JPWO2016181641A1 - 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 a resin and natural fibers are uniformly dispersed and which has an excellent balance of processability, appearance, tensile strength, bending strength, impact property, thermal stability, and the like. In order to solve the above problems, the resin contains at least one resin (A) selected from a thermoplastic resin and a thermosetting resin, a compatibilizer (B), and a natural fiber (C), When the total of (A) and the natural fiber (C) is 100 parts by weight, the resin (A) is 1 to 90 parts by weight, the natural fiber (C) is 10 to 99 parts by weight, and the compatibility A resin composition containing 0.1 to 50 parts by mass of the agent (B) is used.

Description

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

  Conventionally, as a composition for synthetic wood, what consists of wood flour and thermoplastic resins, such as polyethylene and a polypropylene, is known. Synthetic wood can be obtained by molding the composition for synthetic wood into a desired shape by a molding method such as extrusion molding or injection molding.

  However, when a synthetic wood composition is produced by molding a synthetic wood composition, the wood powder may be burnt by heat during molding, resulting in poor appearance of the synthetic wood. Further, when a fluidity improving material such as wax is added to the composition for synthetic wood, the fluidity of the composition is improved and the molding temperature can be lowered, so that the occurrence of scorching as described above can be prevented. On the other hand, problems such as stickiness of the surface of the synthetic wood may occur. On the other hand, Patent Document 1 discloses a composition for synthetic wood that can obtain a synthetic wood having a good appearance and less stickiness on the surface by using a specific wax. However, there are higher demands on the uniform dispersibility of the resin and wood powder, the appearance of the resulting synthetic wood, and the mechanical strength.

JP 2004-026886 A JP 2002-138202 A

  In view of the above-mentioned background art, the problem of the present invention is that the synthetic wood has excellent balance of workability, appearance, tensile strength, bending strength, impact property, thermal stability, etc., in which the resin and the natural fiber are uniformly dispersed. It is providing the resin composition for obtaining.

The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above problem can be solved by using a resin composition having a specific composition, and the present invention has been completed.
That is, the present invention relates to the following [1] to [22].
[1] At least one resin (A) selected from a thermoplastic resin and a thermosetting resin, a compatibilizer (B), and a natural fiber (C), and the resin (A) When the total with the natural fiber (C) is 100 parts by weight, the resin (A) is 1 to 90 parts by weight, the natural fiber (C) is 10 to 99 parts by weight, and the compatibilizer (B ) In a proportion 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-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 300-20000. (Ii) The softening point measured in accordance with JIS K2207 is in the range of 70-170 ° C. (Iii) The density measured by the density gradient tube method is in the range of 830 to 1200 kg / m ³ (iv) The ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography (GPC) (Mw / Mn) [3] The resin composition according to [1] or [2], wherein the compatibilizer (B) is a polyolefin wax (B1).
[4] The polyolefin wax (B1) is an ethylene homopolymer, a propylene homopolymer, a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, and α having 4 to 12 carbon atoms. An unsaturated carboxylic acid derivative monomer modified product of at least one polymer selected from the group consisting of a copolymer with an olefin, a styrene modified product of the copolymer, or an air oxide of the copolymer , [2] or [3].

[5] In the above [4], the polyolefin wax (B1) is an unsaturated carboxylic acid derivative monomer modified product of the polymer or an air oxide of the polymer and has an acid value of 1 to 100 mgKOH / g. The resin composition as described.
[6] In the above [4], the polyolefin wax (B1) is an unsaturated carboxylic acid derivative monomer modified product of the polymer or an air oxide of the polymer and has an acid value of 30 to 87 mgKOH / g. The resin composition as described.
[7] In the above [4], the polyolefin wax (B1) is an unsaturated carboxylic acid derivative monomer modified product of the polymer or an air oxide of the polymer and has an acid value of 40 to 100 mgKOH / g. The resin composition as described.

[8] The compatibilizer (B) comprises two or more compounds, and among the two or more compounds, the softening point of the compatibilizer (BH) having the highest softening point, and the softening point The resin composition according to [1] or [2], wherein the difference from the softening point of the lowest compatibilizer (BL) is 5 ° C or higher.
[9] The compatibilizer (B) comprises two or more compounds, and the softening point of the compatibilizer (BH) having the highest softening point among the two or more compounds, The resin composition according to [1] or [2], wherein the difference from the softening point of the lowest compatibilizer (BL) 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 compatibilizer (BH) is an unsaturated carboxylic acid derivative monomer modified product of the polymer or an air oxide of the polymer, and an acid value is 60 to 90 mgKOH / g. [8] ] Or the resin composition as described in [9].
[12] Any of [2] to [11], wherein the polyolefin wax (B1) has a polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) in the range of 6000 to 12000. The resin composition described in 1.

[13] The resin composition according to any one of [2] to [12], wherein 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 a melting point (Tm) measured by a differential scanning calorimeter (DSC) of the resin (A) is 250 ° C. or lower or is not observed.
[15] The resin composition according to any one of [1] to [14], wherein the density of the resin (A) measured according to a density gradient tube method is in the range of 830 to 1800 kg / m ³ .

[16] The resin composition according to any one of [1] to [15], wherein the resin (A) has a flexural modulus of 1 to 10,000 MPa.
[17] The resin (A) is at least one resin selected from the group consisting of an olefin polymer, polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), and polyvinyl chloride. [1] -The resin composition in any one of [16].
[18] Any of [1] to [17], wherein the natural fiber (C) is at least one fiber selected from the group consisting of wood flour, wood fiber, bamboo, cotton, cellulose, and nanocellulose fibers. A resin composition according to claim 1.
[19] The resin according to any one of [1] to [18], wherein a melt flow rate (MFR) measured at 230 ° C. and a test load of 10 kgf is 0.01 to 100 g / 10 min in accordance with JIS K7210. Composition.

[20] The maximum torque expression time when the resin (A), the compatibilizer (B), and the natural fiber (C) are kneaded in a batch plast mill is T2, and the resin (A) and the resin When the maximum torque expression time when only natural fibers (C) are kneaded in a batch plast mill is T1, the ratio of T1 and T2 (T1 / T2) is 0.5 or more, [1] to [1] [19] The resin composition according to any one of [19].
[21] 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 wood deck or flooring.

  In the resin composition of the present invention, the resin and the natural fiber are uniformly dispersed. Therefore, according to the resin composition, a synthetic wood having an excellent balance of workability, appearance, tensile strength, bending strength, impact property, thermal stability, and the like is provided. In addition, since the processability of the resin composition is particularly high, it becomes possible to efficiently mold the resin composition or to efficiently process the synthetic wood. Furthermore, it is possible to improve the low-temperature formability of the synthetic wood, reduce the defective rate generated by burning, and the like. In addition, since the resin composition has high mechanical properties, it is possible to reduce the thickness and weight of the molded product, improve workability, improve designability, and suppress water-resistant deterioration.

FIG. 1 is an external view photograph 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). To do.
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 to 90 parts by weight, preferably 10 to 80 parts by weight. Yes, more preferably 25 to 75 parts by mass. When the molded product of the resin composition is required to have tensile strength, bending strength, and heat resistance, the upper limit is preferably 70 parts by mass, more preferably 60 parts by mass, and particularly preferably 55 parts by mass. When the molded article of the resin composition is required to have impact resistance, flexibility, grip properties, and impact absorption, the lower limit is preferably 30 parts by mass, more preferably 55 parts by mass, and particularly preferably Is 60 parts by mass.

  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 to 99 parts by weight, preferably 20 to 90 parts by weight. More preferably, it is 25 to 75 parts by mass. When tensile strength, bending strength, and heat resistance are required for the molded product of the resin composition, the lower limit thereof is preferably 30 parts by mass, more preferably 40 parts by mass, and particularly preferably 45 parts by mass. When the molded article of the resin composition is required to have impact resistance, flexibility, grip properties, and impact absorption, the upper limit is preferably 70 parts by mass, more preferably 45 parts by mass, and particularly preferably Is 40 parts by mass.

  The amount of the compatibilizer (B) when the total of the resin (A) and the natural fiber (C) is 100 parts by weight is 0.1 to 50 parts by weight, preferably It is 0.1-20 mass parts, More preferably, it is 0.2-9 mass parts, More preferably, it is 0.3-7 mass parts, Most preferably, it is 0.4-5 mass parts, Preferably, it is 1-3 mass parts.

  The amount of the resin (A) is preferably 50 to 99.9 parts by mass when the total of the resin (A) and the compatibilizer (B) is 100 parts by weight. Preferably it is 80-99.9 mass parts, More preferably, it is 91-99.8 mass parts, Most preferably, it is 93-99.7 mass parts, Most preferably, it is 95-99.6 mass parts. . On the other hand, the amount of the compatibilizer (B) when the total of the resin (A) and the compatibilizer (B) is 100 parts by weight is 0.1 to 50 parts by mass. More preferably, it is 0.1-20 mass parts, More preferably, it is 0.2-9 mass parts, Most preferably, it is 0.3-7 mass parts, Most preferably, it is 0.4-5 mass Part. The amount of the natural fiber (C) is preferably 1 to 300 parts by mass, more preferably 100 parts by weight of the total of the resin (A) and the compatibilizer (B). Is 1 to 150 parts by mass, more preferably 50 to 150 parts by mass, and particularly preferably 70 to 120 parts by mass.

  Usually, when the amount of the compatibilizer (B) is increased, the processability of the resin composition is improved, but when the amount is excessive, the kneadability and the heat resistance stability tend to deteriorate. On the other hand, when 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 kneading and processing of the resin composition is facilitated, but the influence on the molding work environment such as smoke and odor generated during the molding process is small. There is little thermal deterioration such as generation of burnt resin, low molecular weight substances, additives, etc.) and scorch. Furthermore, since the dispersibility of the natural fiber (C) is increased, it is preferable in that the influence on the appearance is small and the balance between mechanical strength and heat resistance is good.

Further, if the amount of the natural fiber (C) is in a relatively small range, sludge hardly remains after combustion. In such a case, the natural fiber (C) functions as a modifier or reinforcing agent for the resin (A) and the compatibilizer (B). On the other hand, by making the natural fiber (C) 10 parts by mass or more with respect to a total of 100 parts by mass of the resin (A) and the natural fiber (C), a resin composition having an excellent balance of mechanical strength and heat resistance is obtained. 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 may be used alone or in combination of two or more. Definitions and production methods for thermoplastic resins or thermosetting resins are well known, and are described in publications such as “Practical Plastics Dictionary” (edited by the Practical Plastics Dictionary Editorial Board, published by Industrial Research Co., Ltd.). In the present invention, the resin (A) is more preferably a thermoplastic resin.

1-1. Thermosetting resin Examples of the thermosetting resin include polyurethane, epoxy resin, thermosetting unsaturated polyester resin, urea resin, melamine resin and phenol resin, and mixed resins thereof. Among these, (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 An epoxy resin is typically a resin obtained by reacting an aromatic diol (for example, bisphenol A) and epichlorohydrin in the presence of an alkali. In the present invention, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a bisphenol S type epoxy resin having an epoxy equivalent of 170 to 5000 is preferable. Such epoxy resins are commercially available, and examples include the brand name Epomic (Mitsui Chemicals Co., Ltd.), Epicron (Dainippon Ink Chemical Co., Ltd.), Sumi Epoxy (Sumitomo Chemical Co., Ltd.), etc. These can be preferably used in the present invention.

(2) Thermosetting unsaturated polyester resin The thermosetting unsaturated polyester resin is typically a resin obtained by an esterification reaction between 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 and a diol such as ethylene glycol or diethylene glycol is preferred. Such thermosetting unsaturated polyester resins are commercially available. Examples thereof include Rigolac (Showa High Polymer Co., Ltd.), Sumicon (Sumitomo Bakelite Co., Ltd.), and the like. It can be preferably used for the composition.

(3) Phenolic resin In the present invention, the phenolic resin includes both so-called novolak type and resol type, and the phenolic resin used in the resin composition of the present invention includes novolak type and dimethylene cured with hexamethylenetetramine. A solid resol type resin mainly composed of an ether bond is preferred. Such a phenol resin is commercially available, and examples thereof include trade name Sumicon PM (Sumitomo Bakelite Co., Ltd.), Nikkaline (Nippon Synthetic Chemical Industry Co., Ltd.), etc., which are preferably used in the present invention. Can do.

1-2. The following (1)-(16) is mentioned as a typical thing as a thermoplastic resin. These 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) Styrenic resins such as acrylic ester-styrene resin and styrene-butadiene-styrene resin (6) Acrylic resins such as polymethyl methacrylate and polyethyl methacrylate (7) Polycarbonate (8) Polyphenylene oxide (9) Polyvinyl chloride, Poly Chlorine resins such as vinylidene chloride (10) Vinyl acetate resins such as polyvinyl acetate and ethylene-vinyl acetate resins (11) Ethylene- (meth) acrylic acid ester copolymers (12) Ethylene-acrylic Acid resins, ethylene-methacrylic acid resins and their ionomer resins (13) Vinyl alcohol resins such as polyvinyl alcohol and ethylene-vinyl alcohol resins (14) Cellulose resins (15) Vinyl chloride elastomers, urethane elastomers, polyester elastomers (16) Various copolymer rubbers

Next, specific examples will be given for each thermoplastic resin.
(1) Olefin polymer As the olefin polymer, olefin homopolymers such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, polymethylbutene; ethylene-α-olefin random copolymer Polymer, propylene-ethylene random copolymer, ethylene / α-olefin / non-conjugated polyene copolymer, olefin copolymer such as 4-methyl-1-pentene / α-olefin copolymer; and the like. it can.

  The olefin 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 ultra high 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 91.0 to 99.9 mol. %, More preferably 93.0-99.9 mol%, still more preferably 95.0-99.9 mol%, particularly preferably 95.0-99.0 mol%. is there. On the other hand, the amount of the structural unit (b) derived from the α-olefin having 3 or more carbon atoms is preferably 0.1 to 9.0 mol%, more preferably 0.1 to 7.0 mol. %, More preferably 0.1 to 5.0 mol%, particularly preferably 1.0 to 5.0 mol%. However, (a) + (b) = 100 mol%. The content rate of the structural unit of the said olefin polymer can be calculated | required by the analysis of a < ¹³ > C-NMR spectrum.

  Here, examples of the α-olefin having 3 to 12 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl. Examples thereof include linear or branched α-olefins such as -1-pentene, 1-octene, 1-decene, and 1-dodecene. Preferred are propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene, more preferred are α-olefins having 3 to 8 carbon atoms, and particularly preferred are propylene, 1 -Butene. When ethylene and propylene or 1-butene are copolymerized, the balance of processability, appearance, and mechanical strength of the resin composition is improved. In addition, an alpha olefin may be used individually by 1 type, and may use 2 or more types together.

  The olefin 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 making a propylene (co) polymer into the copolymer of propylene and ethylene, it is good also considering the quantity of the structural unit derived from propylene as 60-99.5 mol%. In this case, the amount of the structural unit derived from propylene is preferably 80 to 99 mol%, more preferably 90 to 98.5 mol%, and still more preferably 95 to 98 mol%. However, the sum total of the quantity of the structural unit derived from propylene and the quantity of the structural unit derived from ethylene is 100 mol%. When a propylene (co) polymer having a large amount of structural units derived from propylene is used, a resin composition having 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 and 1-pentene. Linear or branched α such as 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, etc. -Olefins. Among these, 1-butene is particularly preferable. The propylene / α-olefin copolymer may contain olefins other than those having 4 to 12 carbon atoms. For example, the propylene / α-olefin copolymer contains a small amount of a structural unit derived from ethylene or the like, for example, in an amount of 10 mol% or less. Also good. On the other hand, the fact that a structural unit derived from ethylene is not included is also one of preferred embodiments from the viewpoint of improving the balance between heat resistance and mechanical strength of the resin composition. The α-olefin may be used alone or in combination of two or more.

