of the obtained resin composition were evaluated by the following methods. Table 3 shows the results. In addition, a photograph of the appearance of the strand obtained from this resin composition is shown in FIG. 1. FIG. 1 shows the strands in Example 1, Example 2, and Comparative Example 1 from the left. The strand of Example 1 was excellent in smoothness (evaluated as ○), the strand of Example 2 had surface roughness slightly (evaluated as Δ), and the strand of Comparative Example 1 was confirmed to have large surface roughness (evaluated as ×).

<MFR>

The MFR of the obtained resin composition was measured under the conditions of 230°C and 10 kgf in accordance with JIS K7210.

<torque>

Thirty minutes after the start of melt kneading, the value of the twin-screw extruder when the operating conditions were stable was read.

<resin pressure>

Thirty minutes after the start of melt kneading, the value of the twin-screw extruder when the operating conditions were stable was read.

<mucus>

Thirty minutes after the start of melt-kneading, at the exit of the biaxial kneading machine, it was visually confirmed whether or not mucus (scorched resin, low-molecular-weight substance, additives) was generated, and evaluated as follows.

○: 30 minutes after the start of the compound, there was no accumulation of mucus at the outlet of the twin-screw kneader.

×: 30 minutes after the start of the compound, mucus accumulated at the exit of the twin-screw kneader.

<smoke>

After the start of the melt-kneading, the smoke generated until the end was visually confirmed.

○: Basically not generated.

×: Produced in large quantities.

<flow curve>

For the obtained resin composition, according to JIS K7199, the viscosity (Pa.s) under the conditions of 230° C. and the extrusion speed of 2 mm/min was determined using the capillary size, L=30 mm, and D=1.00 mm. Among them, the system without the addition of the compatibilizer (Comparative Example 1) did not show strands from the nozzle due to poor flow, so the value could not be obtained.

[Evaluation of Example 1 to Example 2, Comparative Example 1]

Compared with Comparative Example 1 not containing a compatibilizer (B), the MFR of Examples 1 and 2 containing a compatibilizer (B) decreased, and a slight increase in torque and resin pressure was observed, and the flow rate was confirmed. There is no problem with the flowability in the curve measurement, and the appearance is also excellent. It is considered that the reason is that the fluidity of the resin composition under heating becomes uniform by the action of the compatibilizer (B) on the wood powder (C). In addition, the appearance of the strand of Example 1 is more excellent than that of Example 2, and it is considered that the reason is that the Mn of the polyolefin wax W1 as a compatibilizer (B) is in a particularly preferable range.

[Example 3 to Example 6, Comparative Example 2]

(Preparation of resin composition)

The strands of the resin composition X1 to the resin composition X3 obtained in Example 1, Example 2, and Comparative Example 1 were cut to produce pellets. Then, these particles were dry blended at the ratio shown in Table 4 to obtain a resin composition. Among them, Comparative Example 2 did not incorporate a compatibilizer (B).

[Example 7 to Example 18]

(Preparation of resin composition)

50 parts by mass or 70 parts by mass of resin (A) (A1: homopolypropylene), and 50 parts by mass or 30 parts by mass of natural fiber (C) (wood flour), compatibilizer (B), as shown in Table 5 Dry blending was performed with the mass ratio shown in Table 6.

Then, using a co-rotating twin-screw extruder HK25D (φ25 mm, L/D=41) manufactured by Paka Corporation, melt-kneading was performed. The screw speed was set to 150 rpm, the feed rate was 2 kg/h, and the outlet temperature was 210° C. The belt conveyor was air-cooled to form strands. Cut to make particles.

[Example 19 to Example 25]

To 50 parts by mass of resin (A) (A1: homopolypropylene) and 50 parts by mass of natural fiber (C) (wood flour), two kinds of compatibilizers were added at the mass ratio shown in Table 7 to perform dry process Blending. Then, using a co-rotating twin-screw extruder HK25D (φ25 mm, L/D=41) manufactured by Paka Corporation, melt-kneading was performed. The screw speed was 150 rpm, the feed rate was 2 kg/h, the outlet temperature was 210° C., and air cooling was performed on the belt conveyor to form strands. Cut to make particles.