  When the propylene (co) polymer is a propylene / α-olefin copolymer, the amount of the structural unit (a ′) derived from propylene is preferably 60 to 90 mol%, more preferably 65 to 88. It is mol%, More preferably, it is 70-85 mol%, Most preferably, it is 75-82 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 to 40 mol%, more preferably 12 to 35 mol%, and still more preferably 15 to 30 mol%, particularly preferably 18 to 25 mol%. However, (a ′) + (b ′) = 100 mol%.

  When the composition of the propylene / α-olefin copolymer is within the above range, a resin composition having an excellent appearance can be obtained. The reason for this is not clear, but since the crystallization speed is slow, the time during which the resin composition can flow is increased on the mold or in the cooling step. And as a result, it is thought that surface property becomes favorable. Further, when the composition is in the above range, the mechanical strength and heat resistance are improved. The melting point Tm obtained from the result of DSC of the propylene / α-olefin copolymer is usually 60 to 120 ° C, preferably 65 to 100 ° C, and more preferably 70 to 90 ° C.

  Furthermore, the olefin polymer may be an ethylene / α-olefin / non-conjugated polyene copolymer. In this case, the copolymer is preferably a copolymer of ethylene [A], an α-olefin [B] having 3 to 12 carbon atoms and a non-conjugated polyene [C], and is a polymer obtained by random copolymerization. Is more preferable. Examples of the α-olefin include α-olefins having 3 to 12 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene. A linear or branched α-olefin having 3 to 12 carbon atoms, such as 3-methyl-1-pentene, 1-octene, 1-decene and 1-dodecene, is used. As the nonconjugated polyene, a cyclic or chain nonconjugated polyene is used. Examples of the cyclic non-conjugated polyene include cyclopentene, cycloheptene, norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, norbornadiene, methyltetrahydroindene, tetracyclododecene, and the like. Examples of the chain non-conjugated polyene include 1,4-hexadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4-ethylidene-1,7-undecadiene, and the like. Is mentioned. Of these, 5-ethylidene-2-norbornene, dicyclopentadiene, and 5-vinyl-2-norbornene are preferable. These cyclic or chain nonconjugated polyenes may be used alone or in combination of two or more.

  Examples of the ethylene / α-olefin / non-conjugated polyene random copolymer include ethylene / propylene / diene terpolymer (EPDM).

  Further, as the olefin polymer, a propylene / α-olefin / non-conjugated polyene copolymer, a 1-butene / α-olefin / non-conjugated polyene copolymer, or the like can be used.

  Furthermore, 4-methyl-1-pentene / α-olefin copolymer may be used as the olefin polymer. Specific examples of the 4-methyl-1-pentene / α-olefin copolymer include polymers disclosed in International Publication No. 2011/055803. The amount of the structural unit derived from 4-methyl-1-pentene in the 4-methyl-1-pentene / α-olefin copolymer is preferably 5 to 95 mol%, and 4-methyl-1-pentene is The amount of structural units derived from at least one α-olefin selected from α-olefins having 2 to 20 carbon atoms to be excluded is preferably 5 to 95 mol%. Further, a part of the 4-methyl-1-pentene / α-olefin copolymer may contain a non-conjugated polyene, and the amount of the structural unit derived from the non-conjugated polyene is 0 to 10 mol%. Preferably there is. The total amount of these is 100 mol%.

The stereoregularity of the olefin polymer is not particularly limited, but when the olefin polymer is a propylene (co) polymer, the propylene (co) polymer is substantially syndiotactic. It preferably has a tick structure. For example, if the propylene-based (co) polymer has a substantially syndiotactic structure, the molecular weight (Me) between the entanglement points becomes small at the same molecular weight, and the entanglement of the molecules increases. It becomes difficult to wake up anyone. Moreover, when manufacturing a molded object using the resin composition containing a propylene type | system | group (co) polymer, it becomes easy to adhere | attach moderately to the metal mold | die and roll for shaping | molding. In addition, the propylene-based (co) polymer having a syndiotactic structure has a slow crystallization rate compared to a general isotactic polypropylene-based (co) polymer, and cooling with a mold or roll is slow. Thus, the adhesion is improved. As a result, it is presumed that the gloss of the surface of the molded product is increased, and the wear resistance, scratch resistance, impact resistance and the like are increased. The propylene-based (co) polymer has a substantially syndiotactic structure when the peak area corresponding to 19.5 to 20.3 ppm in the ¹³ C-NMR spectrum is relatively 0.5 or more. It means that. When the syndiotacticity is within the above range, the crystallization speed becomes slow enough to allow molding, and the processability becomes very good. In addition, propylene-based (co) polymers whose structural units derived from propylene have a substantially syndiotactic structure are more resistant to abrasion and scratches than polyethylene, block polypropylene, and isotactic polypropylene, which are general-purpose polyolefin resins. The stickiness is very good. In addition, the propylene-type (co) polymer which has a syndiotactic structure can be manufactured with a various well-known manufacturing method.

<Graft modification>
When the resin (A) is the olefin polymer, the olefin polymer may be unmodified, but as described below, the olefin polymer is graft-modified with a polar compound containing a double bond. May be. When the olefin polymer is graft-modified, the compatibility between the resin (A) and the natural fiber (C) increases, and a resin composition having excellent heat resistance and mechanical strength is obtained.

  The graft modification of the olefin polymer can be performed by a known method. For example, an 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 are added to the obtained solution, and usually 60 to 350 ° C., preferably 80 to The method of making it react at the temperature of 190 degreeC for 0.5 to 15 hours, Preferably it is 1 to 10 hours can be illustrated.

  The organic solvent can be used without particular limitation as long as it is an organic solvent capable of dissolving the olefin polymer. Examples of such an organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane and heptane.

  As another graft modification method, a method of reacting an olefin polymer with a polar compound containing a double bond such as an unsaturated carboxylic acid without using a solvent, preferably using an extruder or the like. Is mentioned. The reaction conditions in this case are such that the reaction temperature is usually not lower than the melting point of the olefin polymer, specifically 100 to 350 ° C. The reaction time can usually be 0.5 to 10 minutes.

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

  As radical initiators, organic peroxides and organic peroxides (for example, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (peroxidebenzoate) hexyne- 3,1,4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperoxyacetate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5- Dimethyl-2,5-di (t-butylperoxy) hexane, t-butylperoxybenzoate, t-butylperoxyphenyl acetate, t-butylperoxyisobutyrate, t-butylperoxy-sec-octoate, t-butylperoxypi Rate, cumylperoxypivalate, t-butylperoxydiethyl acetate, t-butylperoxyisopropylmonocarbonate and t-butylperoxy-2-ethylhexylmonocarbonate), azo compounds (eg azobisisobutyronitrile, dimethylazoisobutyrate) Rate) or the like. Among these, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (t Dialkyl peroxides such as -butylperoxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene are preferred. The radical initiator is usually used in a ratio of 0.001 to 1 part by weight with respect to 100 parts by weight of the olefin polymer before modification.

  The shape of the graft-modified olefin polymer is not particularly limited, and may be, for example, particulate. As an example of a suitable method for obtaining a particulate graft-modified olefin polymer, it is composed of one or more α-olefins selected from α-olefins having 2 to 18 carbon atoms and has a melting point of 50 ° C. Examples thereof include a method in which a particle having a temperature lower than 250 ° C. and a monomer having an ethylenically unsaturated group and a polar functional group in the same molecule are subjected to a graft reaction. The graft reaction can be performed at a temperature below the melting point (Tm) of the polyolefin particles using the above-described radical initiator. The average particle diameter of the particles of the graft-modified olefin polymer can be, for example, 0.2 mm to 2.5 mm, but is not limited thereto. The melting point of the polyolefin particles used for the preparation of the particulate graft-modified olefin polymer is 50 ° C. or more and less than 250 ° C. in one exemplary embodiment of the present invention, but is not limited thereto. The graft reaction can be carried out without a solvent, but is preferably carried out in the presence of an organic solvent.

(2) Polyamide As polyamide, Nylon-6, Nylon-66, Nylon-10, Nylon-11, Nylon-12, Nylon-46, Nylon 66, Nylon-610, Nylon-612, etc., aliphatic polyamide, aromatic An aromatic polyamide produced from a dicarboxylic acid and an aliphatic diamine can be mentioned, and nylon-6 is preferred.

(3) Polyester Examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polycaprolactone, polyhydroxybutyrate, and polyester elastomers. Polyethylene terephthalate is preferable.

(4) Polyacetal Examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, and polybutyraldehyde, and polyformaldehyde is particularly preferable.

(5) Styrene resin The styrene resin may be a homopolymer of styrene, and is a binary copolymer of styrene and acrylonitrile, methyl methacrylate, α-methylstyrene or the like, for example, acrylonitrile-styrene copolymer. It may be a coalescence. Further, acrylonitrile-butadiene-styrene resin, acrylonitrile-acrylic rubber-styrene resin, acrylonitrile-ethylene rubber-styrene resin, (meth) acrylic ester-styrene resin, or various styrene-based elastomers may be used. As an acrylonitrile-butadiene-styrene (ABS) resin, it contains a structural unit derived from acrylonitrile in an amount of 20 to 35 mol%, a structural unit derived from butadiene in an amount of 20 to 30 mol%, What contains the structural unit derived from styrene in the quantity of 40-60 mol% is used preferably. The total of these structural units is 100 mol%.

  Moreover, as a styrene-type elastomer, the well-known styrene-type elastomer which has a polystyrene phase as a hard segment can also be used. Specifically, styrene / butadiene copolymer (SBR), styrene / isoprene / styrene copolymer (SIS), styrene / butadiene / styrene copolymer (SBS), styrene / ethylene / butadiene / styrene copolymer ( SEBS) and hydrides thereof, styrene / isobutylene / styrene triblock copolymer (SIBS), and styrene / isobutylene diblock copolymer (SIB). Preferred are styrene / isobutylene / styrene triblock copolymer (SIBS) and styrene / isobutylene diblock copolymer (SIB).

(6) Acrylic resin Examples of the acrylic resin fat include polymethacrylate and polyethyl methacrylate, and polymethyl methacrylate (PMMA) is preferable.

(7) Polycarbonate As the polycarbonate, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4 Examples thereof include those obtained from -hydroxyphenyl) butane, and polycarbonates obtained from 2,2-bis (4-hydroxyphenyl) propane are preferred.

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

(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 ester, acrylonitrile, propylene, etc. It may be. On the other hand, polyvinylidene chloride is usually a resin containing 85% or more of vinylidene chloride units. For example, vinylidene chloride is co-polymerized with vinyl chloride, acrylonitrile, (meth) acrylic acid ester, allyl ester, unsaturated ether, styrene, etc. Coalescence is used. A vinyl chloride elastomer may be 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. May be. Of these, ethylene-vinyl acetate copolymer is preferred. Further, it may be a modified ethylene-vinyl acetate copolymer such as a saponified ethylene-vinyl acetate copolymer or a graft-modified ethylene-vinyl acetate copolymer.

(11) Ethylene- (meth) acrylic ester copolymer As ethylene- (meth) acrylic ester copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer Polymers and ethylene-ethyl methacrylate copolymers are preferred.

(12) Ethylene-acrylic acid resins, ethylene-methacrylic acid resins and their ionomer resins. Ethylene-acrylic acid copolymers and ethylene-methacrylic acid copolymers are copolymers of ethylene and various (meth) acrylic acids. It can be. These may be further metallized to form metal salts (ionomers). The metal element of the metal salt is preferably at least one selected from K, Na, Ca and Zn. It is more preferable that the metal element is K, Na, Ca or Zn because modification is easy.

(13) Vinyl alcohol resins such as polyvinyl alcohol and ethylene-vinyl alcohol resin Polyvinyl alcohol, ethylene-vinyl alcohol resin and the like can be mentioned, 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 has high gas barrier properties, oil resistance, and transparency of polyvinyl alcohol, and also has characteristics such as moisture resistance and melt extrusion processability of the ethylene component. Further, the ethylene-vinyl alcohol copolymer resin binds well with the natural fiber (C) and is excellent in the balance between heat resistance and mechanical strength.

(14) Cellulose resin A typical example of the cellulose resin is acetylcellulose. By using a plasticizer such as dibutyl phthalate in combination, it has the characteristics of a thermoplastic resin.

(15) Thermoplastic elastomer The thermoplastic polyurethane material mentioned as a thermoplastic urethane type elastomer is demonstrated. The structure of the thermoplastic polyurethane material is composed of a soft segment made of a polymer polyol (polymeric glycol), a chain extender constituting the hard segment, and a diisocyanate. Here, as the polymer polyol used as a raw material, any of those conventionally used in the technology relating to thermoplastic polyurethane materials can be used, and is not particularly limited. For example, there are a polyester type and a polyether type, and the polyether type is preferable to the polyester type in that a thermoplastic polyurethane material having high rebound resilience and excellent low temperature characteristics can be synthesized. Examples of the polyether polyol include polytetramethylene glycol and polypropylene glycol. Polytetramethylene glycol is particularly preferable from the viewpoint of the resilience modulus and low temperature characteristics. The average molecular weight of the polymer polyol is preferably 1000 to 5000, and particularly preferably 2000 to 4000 in order to synthesize a thermoplastic polyurethane material having high resilience. As the chain extender, those used in the conventional technology relating to thermoplastic polyurethane materials can be suitably used. For example, 1,4-butylene glycol, 1,2-ethylene glycol, 1,3-butanediol, 1 , 6-hexanediol, 2,2-dimethyl-1,3-propanediol and the like, but are not limited thereto. These chain extenders preferably have an average molecular weight of 20 to 15000. As the diisocyanate, those used in the conventional technology relating to thermoplastic polyurethane materials can be suitably used. For example, aromatics such as 4,4′-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate can be used. Aliphatic diisocyanates, aliphatic diisocyanates such as hexamethylene diisocyanate, and the like, but are not limited thereto. In the present invention, 4,4′-diphenylmethane diisocyanate which is an aromatic diisocyanate is particularly preferable. As the thermoplastic polyurethane material composed of the above-mentioned materials, commercially available products can be suitably used. For example, Pandex T-8290, T-8295, T8260 manufactured by DIC Bayer Polymer Co., Ltd., Daiichi Seika Kogyo Co., Ltd. ) Resamine 2593, 2597 and the like.

(16) Various copolymer rubbers Examples of rubbers other than the above-mentioned elastomers include polybutadiene rubber, polyisoprene rubber, neoprene rubber, nitrile rubber, butyl rubber, halogenated butyl rubber, polyisobutylene rubber, natural rubber, and silicone rubber. These rubbers may be used alone or in combination of two or more.

1-3. Preferred resin (A)
Examples of the resin (A) include olefin polymers, acid graft modified products of olefin polymers, styrene resins, chlorine resins, ethylene-acrylic acid resins, ethylene-methacrylic acid resins, and ionomer resins thereof. It is preferably at least one resin selected from the group consisting of thermoplastic elastomers and various copolymer rubbers, from olefin polymers, polystyrene, acrylonitrile / butadiene / styrene copolymer resins (ABS resins), and polyvinyl chloride. More preferably, it is at least one resin selected from the group consisting of polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, polyvinyl chloride, polystyrene, and acrylonitrile-butadiene-styrene copolymer. More preferred to be chosen Arbitrariness. Further, an ethylene (co) polymer or a propylene (co) polymer is particularly preferable. When an ethylene (co) polymer or a propylene (co) polymer is used as the resin (A), it is preferable since the working environment is good during the molding process of the resin composition with less odor and fuming. In addition, it is possible to obtain a good molded product with less scorching. The ethylene (co) polymer is excellent in low-temperature characteristics and processability, and the propylene (co) polymer is 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, still more preferably 200 ° C, and particularly preferably 170 ° C. The lower limit of the melting point is preferably 50 ° C., more preferably 70 ° C., still more preferably 90 ° C., particularly preferably 130 ° C., and most preferably 150 ° C. When the melting point is in the range between the above upper limit and lower limit, the production of the resin composition by melt kneading or the synthetic wood by melt molding has little influence on the molding work environment such as smoke, odor, natural fiber (C), especially It is also preferable because the burning problem of wood powder is reduced. In addition, it is possible to obtain a resin composition with little stickiness and excellent balance of heat resistance, mechanical strength, impact strength, and impact absorption.

  The resin (A) preferably has 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. More preferably, it is the range of -50 degreeC--10 degreeC. When the glass transition temperature is in the above range, the resin composition tends to be excellent in balance between long-term stability, heat resistance, impact resistance, and mechanical strength.

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

  When the density of the resin (A) is in the above range, dimensional stability and mechanical strength are excellent. As the mechanism, the resin having the above density tends to be excellent in water resistance because of relatively few polar groups, and it is considered that the water absorption of the natural fiber (C) can be suppressed. Therefore, it is considered that the load at the interface between the natural fiber (C) and the resin (A) is reduced, resulting in excellent dimensional stability and increased mechanical strength. Moreover, it becomes possible to obtain the mechanical strength equivalent to the conventional one by a lighter resin composition. Furthermore, the resin composition excellent in antifouling property can be obtained. In addition, a resin composition having a good balance of workability, heat resistance, mechanical strength, impact strength, and impact absorption can be obtained.

  The flexural modulus of the resin (A) measured according to JIS K7171: 94 is preferably 1 to 10,000 MPa. Here, when the bending elastic modulus is 500 MPa or more, the bending elastic modulus is preferably 500 to 7000 MPa, more preferably 700 to 5000 MPa, particularly preferably 900 to 3000 MPa, and further preferably 1000 to 2000 MPa. It is. When the flexural modulus falls within the above range, a resin composition having not only excellent workability but also a good balance of scratch resistance, heat resistance and mechanical strength can be obtained. Moreover, when the said bending elastic modulus is less than 500 MPa, Preferably it is less than 300 MPa, More preferably, it is less than 100 MPa, More preferably, it is less than 50 MPa. When the flexural modulus falls within the above range, it is possible to obtain a resin composition excellent not only in flexibility but also in impact absorption, light weight, vibration proofing, vibration damping and sound damping. Furthermore, it is possible to obtain a resin composition excellent in design properties such as mold transfer properties, texture transfer properties, and surface grip properties.

2. Compatibilizer (B)
The compatibilizer (B) is a resin different from the resin (A) and is a compound for compatibilizing the resin (A) and the natural fiber (C). The compatibilizer (B) is preferably a polyolefin wax (B1) or a petroleum resin (B2), which will be described later.
When the natural fiber (C) is blended with the resin (A) as the base of the resin composition, the compatibility of the resin (A) and the natural fiber (C) may be poor and uniform kneading may not be possible. In particular, when 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 achieve compatibility. Therefore, when molding the resin composition containing the resin (A) and the natural fiber (C) and its molded product, the workability is deteriorated or the uniformity of the molded product is insufficient. In many cases, the heat resistance, mechanical strength, or flexibility (elongation) was lowered.

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

  According to the study by the present inventors, it was found that when the compatibilizer (B) has a bulky skeleton in the molecular chain, there is an effect of improving the balance of appearance, heat resistance and mechanical strength. In particular, when the compatibilizer (B) is selected from the group consisting of polyolefin wax (B1) and petroleum resin (B2), it has been found that these effects are high.

  Although the detailed mechanism is not clear, it is considered that the compatibilizer having a bulky skeleton in the molecular chain is easily compatible with natural fibers (C) having a generally bulky skeleton such as cellulose. Therefore, when molding the resin composition of the present invention, the compatibilizer (B) can be localized on the surface of the natural fiber (C), and the dispersibility of the natural fiber (C) in the resin composition Is expected to increase. On the other hand, if the compatibility of the compatibilizer (B) and the natural fiber (C) is poor or excessive in the step of solidifying the resin composition from the molten state, the low molecular weight product is a resin composition. May bleed out and cause appearance deterioration. On the other hand, in the resin composition of the present invention, since the amount of the compatibilizer (B) is in the above-mentioned range, the compatibilizer (B) added to the resin composition is natural fiber (C). It is thought that it can exist uniformly on the surface. Therefore, it is considered that the balance of appearance, heat resistance, processability, and mechanical strength is improved without the compatibilizer (B) and the natural fiber (C) being unevenly distributed in the resin composition.

  Examples of the compound having a bulky skeleton in the molecular chain include petroleum resins (B2) and terpene resins described later. In general, even a wax composed of a polyolefin having no bulky skeleton can be obtained by introducing a bulky structural unit into the molecular chain by modification such as acid modification or styrene modification described later. It can be set as the compound which has.

  When the compatibilizer (B) is an unsaturated carboxylic acid derivative monomer modified product of polyolefin wax (for example, maleic anhydride modified product) or air oxide (a kind of polyolefin wax (B1) described later), natural fibers This is preferable because the compatibility with (C) is particularly increased. Further, a styrene-modified product of polyolefin wax (a kind of polyolefin wax (B1) described later) is also preferable because it is considered to be easily compatible with natural fibers (C) having a bulky skeleton such as cellulose. When the above-mentioned polyolefin wax-modified unsaturated carboxylic acid derivative-modified product, air oxide, or styrene-modified product is used as the compatibilizer (B), the balance of appearance, heat resistance, workability, and mechanical strength is further improved.

2-1. Properties of Polyolefin Wax (B1) and Petroleum Resin (B2) The below-described polyolefin wax (B1) and petroleum resin (B2) used as the compatibilizer (B) preferably satisfy the following requirements (i) to (iv) It is preferable.

  (I) The polystyrene-equivalent number average molecular weight (Mn) of the 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 500-18000, More preferably, it is 1000-12000, More preferably, it is 1500-12000, More preferably, it is 3700-12000, Especially preferably, it is 6000-12000, Most preferably, it is 8000 10,000. When the number average molecular weight is within the above range, the dispersibility of the natural fiber (C) in the resin composition is increased, and the appearance, heat resistance, and mechanical strength are excellent. Moreover, the workability and kneadability of the resin composition tend to be good.

  (Ii) The softening point of the polyolefin wax (B1) and petroleum resin (B2) measured in accordance with JISK 2207 is preferably in the range of 70 to 170 ° C. The upper limit of the softening point is more preferably 160 ° C, still more preferably 150 ° C, and particularly preferably 145 ° C. Further, the lower limit is more preferably 80 ° C., still more preferably 90 ° C., particularly preferably 95 ° C., and most preferably 105 ° C. When the softening point is in the above range, the appearance, workability, heat resistance, and mechanical strength of the resin composition are excellent.

(Iii) The density of the polyolefin wax (B1) and petroleum resin (B2) measured by the density gradient tube method is preferably in the range of 830 to 1200 kg / m ³ . More preferably, it is 860-1100 kg / m < ³ >, More preferably, it is 890-1000 kg / m < ³ >, Especially preferably, it is 895-960 kg / m < ³ >, More preferably, it is 895-935 kg / m < ³ >. When the density is in the above range, the dispersibility of natural fibers is enhanced and the appearance, heat resistance, and mechanical strength of the resin composition are excellent. In addition, processability and kneadability tend to be good. The reason for this is not clear, but in general, the density of the natural fiber (C) is 1000 kg / m ³ or more. On the other hand, when a compatibilizer (B) having a lower density is used, the surface tension of the natural fiber (C) surface is lowered when the compatibilizer (B) is localized on the natural fiber (C) surface. There exists an effect and, as a result, the cohesive force of a natural fiber (C) can be reduced. And it is thought that natural fiber can be disperse | distributed uniformly, is excellent in workability and kneadability, and is excellent in the external appearance of a resin composition, heat resistance, and mechanical strength.

Moreover, the difference between the density of the density and the compatibilizer resin (A) (B) is preferably smaller than 50 kg / ^{m 3,} more preferably less than 30kg / ^{m 3,} less than 15 kg / ^{m 3} Particularly preferred. When the density difference is in the above range, the processability, appearance, heat resistance, and mechanical strength are excellent. For this reason, it is considered that substances having similar densities tend to be mixed with each other. That is, since the compatibility of the resin (A) and the compatibilizer (B) is high, as a result, the dispersibility of the natural fiber (C) coated with the compatibilizer (B) is increased. It is thought that workability is improved. At the same time, bleeding out due to the compatibilizing agent (B) from the resin (A) is suppressed, so that it is considered that the appearance, heat resistance, and mechanical strength can be compatible.

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

  Here, as the compatibilizer (B), any two or more compatibilizers may be selected from the polyolefin wax (B1), petroleum resin (B2), and other compatibilizer (B) described later. These may be selected and used in combination. At this time, if the melting point and the softening point of the compatibilizer used in combination are different from each other, it becomes easy to achieve both the workability and the mechanical strength of the resin composition.

  When two or more compatibilizers (B) are used in combination, the softening point of the compatibilizer (BH) having the highest softening point and the softening point of the compatibilizer (BL) having the lowest softening point The difference is preferably 5 ° C. or more, more preferably 10 ° C. or more, further preferably 20 ° C. or more, still more preferably 30 ° C. or more, and particularly preferably 40 ° C. or more.

  If the difference between the softening point of the compatibilizer (BH) and the softening point of the compatibilizer (BL) is in the above range, it is preferable because the processability and mechanical strength of the resulting resin composition are excellent. In particular, the torque of the extruder can be reduced and shearing heat generation can be suppressed. The reason is not clear, but for example, when an acid-modified polypropylene wax (BH) having a high softening point and a polyethylene wax (BL) having a low softening point are used in combination as the compatibilizer (B), the softening point is lower. It is considered that the dispersibility of the natural fiber (C) in the resin (A) is increased and the torque of the extruder is effectively reduced by melting the polyethylene wax (BL) earlier in the system. Furthermore, since the melted polyethylene wax (BL) suppresses shearing heat generation in the system, it is considered that scorching of natural fibers is suppressed as a result. That is, it is considered that excellent processability is exhibited by the compatibilizer (BL) having a low softening point. On the other hand, after the dispersibility of the natural fiber (C) is increased, the acid-modified polypropylene (BH) having a high softening point melts, so that the contact efficiency between the acid-modified polypropylene wax (BH) and the natural fiber (C) is good. Thus, the modification effect of the natural fiber (C) by the acid-modified polypropylene wax (BH) is enhanced. Therefore, it is considered that the mechanical properties can be effectively improved while improving the processability of the resin composition.

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

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

  Moreover, the dispersibility of the natural fiber (C) tends to increase as the amount of the compatibilizer (BL) having the lowest softening point increases. Specifically, the mass ratio (BH) / (BL) between (BH) and (BL) is preferably in the range of 1/200 to 1/1, and 1/50 to 1 / 1.1. More preferably, it is more preferably 1/20 to 1 / 1.3, and most preferably 1/10 to 1 / 1.5. In addition, when arbitrary 2 or more types of compatibilizers are selected from the group consisting of polyolefin wax (B1) and they are used in combination, the balance between processability and mechanical strength tends to be particularly good.

  The compatibilizer (BH) having the highest softening point is preferably a modified polyolefin wax (B1) described later, and the compatibilizer (BH) having the highest softening point and the compatibilization having the lowest softening point. The agent (BL) is preferably selected from polyolefin wax (B1). In particular, the polyolefin wax (B1) is preferably an unsaturated carboxylic acid derivative monomer modified product of an olefin wax.

  The compatibilizer (BH) having the highest softening point is an unsaturated carboxylic acid derivative monomer modified product (for example, a maleic anhydride modified product) or an oxide (described later polyolefin wax (B1)) of a polyolefin wax. 1 type), the acid value range of the compatibilizer (BH) having the highest softening point is preferably 40 to 100 mgKOH / g, more preferably 50 to 100 mgKOH / g, and still more preferably It is 60-100 mgKOH / g, More preferably, it is 60-95 mgKOH / g, More preferably, it is 60-90 mgKOH / g, Most preferably, it is 80-90 mgKOH / g. When the acid value of the compatibilizer (BH) having the highest softening point falls within the above range, a resin composition having excellent heat resistance and mechanical strength can be obtained.

  Here, the compatibilizer (BL) having the lowest softening point is an unsaturated carboxylic acid derivative monomer modified product (for example, a maleic anhydride modified product) or an oxide (described later polyolefin wax (described later) of the polyolefin wax described later. In the case of B1), 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. When the compatibilizer (BL) having the lowest softening point has an acid value in the above range, the processability is maintained, the deflection temperature under load as the resin composition, the softening point, etc. are increased, and the heat resistance is excellent. It can be set as a resin composition. Although the reason is not clear, the compatibilizer (BL) having the lowest softening point is the natural fiber (C) because the acid value is in the above range even when the resin composition is subjected to a temperature higher than the softening point. It is easy to localize and immobilize on the surface. As a result, it is considered that the heat resistance of the resin composition is increased without increasing the molecular mobility even at high temperatures.

  On the other hand, when the acid value of the compatibilizer (BL) having the lowest softening point is low, the processability of the resin composition is particularly good. Specifically, the acid value is preferably 3 mgKOH / g or less, and the acid value is more preferably 1 mgKOH / g or less. The compatibilizer (BL) having the lowest softening point is particularly preferably an unmodified polyolefin wax (B1). The smaller the acid value of the polyolefin wax (B1), which is the compatibilizer (BL) having the lowest softening point, is the interaction between the polyolefin wax (B1) and the natural fiber (C) at the extrusion temperature of the resin composition. Is considered to be small, and the workability is considered to be superior.

  It is also preferable to use the polyolefin wax (B1) and the petroleum resin (B2) in combination. In this case, the greater the ratio of the polyolefin wax (B1), the more the dispersibility, appearance, and mechanical properties of the natural fiber (C). , Easy to process, heat resistance. On the other hand, the greater the ratio of petroleum resin (B2), the more easily the kneadability between resin (A) and natural fiber (C) is significantly improved.

2-2. Polyolefin wax (B1)
In the present invention, the concept of “polyolefin wax” includes not only a general polyolefin wax (hereinafter also referred to as “unmodified polyolefin wax”) but also a modified product thereof (hereinafter also referred to as “modified polyolefin wax”). A preferred polyolefin wax (B1) as a compatibilizer (B) for the resin composition of the present invention is at least one homopolymer or copolymer selected from ethylene or an α-olefin having 3 to 12 carbon atoms, Or the unsaturated carboxylic acid derivative monomer modified product (for example, maleic anhydride modified product), air oxide, or styrene modified product. More preferably, an ethylene homopolymer, a propylene homopolymer, a copolymer of 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. A polymer selected from the group consisting of copolymers with at least one α-olefin selected from 12 α-olefins, or an unsaturated carboxylic acid derivative monomer-modified product of the polymer (for example, a maleic anhydride-modified product) Or modified styrene or air oxide. The polyolefin wax (B1) can also be used for toner additives, hot melt additives, pigment dispersants, molding processing aids, electrical cable compound additives, 3D printer resin compounding agents, and the like.

  Here, the α-olefin having 3 to 12 carbon atoms (or 4 to 12 carbon atoms) to be polymerized with ethylene or propylene includes propylene having 3 carbon atoms, 1-butene having 4 carbon atoms, and 5 carbon atoms. 1-pentene, 1-hexene having 6 carbon atoms, 4-methyl-1-pentene, 1-octene having 8 carbon atoms and the like, more preferably propylene, 1-butene, 1-hexene, 4- Methyl-1-pentene.

  Hereinafter, the unmodified polyolefin wax and the production method thereof will be described first, and then the modified polyolefin wax modified with these will be described.

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

-Polyethylene-based wax When the polyolefin wax (B1) is a polyethylene-based wax, examples of preferable polyethylene-based wax are described in, for example, JP-A 2009-144146.

  When the polyolefin wax (B1) is a polyethylene wax, an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms is preferable. 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, when the polyethylene 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 91.0 to 99.9 mol%. More preferably, it is 93.0-99.9 mol%, More preferably, it is 95.0-99.9 mol%, Most preferably, it is 95.0-99.0 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 to 9.0 mol%, preferably 0.1 to 7.0 mol%, More preferably, it is 0.1-5.0 mol%, Most preferably, it is 1.0-5.0 mol%. However, (a) + (b) = 100 mol%. The content rate of the structural unit of the said olefin polymer can be calculated | required by the analysis of a < ¹³ > C-NMR spectrum.