[Example 26 and Comparative Example 3]

To 50 parts by mass of resin (A) (A1: homopolypropylene) and 50 parts by mass of natural fiber (C) (wood flour), 2 parts by mass of compatibilizer (B) shown in Table 8 was added ( (Polyolefin wax W8) or (calcium stearate W16)) for dry blending. Then, using a co-rotating twin-screw extruder HK25D (φ25 mm, L/D=41) manufactured by Paka Corporation, melt-kneading was performed. The screw speed was 150 rpm, the feed rate was 2 kg/h, the outlet temperature was 210° C., and air cooling was performed on the belt conveyor to form strands. Cut to make particles.

(Evaluation of resin composition)

[Production of test piece]

After drying the granular resin compositions obtained in Examples 3 to 26, Comparative Example 2, and Comparative Example 3 at 100°C for 4 hours, an injection molding machine (Niigata (NNigata) NN100, Niigata Machinery) was used. Manufactured by Niigata Machine Techno), injection molding was carried out under the conditions of a barrel temperature of 190°C, a screw rotation speed of 60 rpm, an injection pressure of 180 MPa, and a mold temperature of 60°C to produce test pieces.

[Evaluation of test piece]

For the obtained test piece, the appearance, tensile test (tensile strength, elongation), bending test (bending strength, deformation, bending modulus of elasticity), Charpy impact test (room temperature and -30°C) were performed as follows 1. Measurement of load deformation temperature and evaluation of wood powder dispersion. The evaluation results are shown in Table 4 to Table 8.

<Appearance>

◎: The surface of the injection molded product is uniform.

○: The unevenness of the surface of the injection molded product is small.

△: There is much unevenness on the surface of the injection molded product.

×: There is much unevenness on the surface of the injection molded product, and the molded product is discolored.

<Tensile test (tensile strength, elongation)>

Based on JIS K-7162, the tensile strength and tensile elongation were measured under the conditions of a load range of 2 kN and a test speed of 50 mm/min. The tensile strength and tensile elongation were evaluated according to the following criteria.

. Tensile Strength

◎: The tensile strength is 39 MPa or more.

○: The tensile strength is 37 MPa or more and less than 39 MPa.

△: The tensile strength is 25 MPa or more and less than 37 MPa.

×: The tensile strength is less than 25 MPa.

. Tensile elongation

○: The tensile elongation is 2.8% or more.

△: The tensile elongation is 2.0% or more and less than 2.8.

×: The tensile elongation is less than 2.0%.

<Bending test (bending strength, deformation, bending elastic coefficient)>

Based on JIS K-7171, the bending strength, deformation, and bending elasticity coefficient were measured under the conditions of a load range of 200 N, a test speed of 2 mm/min, and a bending span of 64 mm. These were evaluated based on the following criteria.

. Bending strength

◎: The bending strength is 58 MPa or more.

○: The bending strength is 55 MPa or more and less than 58 MPa.

△: The bending strength is 37 MPa or more and less than 55 MPa.

×: The bending strength is less than 37 MPa.

. Deformation

○: The deformation is 5.0% or more.

△: The deformation is 3.0% or more and less than 5.0%.

×: The deformation is less than 3.0%.

. Bending elastic coefficient

○: The bending elastic coefficient is 3700 MPa or more.

×: The bending elastic coefficient is less than 3700 MPa.

<Charpy impact test>

According to JIS K7111, the Charpy impact test at room temperature and -30°C was performed. The notch is set to machining, and the test piece is set to 10 mm (width)×4 mm (thickness)×80 mm (length). These were evaluated based on the following criteria.

. Charpy impact value (room temperature) (kJ/m ² )

◎: The Charpy impact value is 4.1 kJ/m ² or more.

○: The Charpy impact value is 3.8 kJ/m ² or more and less than 4.1 kJ/m ² .

△: Charpy impact value 3.0kJ / m ² or more and less than 3.8kJ / m ^2.