  Here, examples of the α-olefin having 3 to 12 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl. Linear or branched α-olefins such as -1-pentene, 1-octene, 1-decene, 1-dodecene and the like, preferably propylene, 1-butene, 1-hexene, 4-methyl-1- Pentene and 1-octene are more preferable, α-olefins having 3 to 8 carbon atoms, particularly preferable are propylene and 1-butene, and most preferable is 1-butene. When ethylene and propylene or 1-butene are copolymerized, the compatibilizing agent (B) becomes hard and tends to be less sticky, so that the surface property of the molded article is improved. Moreover, it is preferable also from the point which improves mechanical strength and heat resistance. The reason why the compatibilizer (B) becomes harder and less sticky by combining ethylene with propylene and 1-butene is not clear, but propylene and 1-butene are compared with other α-olefins. In order to efficiently lower the melting point with a small amount of copolymerization, the degree of crystallinity tends to be higher than that at the same melting point, which is assumed to be a factor. The α-olefin may be used alone or in combination of two or more.

  The polyethylene wax is particularly preferably used when the resin (A) is a polyethylene resin. When these are combined, the compatibility between the resin (A) and the compatibilizer (B) increases, and the resulting molded article has a good balance of appearance, workability, mechanical strength, and heat resistance.

-Polypropylene wax The polyolefin wax (B1) may be a polypropylene wax. Polypropylene wax is a homopolymer of propylene obtained by copolymerizing propylene and other monomers as required in the presence of a stereospecific catalyst, or a copolymer mainly composed of propylene. It may be obtained by thermally decomposing high molecular weight polypropylene. In addition, the polypropylene wax may be purified by a method such as solvent fractionation that is fractionated based on a difference in solubility in a solvent, or molecular distillation that is fractionated based on a 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.

  When the polypropylene wax is a copolymer of propylene and ethylene, the structural unit derived from propylene may be 60 to 99.5 mol%. The structural unit amount derived from propylene is preferably 80 to 99 mol%, more preferably 90 to 98.5 mol%, still more preferably 95 to 98 mol%. By using the propylene copolymer, a resin composition having an excellent balance of appearance, mechanical strength, and heat resistance can be obtained.

  When 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, 3- Linear or branched α-olefins such as methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene Can be mentioned. Among these, 1-butene is particularly preferable.

  When the polypropylene wax is a propylene / α-olefin copolymer, the amount of the structural unit (a ′) derived from propylene is preferably 60 to 90 mol%, more preferably 65 to 88 mol%. More preferably, it is 70-85 mol%, Most preferably, it is 75-82 mol%. On the other hand, the amount of the structural unit (b ′) derived from the α-olefin having 4 or more carbon atoms is preferably 10 to 40 mol%, more preferably 12 to 35 mol%, still more preferably 15 to 30 mol%. And particularly preferably 18 to 25 mol%. However, (a ′) + (b ′) = 100 mol%.

  When the polypropylene wax is a propylene / α-olefin copolymer and the composition is in the above range, a resin composition excellent in appearance can be obtained. The reason is that it takes time for the compatibilizer to crystallize, so that a long time during which the resin composition can flow can be secured on the mold or in the cooling step. As a result, it is considered that the surface property of the obtained molded product is improved. Also, heat resistance and mechanical strength tend to be excellent.

  The polypropylene wax is particularly preferably used when the resin (A) is a polypropylene resin. When these are combined, the compatibility between the resin (A) and the compatibilizer (B) increases, and the resulting molded article has a good balance of appearance, workability, mechanical strength, and heat resistance.

-4-Methyl-1-pentene wax Polyolefin wax (B1) was obtained by thermally decomposing 4-methyl-1-pentene / α-olefin copolymer disclosed in International Publication No. 2011/055803. Or 4-methyl-1-pentene polymer as disclosed in JP-A-2015-028187.

(Method for producing unmodified polyolefin wax)
The unmodified polyolefin wax such as polyethylene wax and polypropylene wax described above may be obtained by directly polymerizing ethylene or α-olefin, etc., and is obtained by pyrolyzing a high molecular weight copolymer. May be used. In the case of thermal decomposition, it is preferable to perform thermal decomposition at 300 to 450 ° C. for 5 minutes to 10 hours. In this case, the unmodified polyolefin wax has an unsaturated end. Specifically, the number of vinylidene groups per 1000 carbon atoms, as measured by ¹ H-NMR, is particularly preferably 0.5 to 5 because the compatibilizing effect on the natural fiber (C) is enhanced. In addition, the unmodified polyolefin wax may be purified by a method such as solvent fractionation that is fractionated based on a difference in solubility in a solvent, or distillation. Moreover, what consists of a single type of polymer may be sufficient, and the thing formed by mixing 2 or more types of polymers may be sufficient.

  When ethylene or α-olefin is directly polymerized, various known production methods such as a production method of polymerizing ethylene or α-olefin with a Ziegler / Natta catalyst or a metallocene catalyst can be applied.

  For example, in the state where the monomer for polymerization and its polymer are present as particles in an inert hydrocarbon medium such as hexane, suspension polymerization for polymerizing them, gas phase polymerization for polymerizing without using a solvent, etc. Can be applied. Moreover, the solution polymerization method etc. which superpose | polymerize in the state which melt | dissolved the monomer for polymerization and its polymer in the inert hydrocarbon medium are applicable. Among these, the solution polymerization method is particularly preferable in terms of both economy and quality. The polymerization reaction can be performed by any method such as a batch method or a continuous method. The polymerization can also be carried out in two or more stages having different reaction conditions.

  Examples of the inert hydrocarbon medium used in the suspension polymerization method and the solution polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, Examples include alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. An inert hydrocarbon medium may be used individually by 1 type, and 2 or more types may be mixed and used for it. Moreover, what is called bulk polymerization method using (alpha) -olefin itself as a solvent can also be used.

  As the catalyst, a metallocene catalyst is preferable. As a metallocene catalyst, it reacts with (a) a metallocene compound of a transition metal selected from Group 4 of the periodic table, (b) (b-1) an organoaluminum oxy compound, and (b-2) a metallocene compound (a). And (b-3) at least one compound selected from organoaluminum compounds, and a catalyst that forms an ion pair (hereinafter sometimes abbreviated as “ionized ionic compound”). (See Japanese Patent Application Laid-Open No. 08-239414, pamphlet of International Publication No. 2007/114102).

  Examples of transition metal metallocene compounds (a) selected from Group 4 of the periodic table include metallocene compounds described in JP-A-08-239414 and International Publication No. 2007/114102 pamphlet. (N-Butylcyclopentadienyl) zirconium dichloride and bis (n-butylcyclopentadienyl) zirconium dimethyl are particularly preferably used.

  As the organoaluminum oxy compound (b-1), a conventionally known aluminoxane can be used as it is. Examples thereof include organoaluminum oxy compounds described in JP-A-08-239414 and International Publication No. 2007/114102. As the organoaluminum oxy compound (b-1), methylaluminoxane which is easily available for commercial products and modified methylaluminoxane (MMAO) prepared using trimethylaluminum and triisobutylaluminum are preferable.

  Examples of the ionized ionic compound (b-2) include ionized ionic compounds described in JP-A-08-239414 and International Publication No. 2007/114102. As the ionized ionic compound (b-2), since it is easily available as a commercial product and greatly contributes to the improvement of polymerization activity, triphenylcarbenium tetrakis (pentafluorophenyl) borate and N, N-dimethyl are used. Anilinium tetrakis (pentafluorophenyl) borate is preferred.

  As an organoaluminum compound (b-3), the organoaluminum compound described in the international publication 2007/114102 pamphlet can be mentioned, for example. As the organoaluminum compound (b-3), trimethylaluminum, triethylaluminum and triisobutylaluminum that are easily available for commercial products are preferable. Of these, triisobutylaluminum that is easy to handle is particularly preferred.

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

  When the monomer is polymerized using the metallocene catalyst, the content of each component can be set as follows.

(1) The metallocene compound (a) can be used in an amount of 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² mol, per liter of reaction volume.
(2) When a catalyst containing a metallocene compound (a) and an organoaluminum oxy compound (b-1) is used, the compound (b-1) is composed of an aluminum atom (Al) in the compound (b-1) and The metallocene compound (a) can be used in such an amount that the molar ratio [Al / M] to all the transition metal atoms (M) is 0.01 to 5000, preferably 0.05 to 2000.
(3) In the case of using a catalyst containing the metallocene compound (a) and the ionic compound (b-2), the compound (b-2) is the total amount of the compound (b-2) and the metallocene compound (a). It can be used in such an amount that the molar ratio [(b-2) / M] to the transition metal atom (M) is 1 to 10, preferably 1 to 5.
(4) When a catalyst containing the metallocene compound (a) and the organoaluminum compound (b-3) is used, the compound (b-3), all transition metal atoms (M) in the metallocene compound (a), and The molar ratio [(b-3) / M] is usually 0.01 to 50000, preferably 0.05 to 10000.

  The polymerization temperature is usually in the range of 10 to 200 ° C., but from the viewpoint of producing the unmodified polyolefin wax having the above-mentioned preferred structural unit amount, the polymerization temperature is preferably in the range of 60 to 180 ° C., More preferably, it is the range of 75-170 degreeC. The polymerization pressure can be normal pressure to 7.8 MPa-G (G is a gauge pressure) or less, more preferably normal pressure to 4.9 MPa-G (G is a gauge pressure) or less.

  In the polymerization, ethylene and α-olefin are supplied to the polymerization system in such an amount ratio that an unmodified polyolefin wax having the specific composition described above can be obtained. In the polymerization, a molecular weight regulator such as hydrogen can be added.

  An unmodified polyolefin wax can be obtained by treating the polymerization solution thus polymerized by a conventional method.

  The polymer obtained by the above method is degassed under vacuum at a temperature equal to or higher than the melting point, for example, once dissolved in a solvent such as toluene, xylene, hexane or heptane, and then a polar solvent such as methanol or acetone is added. Further purification may be performed by a method of filtering and removing the low molecular weight part or a method of dissolving the whole amount in a solvent and then precipitating at a specific temperature to remove the high molecular weight part or the low molecular weight part.

  When the polyolefin wax (B1) is an unmodified polyolefin wax, its number average molecular weight (Mn) and intrinsic viscosity [η] tend to decrease when the polymerization temperature during polymerization is increased or when the hydrogen concentration is increased. Can be controlled within. Or it can adjust with the usage-amount of the organoaluminum oxy compound and / or ionized ionic compound used as a cocatalyst. Further, it can be adjusted by purification after polymerization.

  The content of units derived from ethylene or each α-olefin can be controlled by adjusting the blending amount during polymerization, as well as by the catalyst type and polymerization temperature.

  Mw / Mn of the polyolefin wax (B1) (unmodified polyolefin wax) can be controlled by the catalyst type, polymerization temperature, and the like. In general, a Ziegler-Natta catalyst or a metallocene catalyst is used for the polymerization, but a metallocene catalyst is preferably used in order to obtain a suitable range of Mw / Mn. Moreover, it can also be made a suitable range by refine | purifying by methods, such as solvent fractionation which fractionates with the difference in the solubility with respect to a solvent, or distillation.

  The softening point of the polyolefin wax (B1) (unmodified polyolefin wax) can be adjusted by the composition of ethylene or α-olefin. For example, the content of α-olefin in the case of a copolymer of ethylene and α-olefin. By increasing the number, the tendency to lower the softening point can be obtained. It can also be controlled by the catalyst type, polymerization temperature and the like. Further, 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, the polymerization temperature during polymerization, and the hydrogen concentration.

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

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

  In the oxidative modification, the unmodified polyolefin wax is brought into contact with oxygen or an oxygen-containing gas while stirring in a molten state to carry out an oxidation reaction. In the description of “oxygen or oxygen-containing gas” in the present specification, Not only pure oxygen (oxygen obtained by ordinary liquid air fractionation or electrolysis of water, which may contain other components to the extent of impurities), but also a mixed gas of pure oxygen and other gases, such as air And ozone are also included.

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

  The air oxide acid value (JIS K5902) of the polyolefin wax thus obtained is preferably 1 to 100 mgKOH / g, more preferably 20 to 90 mgKOH / g, more preferably 30 to 87 mgKOH / g. is there. Here, the acid value indicates the number of mg of potassium hydroxide required for neutralization per 1 g of the sample.

  When the acid value of the air oxide of the polyolefin wax is in the above range, the appearance, workability, appearance, heat resistance, and mechanical strength are particularly excellent. This is probably because the balance of the compatibilizing effect between the natural fiber (C) and the resin (A) is excellent. Although the detailed mechanism is not clear, when the acid value is in the above range, the affinity between the natural fiber (C) and the compatibilizer (B) is moderately increased, and the familiarity with the resin (A) is increased. Therefore, as a result, the uniformity of the entire system is increased, the dispersibility of the natural fiber (C) is improved, the appearance and workability are improved, and the appearance is considered to be improved. As a result, it is considered that the heat resistance and mechanical strength of the resin composition are increased despite the addition of a low molecular weight wax.

  In particular, when obtaining a resin composition having excellent processability and appearance, the acid value range of the polyolefin wax air oxide is preferably 1 to 55 mgKOH / g, and the lower limit is more preferably 20 mgKOH / g. Yes, particularly preferably 30 mg KOH / g, most preferably 42 mg KOH / g. 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 having excellent heat resistance and mechanical strength, the acid value range of the polyolefin oxide air oxide is preferably 40 to 100 mgKOH / g, more preferably 50 to 100 mgKOH / g. More preferably 60 to 100 mg KOH / g, still more preferably 60 to 95 mg KOH / g, still more preferably 60 to 90 mg KOH / g, and particularly preferably 80 to 90 mg KOH / g.

-Graft-modified product of polyolefin wax The graft-modified product of polyolefin wax is, for example, modified polyolefin wax obtained by acid-grafting unmodified polyolefin wax (hereinafter also referred to as acid-modified polyolefin wax (B1 ')) or styrene graft-modified with styrene. It may be a modified polyolefin wax, a polyolefin wax graft-modified with a mixture thereof, or the like. These can be prepared by a conventionally known method. For example, (1) an unmodified polyolefin wax used as a raw material, and (2) an unsaturated carboxylic acid or derivative thereof, styrenes, or sulfonate, and (3) in the presence of a polymerization initiator such as an organic peroxide. In a solution in which (1) an unmodified polyolefin wax as a raw material and (2) an unsaturated carboxylic acid or derivative thereof, styrenes or sulfonate are dissolved in an organic solvent; It can be obtained by kneading in the presence of a polymerization initiator such as an oxide.

  For melt kneading, for example, an autoclave, a Henschel mixer, a V-type blender, a tumbler blender, a ribbon blender, a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer and the like are used. Among these, when an apparatus excellent in batch type melt kneading performance such as an autoclave is used, a polyolefin wax in which each component is more uniformly dispersed and reacted can be obtained. Compared to the continuous method, the batch method is easy to adjust the residence time, and since the residence time can be made longer, it is relatively easy to increase the modification rate and modification efficiency, and is the most preferred embodiment in the present invention.

  When the acid-modified polyolefin wax (B1 ′) is a wax graft-modified with an unsaturated carboxylic acid derivative monomer and a styrene monomer, the graft amount ratio “(unsaturated carboxylic acid derivative monomer) / (styrene type) Monomer) ”is preferably from 0.01 to 1, more preferably from 0.03 to 0.8, and particularly preferably from 0.05 to 0.6. When the graft ratio is less than 0.01, the interaction with the surface of the natural fiber (C) of the unsaturated carboxylic acid derivative monomer is reduced, so that the impact resistance is hardly improved. On the other hand, when the graft amount ratio is larger than 1, the melt viscosity of the acid-modified polyolefin wax (B1 ′) becomes high, making it difficult to produce.

  Examples of unsaturated carboxylic acids or derivatives thereof used for acid graft modification include methyl acrylate, ethyl acrylate, butyl acrylate, acrylate-sec-butyl, isobutyl acrylate, propyl acrylate, isopropyl acrylate, acrylic 2-octyl acid, dodecyl acrylate, stearyl acrylate, hexyl acrylate, isohexyl acrylate, phenyl acrylate, 2-chlorophenyl acrylate, diethylaminoethyl acrylate, 3-methoxybutyl acrylate, diethylene glycol ethoxy acrylate Rate, acrylic acid esters such as acrylic acid-2,2,2-trifluoroethyl; methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylate-sec-butyl, methacrylate Isobutyl phosphate, propyl methacrylate, isopropyl methacrylate, -2-octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, stearyl methacrylate, hexyl methacrylate, decyl methacrylate, phenyl methacrylate, 2-chlorohexyl methacrylate , Methacrylate esters such as diethylaminoethyl methacrylate, 2-hexylethyl methacrylate, and 2,2,2-trifluoroethyl methacrylate; ethyl maleate, propyl maleate, butyl maleate, diethyl maleate, maleate Maleic acid esters such as dipropyl acid and dibutyl maleate; fumaric acid esters such as ethyl fumarate, butyl fumarate and dibutyl fumarate; maleic acid, fumaric acid, itaconic acid, crotonic acid, nadi Click acid, dicarboxylic acids such as methyl hexahydrophthalic acid; maleic anhydride, itaconic anhydride, citraconic anhydride, allyl succinic anhydride, glutaconic acid, and the like anhydrides such as nadic. Among these, maleic anhydride is preferable. Maleic anhydride has a relatively high reactivity with the unmodified polyolefin wax that is a raw material, and itself has a small structural change due to polymerization and tends to be stable as a basic structure. For this reason, when the compatibilizer (B) is a maleic anhydride-modified polyolefin wax, the maleic anhydride-modified polyolefin wax remains stable even in a high temperature environment during molding, It becomes possible to act on the fiber (C) surface efficiently. As a result, it is considered that the resin composition has a good balance of appearance, heat resistance, workability, and mechanical strength.

  The acid value (JIS K5902) of the acid-modified polyolefin wax (B1 ′) thus obtained is preferably 1 to 100 mgKOH / g, more preferably 20 to 90 mgKOH / g, and more preferably 30 to 87 mg KOH / g. Here, the acid value refers to the number of mg of potassium hydroxide required for neutralization per 1 g of the sample.

  When the acid value of the acid-modified polyolefin wax (B1 ') is in the above range, the appearance, workability, appearance, heat resistance, and mechanical strength are particularly excellent. This is probably because the balance of the compatibilizing effect between the natural fiber (C) and the resin (A) is excellent. Although the detailed mechanism is not clear, when the acid value is in the above range, the affinity between the natural fiber (C) and the compatibilizer (B) is moderately increased, and the familiarity with the resin (A) is increased. Therefore, as a result, the uniformity of the entire system is increased, the dispersibility of the natural fiber (C) is improved, the appearance and workability are improved, and the appearance is considered to be improved. As a result, it is considered that the heat resistance and mechanical strength of the resin composition are increased despite the addition of a low molecular weight wax.

  Further, when obtaining a resin composition excellent in processability and appearance, the acid value range of the acid-modified polyolefin wax (B1 ′) is preferably 1 to 55 mgKOH / g, and the lower limit is more preferably 20 mgKOH / g. g, particularly preferably 30 mg KOH / g, most preferably 42 mg KOH / g. 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 and mechanical strength, the acid value range of the acid-modified polyolefin wax (B1 ′) is preferably 40 to 100 mgKOH / g, more preferably 50 to 100 mgKOH / g. g, more preferably 60 to 100 mg KOH / g, still more preferably 60 to 95 mg KOH / g, still more preferably 60 to 90 mg KOH / g, and particularly preferably 80 to 90 mg KOH / g.

  Examples of styrenes when the polyolefin wax is graft-modified with styrenes include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene, m-chloro. Styrene and p-chloromethylstyrene, 4-vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, 2-isopropenylpyridine, 2-vinylquinoline, 3-vinyl Isoquinoline, N-vinylcarbazole, N-vinylpyrrolidone and the like can be mentioned.

  When the polyolefin wax is graft-modified with styrenes, the content of styrenes is preferably 1 to 500 parts by mass, more preferably 5 to 200 parts by mass when the polyolefin wax is 100 parts by mass. More preferably, it is 20-160 mass parts, Most preferably, it is 22-30 mass parts. When the content of styrenes in the modified polyolefin wax is within the above range, the compatibility between the modified polyolefin wax and the natural fiber (C) is improved, and excessive interaction that causes an increase in viscosity is suppressed. Therefore, it is excellent in balance of workability, appearance, heat resistance, and mechanical strength.

  The polyolefin wax or the above-mentioned graft-modified polyolefin wax may be modified with a sulfonate. In this case, the modification amount is preferably 0.1 to 100 mmol, more preferably 5 to 50 mmol, per 1 g of the polymer. When the modification amount with the sulfonate is within the above range, the dispersibility of the natural fiber (C) is improved, and the mechanical strength of the molded product obtained from the resin composition is improved.

  The acid-modified polyolefin wax (B1 ′) may be a commercially available product. Examples of commercially available acid-modified polyolefin wax (B1 ′) include Diacarna-PA30 (Mitsubishi Chemical Corporation), high wax acid-treated type 2203A (Mitsui Chemicals) and oxidized paraffin (Nippon Seiwa ( Etc.)).

2-3. Petroleum resin (B2)
The compatibilizer (B) may be a petroleum resin (B2) as described above. Examples of the petroleum resin (B2) include, for example, an aliphatic petroleum resin whose main raw material is a C5 fraction of tarnaphtha, an aromatic petroleum resin whose main raw material is a C9 fraction, and a copolymer petroleum resin thereof. It is. That is, C5 petroleum resin (resin obtained by polymerizing C5 fraction of naphtha cracked oil), C9 petroleum resin (resin obtained by polymerizing C9 fraction of naphtha cracked oil), C5C9 copolymerized petroleum resin (C5 fraction of naphtha cracked oil) And a C9 fraction copolymerized resin). When the compatibilizing agent is petroleum resin (B2), 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 hydrotreated are generally excellent in heat resistance. Therefore, the function as a compatibilizing agent is not impaired even after the thermal process of molding.

  Examples of the petroleum resin (B2) include a coumarone indene resin containing styrenes, indenes, coumarone, other dicyclopentadiene, etc. of a tar naphtha fraction; a condensate of p-tertiarybutylphenol and acetylene And xylene-based resins obtained by reacting o-xylene, p-xylene, or m-xylene with formalin.

  Of the petroleum resins (B2), vinyl aromatic petroleum resins are preferable. Examples of vinyl aromatic petroleum resins include vinyl aromatic hydrocarbon homopolymers; or vinyl aromatic hydrocarbons and fractions of 4 and 5 carbon atoms that are by-produced during petroleum refining and petroleum decomposition. Copolymer resins with any fraction selected, etc. are included.

  Examples of vinyl aromatic hydrocarbons in vinyl aromatic petroleum resins include isopropenyltoluene, styrene, vinyltoluene, α-methylstyrene, etc., and these are used alone or in combination of two or more. Among these, isopropenyltoluene is particularly preferable. In the vinyl aromatic petroleum resin, when the vinyl aromatic hydrocarbon is isopropenyltoluene, the kneadability of the resin composition is particularly good.

  The fractions having 4 and 5 carbon atoms that are copolymerized with vinyl aromatic hydrocarbons (hereinafter referred to as C4 fraction and C5 fraction) are by-produced during petroleum refining, petroleum cracking, etc .; Boiling point is −15 ° C. to + 45 ° C., and 1-butene, 2-butene, isobutene, butadiene, 1-pentene, 2-pentene, cyclopentene, 1,3-piperylene, isoprene, cyclopentadiene, 2-methyl-1 It may contain a polymerizable monomer such as -butene, 2-methyl-2-butene, 3-methyl-1-butene.

  The fractions having 4 and 5 carbon atoms to be copolymerized with the vinyl aromatic hydrocarbon are arbitrary fractions selected from C4 and C5 fractions, except for butadiene as well as C4 fraction and C5 fraction. It may be a C4 fraction, a C5 fraction excluding isoprene, a C5 fraction excluding cyclopentadiene, and the like.

  The polymerization reaction for obtaining the vinyl aromatic petroleum resin may be performed in the presence of a polymerization catalyst. The polymerization catalyst is, for example, a commonly used Friedel-Crafts catalyst. Examples of Friedel-Crafts catalysts include aluminum chloride, aluminum bromide, ethyldichloroaluminum, boron trifluoride, boron trifluoride complexes, and the like. Is included. The polymerization reaction may be performed in a suitable solvent. Examples of suitable solvents include hydrocarbon solvents such as pentane, hexane, octane, kerosene, cyclopentane, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene, mesitylene. The polymerization reaction temperature is usually −50 ° C. to + 80 ° C. The vinyl aromatic petroleum resin may be graft-modified with an unsaturated carboxylic acid derivative monomer or the like, like the polyolefin wax.

2-4. Other compatibilizers (B)
In addition to the polyolefin wax (B1) and the petroleum resin (B2), a rosin resin and a terpene resin may be used as the compatibilizer (B). Examples of the rosin resin include natural rosin, polymerized rosin, modified rosin and rosin derivatives modified with maleic acid, fumaric acid, (meth) acrylic acid, and the like. Examples of the rosin derivative include the above-mentioned natural rosin, polymerized rosin or esterified product of modified rosin, phenol-modified product and esterified product thereof. Furthermore, these hydrogenated products can also be mentioned as rosin derivatives.

Examples of the terpene resin include resins composed of α-pinene, β-pinene, limonene, dipentene, terpene phenol, terpene alcohol, terpene aldehyde, etc., and α-pinene, β-pinene, limonene, dipentene, and the like. An aromatic modified terpene resin obtained by polymerizing aromatic monomers such as α-methylstyrene and isopropenyltoluene. Moreover, these hydrogenated substances can also be mentioned.
One or more resins selected from the group consisting of rosin resins, terpene resins and petroleum resins are preferably hydrogenated derivatives from the viewpoint of excellent weather resistance and discoloration resistance.

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

2-5. Form of compatibilizer (B) At the time of preparing the resin composition, the compatibilizer (B) may be a solid such as a powder, a tablet, or a block, and is dispersed in water or a solvent. Or it may be dissolved. The method of dissolving or dispersing the compatibilizer (B) in water or an organic solvent is not particularly limited, but the method of dissolving and dispersing the compatibilizer (B) in water or an organic solvent under stirring, And a method in which a mixture of the compatibilizer (B) and water or an organic solvent is heated and gradually cooled or finely divided from a completely or incompletely dissolved state. As a method for making fine particles, for example, a solvent composition is set so as to precipitate in advance at 60 to 100 ° C., and the average cooling rate during this period is adjusted to 1 to 20 ° C./hour, preferably 2 to 10 ° C./hour. And a method of precipitation. Alternatively, the compatibilizer (B) may be dissolved in a parent solvent, and then the poor solvent may be added to the solution to cause precipitation. Further, after removing the water or the organic solvent from the solution in which the compatibilizer (B) is dispersed in water or a solvent, the compatibilizer (B) may be used after being dissolved and dispersed in an arbitrary solvent.

3. Natural fiber (C)
Natural fiber (C) is preferably wood flour, wood fiber, bamboo, bamboo fiber, cotton, cellulose, nanocellulose, wool, or agricultural fiber (straw, hemp, flax, kenaf, kapok, jute, ramie, sisal) , Henkenken, corn fiber or coir, or nut shells or rice husks), NBKP (conifer bleached kraft pulp), LBKP (hardwood bleached kraft pulp), and non-wood such as manila hemp, straw, cocoon, husk Examples include natural pulp such as pulp, rayon, and cotton. More preferably, it is wood powder, wood fiber, bamboo, bamboo fiber, or nanocellulose, and considering the production cost and performance balance, wood powder and wood fiber are particularly preferred, and wood powder is most preferred. .

  Wood flour, wood fiber, and the like are not particularly limited to raw wood and tree species, and wood material produced as industrial waste in the wood industry, or wood powder and wood fiber obtained from unused wood material can be used. The wood powder may be a wood powder obtained from one kind of tree species, or may be a mixed powder comprising two or more kinds of tree species. Since wood powder easily absorbs moisture in the air, it is desirable to reduce the moisture in the wood powder by heating and drying in advance, for example, 20% by mass or less, preferably 1% by mass or less. By reducing the moisture concentration in the wood flour, the mixability (kneading property) between the wood flour and the resin (A) can be improved, a more uniform resin composition can be obtained, and good performance as a synthetic wood Can be demonstrated. As the heating and drying conditions, a temperature of 100 to 130 ° C. and a condition of 30 minutes to 4 hours are preferably employed.

4). Other Resins Furthermore, the resin composition of the present invention may contain a polymer other than the resin (A) as an optional component as long as the object of the present invention is not impaired. Although there is no restriction | limiting in particular in a compounding quantity, It is preferable that it is about 0.1-30 mass parts with respect to 100 mass parts of resin (A).

5. Foaming agent The resin composition may contain a foaming agent (D). A foaming agent (D) can be used individually by 1 type or in combination of 2 or more types. As the foaming agent (D), foaming agents generally used for foam molding can be widely used. Specifically, inorganic materials such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, and ammonium nitrite are used. Foaming agents; nitroso compounds such as N, N′-dimethyl-N, N′-dinitrosoterephthalamide, N, N′-dinitrosopentamethylenetetramine (DPT); azodicarboxylic acid amide (ADCA), azobisisobuty Azo compounds such as rhonitrile (AIBN), azocyclohexyl nitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide) (OBSH), diphenylsulfone- 3,3'-di Sulfonyl hydrazide compounds such as sulfo hydrazide; calcium azide, 4,4-diphenyl disulfonyl azide, azide compounds such as p- toluenesulfonyl Le azide and the like. Of these, nitroso compounds, azo compounds, and azide compounds are preferred.

  When the resin composition contains a foaming agent (D), 1 to 20 parts by weight, preferably, preferably 100 parts by weight of the total amount of the thermoplastic resin (A) and the compatibilizer (B). Is 1 to 15 parts by weight, more preferably 1 to 10 parts by weight. When the foaming agent (D) is contained in the above ratio, a molded article having a high compressive strength with a high cell ratio can be obtained.

6). Filler The resin composition of the present invention can contain a filler for the purpose of improving the rigidity of the resulting synthetic wood.
Examples of the filler 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, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate) and various metals (magnesium, silicon, aluminum, titanium, copper, etc.) powder, mica, glass flakes Etc. Furthermore, pumice powder, pumice balun, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium titanate, calcium sulfite, asbestos, montmorillonite, bentonite, molybdenum sulfide and the like can be mentioned.
Moreover, it may be an organic filler, and examples of the organic filler include lignin, starch, and products containing the same.

  These fillers can be used alone or in combination of two or more. The addition amount of these fillers is not particularly limited, but is generally 70 parts by mass or less, more preferably 30 parts by mass or less in total with respect to 100 parts by mass of the total mass of the resin (A) and the compatibilizer (B). It is.

7). Other Additives The resin composition of the present invention may contain additives other than the foaming agent and filler described above. Other additives include those known in the field of polyolefins, for example, nucleating agents, anti-blocking agents, pigments, dyes, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, UV absorbers. Agent, antibacterial agent, surfactant, antistatic agent, weather stabilizer, heat stabilizer, anti-slip agent, foaming agent, crystallization aid, anti-fogging agent, anti-aging agent, hydrochloric acid absorbent, impact modifier, crosslinking Agents, co-crosslinking agents, crosslinking aids, pressure-sensitive adhesives, softeners, processing aids and the like.