×: Charpy impact value is less than 3.0 kJ/m ² .

. Charpy impact value (-30℃)

○: Charpy impact value is 2.0 kJ/m ² or more.

△: The Charpy impact value is 1.5 kJ/m ² or more and less than 2.0 kJ/m ² .

×: Charpy impact value is less than 1.5 kJ/m ² .

<load deformation temperature>

According to ISO75, the load deformation temperature was measured under the following conditions. The test piece was set to 10 mm (width) × 4 mm (thickness) × 80 mm (length), and the load was set to 0.45 MPa. The load deformation temperature is evaluated based on the following criteria.

◎: The load deformation temperature is 149°C or higher.

○: The load deformation temperature is 145°C or more and less than 149°C.

△: The load deformation temperature is 142°C or more and less than 145°C.

×: The load deformation temperature is less than 142°C.

<wood powder dispersion>

The dispersion state of the wood powder in the injection test piece was observed with a scanning electron microscope (SEM), and the evaluation was performed according to the following criteria.

○: The wood powder was uniformly dispersed, and no coarse wood powder of 1 mm or more was confirmed.

×: The dispersion of wood powder is uneven, and coarse wood powder of 1 mm or more exists.

[Torque change and resin pressure change]

For Example 7 to Example 26 and Comparative Example 3, the torque change and resin pressure change of the twin-screw extruder when the resin composition was obtained were evaluated by the following method. The results are shown in Table 5 to Table 8.

<torque change>

The torque change TC (N.m) when the compatibilizer was added was evaluated by the following formula.

TC=TA-TB

TA is the value of torque (N.m) of the twin-screw extruder when the running condition is stable 30 minutes after the start of melt kneading. In addition, TB is the torque value (N.m) of the twin-screw extruder when no compatibilizer is added in Comparative Example 1. The lower the value of TC, the easier it is to mix when a compatibilizer is added.

<resin pressure change>

Use the following formula to evaluate the resin pressure change PC when a compatibilizer is added (MPa).

PC=PA-PB

PA is the numerical value (MPa) of the resin pressure of the twin-screw extruder when the running condition is stable 30 minutes after the start of melt kneading. In addition, PB is the numerical value (MPa) of the resin pressure of the twin-screw extruder when no compatibilizer was added in Comparative Example 1. The lower the value of PC (MPa), the easier the mixing when the compatibilizer is added.

[Evaluation of Example 3 to Example 6, Comparative Example 2]

Compared with Comparative Example 2 not containing the compatibilizer (B), the appearance and various physical properties of the test pieces (molded bodies) obtained in Examples 3 to 6 containing the compatibilizer (B) were excellent. different. In addition, Examples 4 and 6 containing 1 part by mass of the compatibilizer (B) are superior in appearance and various physical properties relative to Examples 3 and 5 containing 0.5 part by mass of the compatibilizer (B).

[Evaluation of Example 7 to Example 18]

In addition, with respect to Example 7 containing 1 part by mass of polyolefin wax W1 as a compatibilizer (B), Example 11 containing 1 part by mass of polyolefin wax W10 or polyolefin wax W11 as a compatibilizer (B) And Example 13 is excellent in load deformation temperature. The following aspects are considered to be the main reasons: the acid value of polyolefin wax W10 is higher than that of polyolefin wax W1, and the molecular weight of polyolefin wax W11 is higher than that of polyolefin wax W1. On the other hand, Example 7 is superior to Example 11 and Example 13 in terms of torque change, resin pressure change, and appearance.

In addition, in Example 7 and Example 4, although the manufacturing method of the resin composition is different, the composition is the same, and the appearance and physical properties of the obtained test piece (molded body) are the same.

On the other hand, as opposed to using 0.5 mass of polyolefin wax W1 as In Example 3 of the compatibilizer (B), Examples 10 and 12 in which 0.5 parts by mass of polyolefin wax W10 or polyolefin wax W11 was used as the compatibilizer (B) were excellent in load deformation temperature. In the case of olefin wax W10 (Example 10), the tensile strength was also excellent. In addition, as compared to Examples 3 and 4 (or Example 7) using polyolefin wax W1 as a compatibilizer (B), Examples 14 and 4 using polyolefin wax W12 as a compatibilizer (B) In Example 15, various strengths tend to deteriorate. The reason is considered to be that the acid value of polyolefin wax W12 used as a compatibilizer (B) is relatively low.