  These additives may be used alone or in combination of two or more. The content of these additives is not particularly limited depending on the use within the range not impairing the object of the present invention, but with respect to 100 parts by mass of the total mass of the resin (A) and the compatibilizer (B), About each additive mix | blended, Preferably it is about 0.05-70 mass parts. The upper limit is more preferably 30 parts by mass.

  As the nucleating agent, when the resin (A) is an olefin polymer, a known nucleating agent is used to further improve the moldability of the olefin polymer, that is, to increase the crystallization temperature and increase the crystallization speed. Is possible. Specifically, dibenzylidene sorbitol nucleating agent, phosphate ester nucleating agent, rosin nucleating agent, benzoic acid metal salt nucleating agent, fluorinated polyethylene, 2,2-methylenebis (4,6-di-t -Butylphenyl) sodium phosphate, pimelic acid and its salt, 2,6-naphthalene dicarboxylic acid dicyclohexylamide and the like.

  Although the compounding quantity of a nucleating agent is not specifically limited, Preferably it is 0.1-1 mass part with respect to 100 mass parts of total mass of resin (A) and a compatibilizer (B). The nucleating agent can be appropriately added during polymerization, after polymerization, or during molding.

  As the anti-blocking agent, known anti-blocking agents can be used. Specifically, fine powder silica, fine powder aluminum oxide, fine powder clay, powdered or liquid silicon resin, tetrafluoroethylene resin, fine powder cross-linked resin, for example, cross-linked acrylic, methacrylic resin powder and the like can be mentioned. Of these, fine powder silica and crosslinked acrylic and methacrylic resin powders are preferred.

  Examples of the pigment include inorganic contents (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake type, thioindigo type, phthalocyanine type, anthraquinone type). Examples of the dye include azo series, anthraquinone series, and triphenylmethane series. The addition amount of these pigments and dyes is not particularly limited, but is generally 5 parts by mass or less, preferably 0.1 parts by mass with respect to 100 parts by mass of the total mass of the resin (A) and the compatibilizer (B). ~ 3 parts by mass.

  Examples of lubricants include waxes other than the above-mentioned compatibilizers (Vaseline, tall oil, castor oil, rapeseed oil, soybean oil, coconut oil, beeswax, paraffin, liquid paraffin, carnauba wax, montanic acid wax, microcrystalline wax. Etc.), higher fatty acids (such as stearic acid), and metal salts thereof (such as zinc stearate and calcium stearate), higher alcohols (such as stearyl alcohol), esters thereof (such as butyl stearate), higher fatty acid amides (such as stearic acid amide) ), Process oil and various lubricants. For example, Lucant (manufactured by Mitsui Chemicals) is used as the lubricant. The Lucant may be denatured. The lubricant is preferably used in a proportion of 0.05 to 10 parts by mass with respect 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 to 2 parts by mass, and more preferably at a ratio of 0.05 to 1 part by mass.

  Examples of the plasticizer include aromatic carboxylic acid esters (such as dibutyl phthalate), aliphatic carboxylic acid esters (such as methylacetylricinoleate), aliphatic dialcolic acid esters (such as adipic acid-propylene glycol polyester), and aliphatics. Examples include tricarboxylic acid esters (such as triethyl citrate), phosphoric acid triesters (such as triphenyl phosphate), epoxy fatty acid esters (such as epoxybutyl stearate), and petroleum resins.

  A known antioxidant can be used as the antioxidant. Specifically, phenolic (2,6-di-t-butyl-4-methylphenol and the like), polycyclic phenolic (2,2′-methylenebis (4-methyl-6-t-butylphenol and the like), phosphorus System (tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylenediphosphonate, etc.), sulfur system (dilauryl thiodipropionate, etc.), amine system (N, N-diisopropyl-p-) Phenylenediamine, etc.) and lactone antioxidants.

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

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

  Examples of the antibacterial agent include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, and organic iodine.

  Surfactants can include nonionic, anionic, cationic or amphoteric surfactants. Examples of the nonionic surfactant include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, polyethylene oxide, and glycerin. Polyhydric alcohol type nonionic surfactants such as fatty acid ester, fatty acid ester of pentaerythritol, fatty acid ester of sorbit or sorbitan, alkyl ether of polyhydric alcohol, aliphatic amide of alkanolamine, and the like. Examples of the anionic surfactant include sulfate salts such as alkali metal salts of higher fatty acids, sulfonate salts such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates, higher alcohol phosphate salts, and the like. Examples thereof include phosphate ester salts. Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of the amphoteric surfactant include amino acid-type double-sided surfactants such as higher alkylaminopropionate, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyl hydroxyethylbetaine.

  Examples of the antistatic agent include the above-described surfactants, fatty acid esters, and polymer type antistatic agents. Examples of the polymer type antistatic agent include polyether ester amide.

As the crosslinking agent, for example, an organic peroxide is used.
Examples of the organic peroxide include dicumyl organic peroxide, di-tert-butyl organic peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2,5-dioxide. -(Tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl- 4,4-bis (tert-butylperoxy) valerate, benzoyl organic peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl organic peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropylcarbo Ne Salts, diacetyl organic peroxide, lauroyl organic peroxide, tert-butyl cumyl organic peroxide.

Among these, in terms of odor and scorch stability, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl in terms of odor and scorch stability. -2,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethyl Cyclohexane and n-butyl-4,4-bis (tert-butylperoxy) valerate are more preferably used, and 1,3-bis (tert-butylperoxyisopropyl) benzene is more preferably used.
The organic peroxide is preferably used in a proportion of 0.05 to 10 parts by mass with respect to 100 parts by mass of the total mass of the resin (A) and the compatibilizer (B) of the present invention.

  In the crosslinking treatment with organic peroxide, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, tri Peroxy crosslinking aids such as methylolpropane-N, N′-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, Polyfunctional methacrylate monomers such as allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

  By using the above compound, a uniform and mild crosslinking reaction can be expected. In particular, divinylbenzene is preferably used in the present invention. Divinylbenzene is easy to handle, has good compatibility with the polymer, has an action of solubilizing the organic peroxide, and acts as a dispersant for the organic peroxide. For this reason, a homogeneous cross-linking effect is obtained, and a dynamic heat-treated product having a balance between fluidity and physical properties is obtained. The crosslinking aid is preferably used at a ratio of 0.05 to 10 parts by mass with respect to 100 parts by mass of the total mass of the resin (A) and the compatibilizer (B).

  Examples of the softener include coal tar softeners such as coal tar and coal tar pitch, synthetic polymer substances such as atactic polypropylene, ester plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate, diisododecyl Examples thereof include carbonate plasticizers such as carbonate.

  Although the quantity of a softening agent is not specifically limited, It is preferable that it is the quantity of 1-200 mass parts with respect to 100 mass parts of total mass of resin (A) and a compatibilizer (B). The softening agent facilitates processing and aids dispersion of carbon black and the like when preparing the resin composition.

8). Production Method of Resin Composition The resin composition of the present invention can be produced by dry blending or melt blending using any of various methods. As a specific method, for example, a resin (A), a compatibilizer (B), a natural fiber (C) and other optional components may be added simultaneously or in any order in a tumbler, V-type blender, or Nauta mixer. A method of blending with a Banbury mixer, a kneading roll, a single-screw or twin-screw extruder, or the like is appropriately used. Alternatively, the resin (A), the compatibilizer (B), the natural fiber (C), and other optional components are once dispersed or dissolved in an arbitrary solvent, and then appropriately dried, such as natural drying or heat forced drying. You may blend by drying by the method of.

  In general, melt blending is preferable in terms of appearance and impact resistance over dry blending, and even in melt blending, the appearance and impact resistance tend to be excellent by sufficiently kneading. In particular, when two or more kinds of compounds are used in combination as the compatibilizer (B), it is preferable in terms of handling that two or more compatibilizers (B) are dry blended or melt blended in advance. As a method of melt blending, the above method, a method using a batch kettle, or the like is appropriately used.

  JIS K7210 of the resin composition of the present invention; MFR measured at 230 ° C. with a test load of 10 kgf is preferably 0.01 to 100 g / 10 min, more preferably 0.1 to 50 g / 10 min, and still more preferably. It is 0.5-30 g / 10min, Most preferably, it is 1-20 g / 10min, More preferably, it is 3-15 g / 10min. When the MFR of the resin composition is in the above range, the balance between processability, heat resistance, and mechanical strength is excellent.

  In the resin composition of the present invention, the maximum torque expression time when the resin (A), the compatibilizer (B) and the natural fiber (C) are kneaded in a batch plast mill is T2, and the compatibilization is performed. When the maximum torque expression time when the resin (A) and the natural fiber (C) alone are kneaded with the batch plast mill is T1, and the agent (B) is not included, the ratio of T1 and T2 (T1 / T2) is It is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.1 or more, and particularly preferably 1.4 or more. The compatibilizer (B) has an effect of enhancing the dispersibility of the natural fiber. However, when added in excess, the compatibilizer (B) is converted to oil during kneading (compounding), thereby generating maximum torque. As a result, T1 / T2 is lowered. That is, the kneadability is deteriorated. On the other hand, in the present invention, since the compatibility of the resin (A), the natural fiber (C) and the compatibilizer (B) is good at the time of compounding, the rise of the maximum torque is quickened, and as a result, T1 / T2 is high. Tend to be. As a result of intensive studies this time, T1 / T2 can be set to the above or more by using the above-described composition ratio.

B. Synthetic Wood The synthetic wood according to 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 or the like. The shape of the synthetic wood is not particularly limited, and is, for example, a film shape, a plate shape, a prismatic shape, a cylindrical shape, or the like.

  Synthetic wood, which is a foam, can be produced by melting and heating a resin composition containing a foaming agent (D) (hereinafter also referred to as “synthetic wood composition”) and foam molding. Specifically, the composition for synthetic wood is supplied to a melt extruder, a gas is generated by thermally decomposing the foaming agent (D) while melt kneading at an appropriate temperature, and a molten state containing this gas is generated. A foam can be obtained by discharging the composition from a die. The melt kneading temperature and melt kneading time in this method may be appropriately selected depending on the foaming agent used and the kneading conditions, and the melt kneading temperature is usually 150 to 230 ° C. and the melt kneading time is 1 to 60 minutes.

  The expansion ratio is not particularly limited, but is usually 1.3 to 10 times, particularly 1.6 to 6 times, in terms of lightness, buffering of external stress or compressive strength. . In addition, the closed cell ratio is preferably 50% by volume or more, and more preferably 70% by volume or more from the viewpoint of good external force buffering properties and suitable compressive strength.

[Use of synthetic wood]
The synthetic wood according to the present invention can be used in applications where wood is conventionally used.
For example, it is used as an exterior fence for buildings, wood decks, parola (grape racks), exterior members such as lattices, interior members such as inner wall materials, flooring materials, ceiling materials, furniture materials, and other play equipment.

  It can also be used as an impact absorbing member. Specific examples of the impact absorbing member include health supplies, care products (eg, fall prevention film, mat, sheet), impact absorbing pads, protectors / protectors (eg, helmets, Guards), sports equipment (eg sports grips), sports armor, rackets, balls, transport equipment (eg transport shock absorbing grips, shock absorbing sheets), industrial materials (eg vibration damping pallets, shock absorbing dampers) , Impact-absorbing members for footwear, impact-absorbing foams, impact-absorbing films), impact-absorbing members for automobiles (for example, bumper impact-absorbing members, cushion members) and the like.

  In addition, instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards and other automotive interior components; weather strips, bumpers, bumper guards, side mud guards, body panels, spoilers, Automotive exterior parts such as front grille, strut mount, wheel cap, center pillar, door mirror, center ornament, side molding, door molding, wind molding, window, headlamp cover, tail lamp cover, windshield parts; various front panels for AV equipment, etc. Surface decoration materials such as buttons and emblems; Various parts such as mobile phone housings, display windows, buttons, etc .; Furniture exterior materials; Walls, ceilings, floors, etc. Exterior materials: Exterior walls for siding, fences, roofs, gates, windbreaks, etc .; surface decorations for furniture such as window frames, doors, handrails, sills, duck; various displays, lenses, mirrors, goggles Optical members such as window glass; members for interior and exterior of various vehicles other than automobiles such as trains, airplanes and ships; and various packaging containers such as bottles, cosmetic containers, accessory cases, and miscellaneous goods such as packaging materials, prizes, accessories, etc. It can be suitably used for various other applications.

  Moreover, it is suitable for use in many fields, such as an electrical insulating material, an industrial component material, and a building material. In particular, baseboards, surface decorative boards, door materials, exterior wall materials, bathroom vanities, counter materials, basic backing plates, window frames, wall materials, surrounding edges, handrails, handles, and structural materials as housing materials and building materials Civil engineering squares, pillars, floor pillars, decorative pillars, anti-seismic materials, wallpaper joinery ceiling materials, base materials, tatami mats, floors, concrete panels, scaffolding materials, shielding boards, sound insulation boards, furniture box ceilings, doors, front board back boards Shelf board, sleeve board, curtain board, deck board, back board, seat board, kitchen material, waterproofing material, fungicide, antiseptic material, shutter board, sleeve board, waist board, side board, bath unit, floor pan, bath ceiling, bus Wall, bath, fence, sanitary equipment, toilet seat, toilet lid, home appliances, radio TV receiver, cabinet, stereo cabinet, amplifier cabinet, speaker, piano organ parent plate, large roof, roll roof, top and bottom scroll plate, etc. Useful for.

The present invention has an advantage that it is possible to effectively use a wood material or an unused wood material as an industrial waste in the wood industry, and is extremely effective industrially.
Furthermore, it can be used as a member for the following applications. Specifically, bicycles, small mobility means such as electric assist bicycles, escalators, elevators, manned aircraft, unmanned aircraft, ultra-high speed passenger aircraft, rockets, satellites and other aviation materials, fuel cell vehicles, hydrogen battery vehicles , Linear motor car and other moving means, various playground equipment, various members of robots, traffic lights, electric wires, water pipes, gas pipes, various infrastructures including optical fibers, liquid crystal panels, solar cells, antennas, transistors, OA equipment interiors, OA equipment Cases, toilet lighting equipment, umbrellas, rain feathers, heat insulating materials, flooring, paints, barrier agents, hydrophilicity / hydrophobicity control agents, papermaking materials, tires, dampers, hoses, anti-vibration rubber, various rubber materials, food and beverage containers, 3D Materials for printers, agricultural films, liquid filters, air filters, semiconductor filters, various nonwoven materials, musical instruments, Speaker, acoustic materials, wig, wig, watches, grave marker, eyeglasses, sunglasses, wearable terminals and the like.

  EXAMPLES Although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.

1. Resin (A)
The following (A1) to (A5) were used as the resin (A).
(A1) Homopolypropylene (230 ° C., melt flow rate 1.5 g / 10 min at 2.16 kgf, melting point 165 ° C., density 910 kg / m ³ , flexural modulus 1200 MPa) was used.
(A2) Novatec PP EA6A (manufactured by Nippon Polypro, 230 ° C., melt flow rate 1.9 g / 10 min at 2.16 kgf, melting point 165 ° C., density 900 kg / m ³ , flexural modulus 2200 MPa) was used.
(A3) Notio SN0285 (Mitsui Chemicals, 230 ° C., melt flow rate 1.4 g / 10 min at 2.16 kgf, melting point 154 ° C., density 864 kg / m ³ , flexural modulus 30 MPa) was used.
(A4) Miralastomer 6030NS (manufactured by Mitsui Chemicals, 230 ° C., melt flow rate 30 g / 10 min at 10 kgf, melting point 165 ° C., density 890 kg / m ³ , flexural modulus 20 MPa) was used.
(A5) Tafmer DF605 (manufactured by Mitsui Chemicals, 230 ° C., melt flow rate 0.9 g / 10 min at 2.16 kgf, melting point <50 ° C., density 861 kg / m ³ , flexural modulus 20 MPa) was used.
These physical properties were measured under the following conditions.

<Melt flow rate (MFR)>
According to JIS K7210, it measured on condition of 230 degreeC and 2.16kgf. (A4) Only Miralastomer 6030NS was measured according to JIS K7210 at 230 ° C. and 10 kgf.

<Melting point>
According to the differential scanning calorimetry (DSC), it was measured by DSC-20 (manufactured by Seiko Denshi Kogyo). About 10 mg of the sample was sealed in an aluminum pan, the temperature was raised 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 once heated to about 200 ° C., held for 5 minutes, and then lowered to −30 ° C. at 10 ° C./min to unify the thermal history of the sample. When there were a plurality of endothermic peaks in the obtained curve, the peak temperature at which the endothermic amount at the endothermic peak was the largest was taken as the melting point (Tm).

<Density>
It was measured according to the density gradient tube method of JIS K7112.

<Bending elastic modulus>
Measured according to JIS K7171: 94.

2. Compatibilizer (B)
As compatibilizers (B), polyolefin waxes W1 to W8 and W10 to W15 shown in Tables 1 and 2 and the following petroleum resin W9 and calcium stearate W16 were used. The melting point of W1 was 129 ° C., and the melting point of W3 was 136 ° C. Melting | fusing point was measured by the method similar to resin (A). W14 is a wax obtained by graft-modifying 20 parts by mass of styrene with respect to 100 parts by mass of the polyolefin wax.
The petroleum resins W9 (isopropenyltoluene / C5 fraction copolymer) and W15 were synthesized by the following method.
Further, calcium stearate W16 (melting point: 149 ° C. (softening point cannot be measured)) does not correspond to the compatibilizer (B) in the present invention.
The composition and physical property values of each compatibilizer (B) are shown in Table 1 and Table 2. Moreover, a composition and the measuring method of each physical-property value are described below.

<Method for synthesizing petroleum resin W9>
In a 1270 ml autoclave equipped with a stirring blade, a mixture of isopropenyltoluene, C5 fraction obtained by thermal decomposition of petroleum naphtha and dehydrated and purified toluene (volume ratio: total of monomers / toluene = 1/1), Boron trifluoride phenolate complex (1.7 times equivalent of phenol) diluted 10-fold with dehydrated and purified toluene was continuously supplied, and a polymerization reaction was carried out at a reaction temperature of 5 ° C. The weight ratio of isopropenyltoluene to C5 fraction was 90/10, the feed rate of the monomer and toluene mixture was 1.0 liter / hour, and the feed rate of the diluted catalyst was 80 milliliter / hour. Subsequently, after the reaction mixture was transferred to the second stage autoclave and the polymerization reaction was continued at 5 ° C., the total residence time in the first and second stage autoclaves was 2 hours. The reaction mixture was continuously discharged, and 1 liter of the reaction mixture was collected when the residence time was three times the residence time, and the polymerization reaction was terminated. After completion of the polymerization, 1N NaOH aqueous solution was added to the collected reaction mixture to deash the catalyst residue. Further, the obtained reaction mixture was washed 5 times with a large amount of water, and then the solvent and unreacted monomers were distilled off under reduced pressure using an evaporator to obtain an isopropenyltoluene / C5 fraction copolymer (W9).

<Method for synthesizing W15>
MFR (230 ° C., 2.16 kg under load) 0.6 g / 10 min, melting point 160 ° C., 100 mass parts of propylene homopolymer particles having an average particle size of 380 μm, a 2 liter planetary mixer (manufactured by Inoue Seisakusho, PLM- The mixture was charged in 2) and heated 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 dropped into the planetary mixer over 4 hours. At the same time, a solution prepared by dissolving 12.3 parts by mass of t-butyl peroxyisopropyl monocarbonate (NOF Corporation, Perbutyl I) as an organic peroxide in 3.5 parts by mass of toluene was dropped over 2 hours and 40 minutes. . After completion of the dropwise addition of the maleic anhydride toluene solution, heating and stirring were continued for another hour to complete the reaction. During the reaction, the planetary mixer was always in a nitrogen atmosphere. After completion of the reaction, it was cooled and the contents of the planetary mixer were extracted. Acetone was added thereto to make the total volume 1 liter, and the mixture was stirred at room temperature for 10 minutes, followed by filtration. The same operation was repeated 4 times in total and vacuum-dried at 70 ° C. for 5 hours to obtain W15.

<Polymer composition>
The content ratio of the structural unit derived from ethylene of the compatibilizer (B) and the structural unit derived from the α-olefin having 3 to 4 carbon atoms was determined by analysis of ¹³ C-NMR spectrum. 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 the molecular weight distribution (Mw / Mn) of the polyolefin waxes W1 to W8 and W10 to W15 were determined from GPC measurement. The measurement was performed under the following conditions. The number average molecular weight Mn and the weight average molecular weight Mw were determined by preparing a calibration curve using a commercially available monodisperse standard polystyrene.
Apparatus: Gel permeation chromatograph Alliance GPC2000 (manufactured by Waters)
Solvent: o-dichlorobenzene Column: TSKgel GMH6-HT × 2, TSKgel GMH6-HTL column × 2 (both manufactured by Tosoh Corporation)
Flow rate: 1.0 ml / min Sample: 0.15 mg / mL o-dichlorobenzene solution Temperature: 140 ° C

Further, the number average molecular weight Mn and the molecular weight distribution (Mw / Mn) of the petroleum resin W9 were also determined from the GPC measurement. The measurement was performed under the following conditions. The number average molecular weight Mn and the weight average molecular weight Mw were determined by preparing a calibration curve using a commercially available monodisperse standard polystyrene.
Apparatus: GPC HLC-8320 (manufactured by Tosoh Corporation)
Solvent: Tetrahydrofuran Column: TSKgel G7000 × 1, TSKgel G4000 × 2, TSKgel G2000 × 1 (all manufactured by Tosoh Corporation)
Flow rate: 1.0 ml / min Sample: 20 mg / mL tetrahydrofuran solution Temperature: room temperature

<Softening point>
It measured according to JIS K2207.

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

<Acid value>
It measured according to JIS K5902.

3. Natural fiber (C)
As natural fiber (C), wood flour controlled to an average particle size of 300 μm was used.

[Examples 1 and 2, Comparative Example 1]
(Preparation of resin composition)
Add 50 parts by mass of resin (A) (A1: homopolypropylene), 50 parts by mass of natural fiber (C) (wood flour), and 2 parts by mass of compatibilizer (B) (W1 or W2) shown in Table 3. Dry blended. However, for Comparative Example 1, no compatibilizer (B) was added.
Then, it melt-kneaded using the Parker Corporation same direction rotation twin-screw extruder, HK25D (phi25mm, L / D = 41). The screw rotation speed was 150 rpm, the feed amount was 2 kg / h, the outlet temperature was 210 ° C., and air-cooled on a belt conveyor to form a strand.

(Evaluation of resin composition)
The MFR, torque, resin pressure, sag, smoke generation, and flow curve (viscosity) of the obtained resin composition were evaluated by the following methods. The results are shown in Table 3. Moreover, the external appearance photograph of the strand obtained from the said resin composition was shown in FIG. In FIG. 1, the strands in Example 1, Example 2, and Comparative Example 1 are shown from the left. The strand of Example 1 was excellent in smoothness (evaluated as ◯), the strand of Example 2 was slightly rough (evaluated as Δ), and the strand of Comparative Example 1 was found to have a large surface roughness (evaluated as x). ).

<MFR>
The MFR of the obtained resin composition was measured under the conditions of 230 ° C. and 10 kgf according to JIS K7210.

<Torque>
After 30 minutes from the start of melt-kneading, the numerical value of the twin screw extruder when the operating condition was stabilized was read.

<Resin pressure>
After 30 minutes from the start of melt-kneading, the numerical value of the twin screw extruder when the operating condition was stabilized was read.

<Meani>
30 minutes after the start of melt-kneading, it was visually confirmed whether or not a sag (burnt resin, low molecular weight product, additive) was generated at the exit of the biaxial kneader, and evaluated as follows.
○: After 30 minutes from the start of compounding, there is no accumulation at the outlet of the twin-screw kneader. ×: After 30 minutes from the start of compounding, there is accumulation at the outlet of the twin-screw kneader.

<Smoke>
After the start of melt-kneading, smoke generated by the end was visually confirmed.
○: Almost no occurrence ×: Large amount

<Flow curve>
About the obtained resin composition, according to JISK7199, capillary size, L = 30mm, D = 1.00mm was used, and the viscosity (Pa * s) in the conditions of 230 degreeC and the extrusion rate of 2 mm / min was calculated | required. However, the system (Comparative Example 1) to which no compatibilizing agent was added could not obtain a numerical value because no strand came out from the nozzle due to poor flow.

[Evaluation of Examples 1 and 2 and Comparative Example 1]
Compared to Comparative Example 1 that does not contain the compatibilizer (B), Examples 1 and 2 that contain the compatibilizer (B) have a lower MFR and a slight increase in torque and resin pressure. There was no problem in fluidity in curve measurement, and the appearance was excellent. This is considered because the fluidity | liquidity of the resin composition under a heating becomes uniform because a compatibilizing agent (B) acts on wood flour (C). Further, Example 1 is more excellent in strand appearance than Example 2, which is considered to be because Mn of W1 as the compatibilizer (B) is in a particularly preferable range.

[Examples 3 to 6, Comparative Example 2]
(Preparation of resin composition)
The strands of the resin compositions X1 to X3 obtained in Examples 1 and 2 and Comparative Example 1 were cut to produce pellets. These were dry blended at the ratios shown in Table 4 to obtain a resin composition. However, Comparative Example 2 did not blend the compatibilizer (B).

[Examples 7 to 18]
(Preparation of resin composition)
Tables 5 and 6 show 50 parts by mass or 70 parts by mass of resin (A) (A1: homopolypropylene), 50 parts by mass or 30 parts by mass of natural fiber (C) (wood flour), and compatibilizer (B). Dry blended at a mass ratio.
Then, it melt-kneaded using the Parker Corporation same direction rotation twin-screw extruder, HK25D (phi25mm, L / D = 41). The screw rotation speed was 150 rpm, the feed amount was 2 kg / h, the outlet temperature was 210 ° C., and air-cooled on a belt conveyor to form a strand. A pellet was prepared by cutting.

[Examples 19 to 25]
Two compatibilizers were added at a mass ratio shown in Table 7 to 50 parts by mass of resin (A) (A1: homopolypropylene) and 50 parts by mass of natural fiber (C) (wood flour), followed by dry blending. . Then, it melt-kneaded using the Parker Corporation same direction rotation twin-screw extruder, HK25D (phi25mm, L / D = 41). The screw rotation speed was 150 rpm, the feed amount was 2 kg / h, the outlet temperature was 210 ° C., and air-cooled on a belt conveyor to form a strand. A pellet was prepared by cutting.

[Example 26 and Comparative Example 3]
The compatibilizer (B) ((W8) or (W16)) shown in Table 8 is added to 50 parts by mass of the resin (A) (A1: homopolypropylene) and 50 parts by mass of the natural fiber (C) (wood flour). 2 parts by mass was added and dry blended. Then, it melt-kneaded using the Parker Corporation same direction rotation twin-screw extruder, HK25D (phi25mm, L / D = 41). The screw rotation speed was 150 rpm, the feed amount was 2 kg / h, the outlet temperature was 210 ° C., and air-cooled on a belt conveyor to form a strand. A pellet was prepared by cutting.

(Evaluation of resin composition)
[Create specimen]
The pellet-shaped resin compositions obtained in Examples 3 to 26 and Comparative Examples 2 and 3 were dried at 100 ° C. for 4 hours, and then cylinder temperature using an injection molding machine (Niigata NN100, manufactured by Niigata Machine Techno Co., Ltd.). A test piece was prepared by injection molding under the conditions of 190 ° C., screw rotation speed 60 rpm, injection pressure 180 MPa, mold temperature 60 ° C.

[Evaluation of specimen]
About the obtained test piece, appearance, tensile test (tensile strength, elongation), bending test (bending strength, deflection, flexural modulus), Charpy impact test (room temperature and -30 ° C), measurement of deflection temperature under load as follows: The wood powder dispersibility was evaluated. The evaluation results are shown in Tables 4-8.

<Appearance>
◎: The surface of the injection molded product is uniform. ○: The surface of the injection molded product is less uneven. △: The surface of the injection molded product is much uneven. ×: The surface of the injection molded product is much uneven. ing

<Tensile test (tensile strength, elongation)>
Based on JIS K-7162, tensile strength and tensile elongation were measured under conditions of a load range of 2 kN and a test speed of 50 mm / min. Tensile strength and tensile elongation were evaluated according to the following criteria.
・ Tensile strength ◎: Tensile strength is 39 MPa or more ○: Tensile strength is 37 MPa or more and less than 39 MPa △: Tensile strength is 25 MPa or more and less than 37 MPa ×: Tensile strength is less than 25 MPa

-Tensile elongation O: Tensile elongation is 2.8% or more Δ: Tensile elongation is 2.0% or more and less than 2.8 ×: Tensile elongation is less than 2.0%

<Bending test (bending strength, deflection, flexural modulus)>
Based on JIS K-7171, bending strength, deflection, and bending elastic modulus 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 according to the following criteria.
・ Bending strength ◎: Bending strength is 58 MPa or more ○: Bending strength is 55 MPa or more and less than 58 MPa Δ: Bending strength is 37 MPa or more and less than 55 MPa ×: Bending strength is less than 37 MPa

Deflection ○: Deflection is 5.0% or more △: Deflection is 3.0% or more and less than 5.0% ×: Deflection is less than 3.0%

-Bending elastic modulus O: Bending elastic modulus is 3700 MPa or more x: Bending elastic modulus is less than 3700 MPa

<Charpy impact test>
In accordance with JIS K7111, a Charpy impact test was performed at room temperature and -30 ° C. The notch was machined, and the test piece was 10 mm (width) × 4 mm (thickness) × 80 mm (length). These were evaluated according to the following criteria.

・ Charpy impact value (room temperature) (kJ / m ² )
◎: Charpy impact value is 4.1kJ / ^{m 2} or more ○: Charpy impact value is less than 3.8kJ / ^{m 2} or more 4.1kJ / ^{m 2} △: Charpy impact value 3.0kJ / ^{m 2} or more Less than 3.8 ×: 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 Δ: Charpy impact value is 1.5 kJ / m ² or more and less than 2.0 kJ / m ² ×: Charpy impact value is 1.5 kJ / m ² Is less than

<Load deflection temperature>
In accordance with ISO75, the deflection temperature under load was measured under the following conditions. The test piece was 10 mm (width) × 4 mm (thickness) × 80 mm (length), and the load was 0.45 MPa. The deflection temperature under load was evaluated according to the following criteria.
◎: Deflection temperature under load is 149 ° C or higher ◯: Deflection temperature under load is 145 ° C or higher and lower than 149 ° C △: Deflection temperature under load is 142 ° C or higher and lower than 145 ° C ×: Deflection temperature under load is lower than 142 ° C

<Wood dispersibility>
The dispersion state of the wood flour in the injection specimen was observed with a scanning electron microscope (SEM) and evaluated according to the following criteria.
○: Wood powder is uniformly dispersed, and coarse wood powder of 1 mm or more is not observed. ×: Wood powder is unevenly dispersed and coarse wood powder of 1 mm or more exists.

[Torque change and resin pressure change]
About Examples 7-26 and Comparative Example 3, the torque change of the twin screw extruder and the resin pressure change when obtaining the resin composition were evaluated by the following methods. The results are shown in Tables 5-8.

<Torque change>
The torque change TC (N · m) when the compatibilizer was added was evaluated by the following equation.
TC = TA-TB
TA is a numerical value (N · m) of the torque of the twin screw extruder when the operation state is stabilized 30 minutes after the start of melt kneading. TB is a numerical value (N · m) of the torque of the twin-screw extruder when no compatibilizer is added in Comparative Example 1. A lower TC value indicates that kneading was easier when the compatibilizer was added.