In addition, in Examples 3 and 4 (or Example 7) using polyolefin wax W1 as a compatibilizer (B), Examples 16 and 16 using polyolefin wax W13 as a compatibilizer (B) In Example 17, various strengths tended to deteriorate slightly. The reason is considered to be that the molecular weight and acid value of polyolefin wax W13 are slightly lower than those of polyolefin wax W1.

In addition, with respect to Example 7 using 1 part by mass of polyolefin wax W1 as a compatibilizer (B), load deformation of Example 8 using 3 parts by mass of polyolefin wax W1 as a compatibilizer (B) The temperature drops.

Furthermore, in Example 7 using polyolefin wax W1 as a compatibilizer (B), Example 18 using polyolefin wax W15 as a compatibilizer (B) had a higher load deformation temperature. It is believed that the molecular weight and acid value of polyolefin wax W15 are higher than polyolefin wax W1, respectively.

[Evaluation of Examples 19 to 26 and Comparative Example 3]

In Examples 19 to 26, the resin pressure at the time of obtaining the resin composition was not increased, and was excellent in this respect. In addition, Examples 19 to 25 in which two types of polyolefin waxes are combined are excellent in appearance and various physical properties. The reason is considered to be due to the high softening point compatibilizer (BH) W1 or W10, and the low softening point compatibilizer (BL) (polyolefin wax W4, polyolefin wax W6, polyolefin wax W8, petroleum resin W9 Or polyolefin wax W14) due to temperature difference. Specifically, in the resin composition in which two compatibilizers (B) are combined, the compatibilizer (BL) with a low softening point is first melted during molding to improve the dispersibility of wood flour. Therefore, the contact efficiency of the later-melted compatibilizer (BH) with a high softening point and the surface of the wood flour is improved. As a result, it is considered that the balance between workability and mechanical properties is excellent.

In addition, especially in Example 20 in which the compatibilizer W1 and the compatibilizer W6 were combined, Example 22 in which the compatibilizer W1 and the compatibilizer W8 were combined was excellent in workability (torque change). It is presumed that the reason is that the softening point temperature difference between the compatibilizers is within a better range (20° C. or higher).

In addition, in Example 19, the acid-modified wax W4 was used as a low softening point compatibilizer (BL), so the load deformation temperature was excellent.

In addition, in Example 22 using polyolefin wax W1 and a compatibilizer W8 as a compatibilizer (B), Example 23 using polyolefin wax W10 and a polyolefin wax W8 as a compatibilizer (B) The load deformation temperature is excellent. The acid value of the polyolefin wax W10 used as a compatibilizer (B) is considered to be a factor.

[Example 27 to Example 32, Comparative Example 4]

(Preparation of resin composition)

50 parts by mass or 70 parts by mass of the resin (A) shown in Table 9 and 50 parts by mass of natural fibers (C) (wood flour) and 1 part by mass of polyolefin wax as a compatibilizer (B) W1 is dry blended. Among them, in Comparative Example 4, the compatibilizer (B) was not used. In addition, in Example 29, Example 31, and Example 32, two resins (A) were used at a ratio of 1:1. Then, using a labo plastomill (Musashino Kikai, NT-16-129), melt-kneading was performed for 10 minutes at a kneading temperature of 190°C and a screw rotation speed of 10 rpm. Then, it is air-cooled on a belt conveyor to form strands. Cut to make particles.

(Evaluation of resin composition)

<torque>

Five minutes after the start of melt kneading in the La Boprasto mill, the torque value when the operating conditions were stable was read.

[Production of test piece]

After the obtained granular resin composition was dried at 100°C for 4 hours, an injection molding machine (Niigata NN100, manufactured by Niigata Machine Techno) was used at a cylinder temperature of 190 The test piece was produced by injection molding under the conditions of ℃, screw rotation speed of 65 rpm, injection pressure of 160 MPa, and mold temperature of 40 ℃.

[Evaluation of test piece]

For the obtained test piece, the appearance and Charpy impact test (room temperature and -30°C) were evaluated as follows. Table 9 shows the evaluation results.

<Appearance>

◎: The surface of the injection molded product is uniform.

○: The unevenness of the surface of the injection molded product is small.

△: There is much unevenness on the surface of the injection molded product.

×: There is much unevenness on the surface of the injection molded product, and the molded product is discolored.

<Charpy impact test>

According to JIS K7111, the Charpy impact test at room temperature and -30°C was performed. The notch is set to machining, and the test piece is set to 10 mm (width)×4 mm (thickness)×80 mm (length).

<impact absorption>

The melt-kneading will be carried out in the evaluation of the workability of the La Boprasto mill The sample was compression-molded under the following conditions to produce a sheet having a thickness of 2 mm.

Press forming conditions

Preheating: 190℃×10min

Pressing: 190℃×10MPa×3min

Cooling: 18℃×10MPa×3min

On the obtained sheet, a steel ball having a diameter of 15 mm and a weight of 13.7 g was dropped from a height of 10 cm, and the impact absorbability (rebound resilience) was evaluated according to the following criteria.

◎: The sound is low and there is basically no rebound.

○: A sound is generated slightly and rebounds slightly.

△: A sound is generated and it is easy to rebound.

×: A loud sound is generated and the rebound is large

[Evaluation of Examples 27 to 32 and Comparative Example 4]

It is considered that Example 27 utilizes the effect of adding polyolefin wax W1 as a compatibilizer (B), while the appearance and impact value are improved relative to Comparative Example 4. In addition, in Example 28, since the content of the resin (A) was increased, the balance between appearance and impact value was further improved.

Furthermore, Examples 29 and 30 were excellent in workability (torque) and appearance, impact value, and impact absorption, and in particular, Example 30 was excellent in workability (torque), appearance, impact value, and impact absorption. It is considered that the reason is that resin (A3) is used as resin (A).

The balance of appearance, impact value, and impact absorption of Example 31 and Example 32 is relatively good. It is considered that the reason is that resin (A4) or resin (A5) is combined with resin (A2).

[Example 33 to Example 43, Comparative Example 5]

First, the pellets including X3 of Comparative Example 1 were melt-kneaded at a kneading temperature of 190°C and a screw rotation speed of 50 rpm for 5 minutes. Let the maximum torque expression time be T1(s) (Comparative Example 5).

On the other hand, in the granules containing X3 of Comparative Example 1, each compatibilizer (B) in the addition amount shown in Table 10 or Table 11 was blended and dry blended (Example 29 to Example 43). This mixture was melt-kneaded at a kneading temperature of 190°C and a screw rotation speed of 50 rpm for 5 minutes, and the maximum torque generation time T2 was obtained. Then, the kneadability and workability were evaluated by the following judgment criteria. In addition, the La Boprasto mill is a La Boprasto mill 4C150 manufactured by Toyo Seiki Co., Ltd. In addition, the heat resistance stability of the obtained sample was evaluated. The evaluation results are shown in Table 10 and Table 11.

<mixedness>

The ratio of T1 to T2 (T1/T2) was used as an index of kneadability, and evaluation was performed according to the following criteria.

◎: T1/T2 is 1.1 or more (especially easy to mix).

○: T1/T2 is 0.8 or more and less than 1.1 (easy to knead).

△: T1/T2 is 0.5 or more and less than 0.8 (slightly difficult to mix).

×: T1/T2 is less than 0.5 (difficult to mix).

<workability>

The value of the maximum torque was used as an index of workability, and evaluation was performed according to the following criteria.

◎: The maximum torque is less than 34N. m.

○: The maximum torque is 34N. m above and below 43N. m.

△: The maximum torque is 43N. m above and less than 50N. m.