<Resin pressure change>
The resin pressure change PC (MPa) when the compatibilizer was added was evaluated by the following equation.
PC = PA-PB
PA is a numerical value (MPa) of the resin pressure of the twin screw extruder when the operation state is stabilized 30 minutes after the start of melt kneading. PB is a numerical value (MPa) of the resin pressure of the twin screw extruder when no compatibilizer is added in Comparative Example 1. A lower PC (MPa) value indicates that kneading was easier when the compatibilizer was added.

[Evaluation of Examples 3 to 6 and Comparative Example 2]
In contrast to Comparative Example 2 that does not include the compatibilizer (B), Examples 3 to 6 that include the compatibilizer (B) are excellent in appearance and various physical properties of the obtained test piece (molded body). It was. Further, in contrast to Examples 3 and 5 containing 0.5 parts by mass of the compatibilizer (B), Examples 4 and 6 containing 1 part by mass of the compatibilizer (B) are excellent in appearance and various physical properties. It was.

[Evaluation of Examples 7 to 18]
Since Example 7 contained much wood powder (C) with respect to Example 8, it was excellent in tensile strength, bending strength, and heat resistance. Further, in contrast to Example 7 containing 1 part by weight of W1 as the compatibilizer (B), Examples 11 and 13 containing 1 part by weight of W10 or W11 as the compatibilizer (B) have a deflection temperature under load. It was excellent. W10 has a higher acid value than W1, and W11 has a higher molecular weight than W1. On the other hand, Example 7 was superior to Examples 11 and 13 in terms of torque change, resin pressure change, and appearance.
Moreover, although Example 7 differs in the manufacturing method of Example 4 and the resin composition, the composition is the same and the external appearance and physical property of the obtained test piece (molded object) were equivalent.

  On the other hand, Examples 10 and 12 using 0.5 parts by mass of W10 or W11 as the compatibilizer (B) are different from Example 3 using 0.5 parts by mass of W1 as the compatibilizer (B). The load deflection temperature was excellent, and when W10 was used (Example 10), the tensile strength was also excellent. Examples 14 and 15 using W12 as the compatibilizer (B) have various strengths compared to Examples 3 and 4 (or Example 7) using W1 as the compatibilizer (B). Tended to be inferior. This is considered to be because the acid value of W12 used as the compatibilizer (B) is relatively low.

Further, Examples 16 and 17 using W13 as the compatibilizer (B) have various strengths compared to Examples 3 and 4 (or Example 7) using W1 as the compatibilizer (B). However, it was slightly inferior. This is probably because the molecular weight and acid value of W13 are slightly lower than W1.
Further, in Example 8 using 3 parts by mass of W1 as the compatibilizer (B), the deflection temperature under load was reduced compared to Example 7 using 1 part by mass of W1 as the compatibilizer (B). .

  Further, Example 18 using W15 as the compatibilizer (B) had a higher deflection temperature under load than Example 7 using W1 as the compatibilizer (B). It is considered that the molecular weight and acid value of W15 are higher than W1, respectively.

[Evaluation of Examples 19 to 26 and Comparative Example 3]
In all of Examples 19 to 26, the resin pressure at the time of obtaining the resin composition did not increase and was excellent in this respect. In particular, Examples 19 to 25, in which two types of polyolefin waxes were combined, were excellent in appearance and various physical properties. This is considered to be caused by a temperature difference between the compatibilizer (BH) W1 or W10 having a high softening point and the compatibilizer (BL) having a low softening point (W4, W6, W8, W9, or W14). It is done. Specifically, in the resin composition in which two kinds of compatibilizers (B) are combined, the compatibilizer (BL) having a low softening point is melted first at the time of molding to improve the dispersibility of the wood flour. Therefore, the contact efficiency between the compatibilizer (BH) having a high softening point that is melted later and the surface of the wood powder is improved. As a result, it is considered that the balance between workability and mechanical properties is excellent.

  Further, in particular, Example 22 in which the compatibilizer W1 and the compatibilizer W8 are combined is more workable (torque change) than the Example 20 in which the compatibilizer W1 and the compatibilizer W6 are combined. ) Was excellent. This is presumably because the softening point temperature difference between the compatibilizers was in a more preferable range (20 ° C. or more).

In Example 19, acid-modified wax W4 was used as a compatibilizer (BL) having a low softening point, and thus the deflection temperature under load was excellent.
Further, Example 23 using W10 and W8 as the compatibilizer (B) has a deflection temperature under load with respect to Example 22 using W1 and the compatibilizer W8 as the compatibilizer (B). It was excellent. The high acid value of W10 used as the compatibilizer (B) is considered as a factor.

[Examples 27 to 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, 50 parts by mass of natural fiber (C) (wood flour), and 1 part by mass of W1 as a compatibilizer (B) were dry blended. However, in Comparative Example 4, no compatibilizer (B) was used. In Examples 29, 31 and 32, two kinds of resins (A) were used at a ratio of 1: 1. Then, using a Laboplast mill (Musashinokikai, NT-16-129), melt kneading was performed at a kneading temperature of 190 ° C. and a screw rotation speed of 10 rpm for 10 minutes. Then, it was air-cooled on a belt conveyor to form a strand. A pellet was prepared by cutting.

(Evaluation of resin composition)
<Torque>
After 5 minutes from the start of melt kneading in a lab plast mill, the torque value when the operating condition was stabilized was read.

[Create specimen]
After drying the obtained pellet-shaped resin composition at 100 ° C. for 4 hours, using an injection molding machine (Niigata NN100, manufactured by Niigata Machine Techno), cylinder temperature 190 ° C., screw rotation number 65 rpm, injection pressure 160 MPa, A test piece was produced by injection molding under the condition of a mold temperature of 40 ° C.

[Evaluation of specimen]
About the obtained test piece, the external appearance and the Charpy impact test (room temperature and -30 degreeC) were evaluated as follows. Table 9 shows the evaluation results.

<Appearance>
◎: The surface of the injection molded product is uniform. ○: The surface of the injection molded product is less uneven. △: The surface of the injection molded product is much uneven. ×: The surface of the injection molded product is much uneven. ing

<Charpy impact test>
In accordance with JIS K7111, a Charpy impact test was performed at room temperature and -30 ° C. The notch was machined, and the test piece was 10 mm (width) × 4 mm (thickness) × 80 mm (length).

<Shock absorption>
A sample that had been melt-kneaded in the above-mentioned lab plast mill processability evaluation was press-molded under the following conditions to produce a sheet having a thickness of 2 mm.
Press molding conditions Preheating: 190 ° C x 10 min
Press: 190 ° C x 10 MPa x 3 min
Cooling: 18 ° C. × 10 MPa × 3 min

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 impact absorbability (repellency) was evaluated according to the following criteria.
◎: Sound is low and hardly repels ○: Some sound is generated and slightly repels △: Sound is generated and repels easily ×: Large sound is generated and repulsion is large

[Evaluation of Examples 27 to 32 and Comparative Example 4]
In Example 27, it is considered that the appearance and impact value were improved with respect to Comparative Example 4 due to the effect of adding W1 as the compatibilizer (B). 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 have good workability (torque), appearance, impact value, and impact absorption, and Example 30 is particularly excellent in processability (torque), appearance, impact value, and impact absorption. It was. This is considered to be because the resin (A3) was used as the resin (A).
Examples 31 and 32 had a relatively good balance of appearance, impact value, and impact absorption. This is considered to be due to the combination of the resin (A4) and the resin (A5) with the resin (A2).

[Examples 33 to 43, Comparative Example 5]
First, the pellet made of X3 of Comparative Example 1 was melt kneaded at a kneading temperature of 190 ° C. and a screw rotation speed of 50 rpm for 5 minutes. The maximum torque expression time was T1 (s) (Comparative Example 5).
On the other hand, each compatibilizer (B) was added to the pellets made of X3 of Comparative Example 1 in the amount shown in Table 10 or 11 and dry blended (Examples 29 to 43). The mixture was melt-kneaded at a kneading temperature of 190 ° C. and a screw rotation speed of 50 rpm for 5 minutes to determine the maximum torque generation time T2. And the kneadability and workability were evaluated according to the following criteria. As the lab plast mill, a lab plast mill 4C150 manufactured by Toyo Seiki Co., Ltd. was used. Moreover, the heat resistance stability of the obtained sample was evaluated. The evaluation results are also shown in Tables 10 and 11.

<Kneadability>
The ratio between T1 and T2 (T1 / T2) was used as an index of kneadability and evaluated according to the following criteria.
A: T1 / T2 is 1.1 or more (particularly easy to knead)
○: T1 / T2 is 0.8 or more and less than 1.1 (easy to knead)
Δ: T1 / T2 is 0.5 or more and less than 0.8 (slightly difficult to knead)
X: T1 / T2 is less than 0.5 (hard to knead)

<Processability>
The maximum torque value was used as an index of workability, and evaluation was performed according to the following criteria.
A: Maximum torque is less than 34 N · m ○: Maximum torque is 34 N · m or more and less than 43 N · m Δ: Maximum torque is 43 N · m or more and less than 50 N · m ×: Maximum torque is 50 N · m m or more

<Evaluation of heat resistance stability>
A sample that had been melt-kneaded in the above-mentioned lab plast mill processability evaluation was press-molded under the following conditions to produce a sheet having a thickness of 2 mm.

<Press molding conditions>
Preheating: 190 ° C x 10 min
Press: 190 ° C x 10 MPa x 3 min
Cooling: 18 ° C. × 10 MPa × 3 min
The obtained sheet was left in a 120 ° C. incubator for 2 hours, and then the surface state was visually observed and evaluated according to the following criteria.
○: Surface condition equivalent to no addition of wax △: Slightly whitening compared to no addition of wax ×: Remarkable whitening, large unevenness

[Evaluation of Examples 33 to 47 and Comparative Example 5]
Examples 33 to 46 were superior to Comparative Example 5 in workability. This is considered to be due to the addition effect of the compatibilizer (B).
Examples 33 and 34 were superior to Comparative Example 5 not only in processability but also in kneadability. This is presumably because the compatibilizer (B) used is an acid-modified product of polypropylene wax, and thus has a large compatibilizing effect with the resin (A) (polypropylene). In addition, Example 33 was more excellent in workability than Example 34. This is probably because W1 used as the compatibilizer (B) has a higher molecular weight than W2, and thus the compatibilizing effect is even greater.
In Example 40, since the amount of the compatibilizer (B) added was small compared to Example 41, the kneadability and heat resistance tended to be excellent. However, the workability of Example 41 was observed to be superior. This is considered due to the amount of the compatibilizer (B).
Examples 45 and 46 were better in processability than Example 44. This is considered due to the amount of the compatibilizer (B). On the other hand, in terms of kneadability, Examples 44 and 45 tended to be superior to Example 46.
In Example 47, kneadability is particularly good, which is presumably because W9 used as the compatibilizer (B) has a bulky skeleton and is easily compatible with the surface of the wood flour (C).

  This application claims the priority based on Japanese Patent Application No. 2015-097482 of an application on May 12, 2015, and Japanese Patent Application No. 2015-233309 of an application on November 30, 2015. The contents described in these application specifications and drawings are all incorporated herein.

  According to the resin composition of the present invention, a resin and natural fiber are uniformly dispersed, and a synthetic wood having an excellent balance of processability, appearance, tensile strength, bending strength, impact properties, thermal stability, etc. can be obtained. . Therefore, the resin composition is very useful for various applications.

Claims (22)

Containing at least one resin (A) selected from a thermoplastic resin and a thermosetting resin, a compatibilizer (B), and a natural fiber (C);
When the total of the resin (A) and the natural fiber (C) is 100 parts by weight, the resin (A) is 1 to 90 parts by weight, the natural fiber (C) is 10 to 99 parts by weight, The resin composition which contains a compatibilizer (B) in the ratio of 0.1-50 mass parts. The resin composition according to claim 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-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 300-20000. (Ii) The softening point measured in accordance with JIS K2207 is in the range of 70-170 ° C. (Iii) The density measured by the density gradient tube method is in the range of 830 to 1200 kg / m ³ (iv) The ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography (GPC) (Mw / Mn) Is 7.0 or less   The resin composition according to claim 1 or 2, wherein the compatibilizer (B) is a polyolefin wax (B1).   The polyolefin wax (B1) is an ethylene homopolymer, a propylene homopolymer, a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, and propylene and an α-olefin having 4 to 12 carbon atoms. An unsaturated carboxylic acid derivative monomer modified product of at least one polymer selected from the group consisting of: a copolymer of styrene, a styrene modified product of the copolymer, or an air oxide of the copolymer. The resin composition according to 2 or 3.   The resin according to claim 4, wherein the polyolefin wax (B1) is an unsaturated carboxylic acid derivative monomer modified product of the polymer or an oxide of the polymer, and has an acid value of 1 to 100 mgKOH / g. Composition.   The resin according to claim 4, wherein the polyolefin wax (B1) is an unsaturated carboxylic acid derivative monomer modified product of the polymer or an air oxide of the polymer, and has an acid value of 30 to 87 mgKOH / g. Composition.   The resin according to claim 4, wherein the polyolefin wax (B1) is an unsaturated carboxylic acid derivative monomer modified product of the polymer or an air oxide of the polymer, and an acid value is 40 to 100 mgKOH / g. Composition. The compatibilizer (B) comprises two or more compounds,
Among the two or more compounds, the difference between the softening point of the compatibilizer (BH) having the highest softening point and the softening point of the compatibilizer (BL) having the lowest softening point is 5 ° C or higher. The resin composition according to claim 1 or 2. The compatibilizer (B) comprises two or more compounds,
Among the two or more compounds, the difference between the softening point of the compatibilizer (BH) having the highest softening point and the softening point of the compatibilizer (BL) having the lowest softening point is 20 ° C or higher. The resin composition according to claim 1 or 2.   The resin composition according to claim 8 or 9, wherein the compatibilizer (BH) and the compatibilizer (BL) are the polyolefin wax (B1).   The compatibilizer (BH) is an unsaturated carboxylic acid derivative monomer modified product of the polymer or an air oxide of the polymer, and has an acid value of 60 to 90 mgKOH / g. The resin composition described in 1.   The polystyrene wax number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the polyolefin wax (B1) is in the range of 6000 to 12000, according to any one of claims 2 to 11. Resin composition.   The resin composition according to any one of claims 2 to 12, wherein Mw / Mn of the polyolefin wax (B1) is 5.0 or less.   The resin composition as described in any one of Claims 1-13 whose melting | fusing point (Tm) measured with the differential scanning calorimeter (DSC) of the said resin (A) is 250 degrees C or less or is not observed. The resin composition as described in any one of Claims 1-14 in which the density measured according to the density gradient tube method of the said resin (A) exists in the range of 830-1800 kg / m < ³ >.   The resin composition as described in any one of Claims 1-15 whose bending elastic modulus of the said resin (A) is 1-10000 MPa.   The resin (A) is at least one resin selected from the group consisting of an olefin polymer, polystyrene, acrylonitrile / butadiene / styrene copolymer resin, and polyvinyl chloride. The resin composition described in 1.   18. The natural fiber (C) is at least one fiber selected from the group consisting of wood powder, wood fiber, bamboo, cotton, cellulose, and nanocellulosic fiber, according to claim 1. Resin composition.   The resin composition according to any one of claims 1 to 18, wherein a melt flow rate (MFR) measured in accordance with JIS K7210 at 230 ° C and a test load of 10 kgf is 0.01 to 100 g / 10 min. The maximum torque expression time when the resin (A), the compatibilizer (B), and the natural fiber (C) are kneaded in a batch plast mill is T2, and the resin (A) and the natural fiber ( When the maximum torque expression time when only C) is kneaded in a batch plast mill is T1,
The resin composition according to any one of claims 1 to 19, wherein a ratio between T1 and T2 (T1 / T2) is 0.5 or more.   A synthetic wood obtained by molding the resin composition according to any one of claims 1 to 20.   The synthetic wood according to claim 21, which is a wood deck or flooring.