×: The maximum torque is 50N. m or more.

<Evaluation of heat resistance stability>

The samples subjected to melt-kneading in the evaluation of the workability of the La Boprasto mill were compression-molded under the following conditions to produce sheets having a thickness of 2 mm.

<Press molding conditions>

Preheating: 190℃×10min

Pressing: 190℃×10MPa×3min

Cooling: 18℃×10MPa×3min

After placing the obtained sheet in a thermostat at 120°C for 2 hours, visually The surface condition was observed and evaluated according to the following criteria.

○: The surface state is the same as that of no wax added.

△: Slightly whitened compared with no wax.

×: Whitening is remarkable, and unevenness is large.

[Evaluation of Examples 33 to 47 and Comparative Example 5]

Compared with Comparative Example 5, Examples 33 to 46 are excellent in workability. think This depends on the addition effect of the compatibilizer (B).

Compared with Comparative Example 5, Example 33 and Example 34 are not only excellent in workability, but also excellent in kneadability. It is considered that the reason is that since the compatibilizer (B) used is an acid-modified product of polypropylene wax, the compatibility effect with the resin (A) (polypropylene) is large. In addition, Example 33 is more excellent in workability than Example 34. The reason is considered to be that the polyolefin wax W1 used as the compatibilizer (B) has a higher molecular weight than the polyolefin wax W2, so the compatibilizing effect is greater.

Compared with Example 41, in Example 40, since the amount of the compatibilizer (B) added is small, it tends to be excellent in kneadability and heat resistance. Among them, regarding workability, it was confirmed that Example 41 was excellent. It is considered that this depends on the amount of the compatibilizer (B).

Compared with Example 44, Example 45 and Example 46 have good processability. It is considered that this depends on the amount of the compatibilizer (B). On the other hand, regarding the kneadability, Example 44 and Example 45 tended to be superior to Example 46.

The mixing performance of Example 47 is particularly good, and it is considered that the reason is that the petroleum resin W9 used as the compatibilizer (B) has a large-volume skeleton and is easily compatible with the surface of the wood powder (C).

This application claims priority based on Japanese Patent Application No. 2015-097482 filed on May 12, 2015 and Japanese Patent Application No. 2015-233309 filed on November 30, 2015. The contents described in the specification and drawings of these applications are all cited in the specification of this application.

[Industry availability]

According to the resin composition of the present invention, it is possible to obtain uniformity of resin and natural fibers Synthetic wood that is dispersed and has excellent balance of workability, appearance, tensile strength, bending strength, impact resistance, thermal stability, and so on. Therefore, this resin composition is very useful for various applications.

Claims (20)

A resin composition containing a thermoplastic resin (A), a compatibilizer (B), and natural fibers (C), and when the total of the thermoplastic resin (A) and the natural fibers (C) is set to 100 In the case of parts by weight, the thermoplastic resin (A) is contained in a ratio of 1 part by mass to 90 parts by mass, the natural fiber (C) is contained in a ratio of 10 parts by mass to 99 parts by mass, and the amount is 0.1 part by mass to 50 parts by mass The ratio of parts contains the compatibilizer (B), and the compatibilizer (B) is a polyolefin wax (B1) or petroleum resin (B2) that satisfies the following (i) to (iv): (i) The polystyrene-converted number-average molecular weight (Mn) measured by gel permeation chromatography is in the range of 300 to 20,000; (ii) The softening point measured in accordance with JIS K2207 is in the range of 70°C to 170°C; (iii) The density measured by the density gradient tube method is in the range of 830kg/m ³ ~ 1200kg/m ³ ; (iv) The ratio of the weight average molecular weight to the number average molecular weight determined by gel permeation chromatography (Mw /Mn) is 7.0 or less, the compatibilizer (B) contains two or more compounds, and among the two or more compounds, the compatibilizer (BH) with the highest softening point has the lowest softening point and the lowest softening point The difference in softening point of the compatibilizer (BL) is above 5°C. The resin composition as described in item 1 of the patent application range, wherein the compatibilizer (B) includes a polyolefin wax (B1). The resin composition as described in item 2 of the patent application range, wherein the polyolefin wax (B1) is selected from the group consisting of ethylene homopolymer, propylene homopolymer, ethylene and a C 3-12 alpha-olefin copolymer Modified monomers, unsaturated carboxylic acid derivative monomer modified products of at least one polymer in the group consisting of copolymers of propylene and α-olefins having 4 to 12 carbon atoms, and styrene modified products of the copolymers Or the air oxide of the copolymer. The resin composition according to item 3 of the patent application scope, wherein the polyolefin wax (B1) is a modified monomer of the unsaturated carboxylic acid derivative monomer of the polymer or an air oxide of the polymer, and The acid value is 1mgKOH/g~100mgKOH/g. The resin composition according to item 3 of the patent application scope, wherein the polyolefin wax (B1) is a modified monomer of the unsaturated carboxylic acid derivative monomer of the polymer or an air oxide of the polymer, and The acid value is 30mgKOH/g~87mgKOH/g. The resin composition according to item 3 of the patent application scope, wherein the polyolefin wax (B1) is a modified monomer of the unsaturated carboxylic acid derivative monomer of the polymer or an air oxide of the polymer, and The acid value is 40mgKOH/g~100mgKOH/g. The resin composition as described in item 1 of the patent application range, wherein the compatibilizer (B) contains two or more compounds, and among the two or more compounds, the compatibilizer (BH) with the highest softening point The difference between the softening point and the softening point of the compatibilizer (BL) with the lowest softening point is 20°C or higher. The resin composition as described in item 2 of the patent application range, wherein the compatibilizer (BH) and the compatibilizer (BL) are the polyolefin wax (B1). The resin composition as described in item 3 of the patent application scope, wherein the compatibilizer (BH) is an unsaturated carboxylic acid derivative monomer modification of the polymer or an air oxide of the polymer, and The acid value is 60mgKOH/g~90mgKOH/g. The resin composition as described in item 2 of the patent application range, wherein the polystyrene wax (B1) has a polystyrene-converted number-average molecular weight (Mn) of 6000 to 12000 as determined by gel permeation chromatography Within range. The resin composition as described in item 2 of the patent application range, wherein the Mw/Mn of the polyolefin wax (B1) is 5.0 or less. The resin composition as described in item 1 of the patent application range, wherein the thermoplastic resin (A) has a melting point (Tm) measured by a differential scanning calorimeter of 250° C. or less or is not observed. The resin composition as described in item 1 of the patent application range, wherein the density of the thermoplastic resin (A) measured according to the density gradient tube method is in the range of 830 kg/m ³ to 1800 kg/m ³ . The resin composition as described in item 1 of the patent application range, wherein the thermoplastic resin (A) has a bending modulus of elasticity of 1 MPa to 10000 MPa. The resin composition as described in item 1 of the patent application, wherein the thermoplastic resin (A) is selected from the group consisting of olefin polymers, polystyrene, and acrylonitrile. Butadiene. At least one resin in the group consisting of styrene copolymer resin and polyvinyl chloride. The resin composition as described in item 1 of the patent application range, wherein the natural fiber (C) is selected from the group consisting of wood flour, wood fiber, bamboo, cotton, cellulose and nanocellulose fiber At least one fiber. The resin composition as described in item 1 of the patent application range, wherein the melt flow rate measured at 230°C and a test load of 10 kgf according to JIS K7210 is 0.01 g/10 min to 100 g/10 min. The resin composition as described in item 1 of the patent application scope, wherein the thermoplastic resin (A), the compatibilizer (B) and the natural fiber ( C) The maximum torque performance time at the time of kneading is set to T2, and the maximum torque performance time at the time of kneading only the thermoplastic resin (A) and the natural fiber (C) using a batch Plastow mill When it is T1, the ratio of T1 to T2 (T1/T2) is 0.5 or more. A synthetic wood obtained by molding the resin composition as described in any one of patent application items 1 to 18. The synthetic wood as described in item 19 of the patent application scope is a wooden deck or floor board.

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