JPH11269316A - Woody resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a woody resin composition capable of inexpensively providing a molding product having extremely improved woody feeling (luster, appearance and touch) on the surface of the molding product and high mechanical strength. SOLUTION: This woody resin composition comprises 100 pts.wt. of the total of (A) 20-80 pts.wt. of a polyolefin-based resin, (B) 80-20 pts.wt. of a cellulose-based granule, (C) 1-20 pts.wt. of a functional group-containing polyolefin-based polymer and (D) 1-30 pts.wt. of one or more selected from the group consisting of a styrene-based resin, a polyphenylene ether-based resin, a polymethyl methacrylate resin and a polycarbonate resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a woody resin composition for providing a molded article having a woody surface.

[0002]

2. Description of the Related Art When a resin molded product having a woody surface is obtained by mixing and kneading cellulosic particles such as wood flour and a polyolefin resin such as polypropylene resin, a sufficiently high mechanical strength is obtained by simple mixing. Target strength is not obtained. Therefore, conventionally, in order to obtain sufficiently high mechanical strength, a small amount of maleic anhydride-modified polypropylene or glycidyl methacrylate-modified polypropylene has been added to a mixture of a polypropylene resin and wood flour.

[0003] However, a molded article obtained by extruding the resin composition may contain a considerable amount of wood powder, for example, about 50%.
There is a drawback that the surface gloss is high and there is almost no woody appearance on the surface of the molded article visually and by touch. In order to improve such surface properties, it is conceivable to roughen the surface of the molded product with sand blasting or wire brushing. It was far from getting). Further, a method of embossing in the form of a conduit on the surface of the molded article is also conceivable. However, the glossiness and tactile feel of the surface other than the embossed surface are still far from woody feeling. Further, the addition of these steps has caused a problem that the cost is increased.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a woody resin composition in which the woody texture (gloss, appearance, touch) of the surface of a molded product is remarkably improved and a molded product having both high mechanical strength is supplied at a low cost. It provides things.

[0005]

The present inventor has made various studies to solve the above-mentioned problems. As a result, one of the group consisting of styrene resin, polyphenylene ether resin, polymethyl methacrylate resin and polycarbonate resin
If the seed or more resin is blended in the following predetermined amount, it is possible to solve all the above-mentioned problems by being unexpectedly combined with a polyolefin-based resin, a cellulose-based powder and a functional group-containing polyolefin-based polymer. This led to the completion of the present invention.

That is, the present invention relates to (C) functional (C) functional groups based on (A) 20 to 80 parts by weight of a polyolefin resin and (B) 80 to 20 parts by weight of a cellulose powder. Group-containing polyolefin polymer 1-2
A wood resin composition comprising 0 parts by weight and (D) 1 to 30 parts by weight of one or more resins selected from the group consisting of styrene resins, polyphenylene ether resins, polymethyl methacrylate resins and polycarbonate resins. .

According to the present invention, not only can the surface of a molded product obtained by mixing a polyolefin resin such as a polypropylene resin and a cellulosic powder such as wood flour be matted, but also the surface of the molded product has a straight grain. It is possible to obtain a molded product that is very similar to wood as a whole. Furthermore,
Since sandblasting and embossing rolls are not required, production costs can be significantly reduced.

In a preferred embodiment, (2) 1 to 20 parts by weight of (D) one or more resins selected from the group consisting of styrene resins, polyphenylene ether resins, polymethyl methacrylate resins and polycarbonate resins. The woody resin composition described in the above (1), (3) (D) one or more resins selected from the group consisting of a styrene-based resin, a polyphenylene ether-based resin, a polymethyl methacrylate resin, and a polycarbonate resin; The woody resin composition according to the above (1) containing 10 parts by weight, (4)
(A) 30 to 70 parts by weight of a polyolefin resin,
And (B) the woody resin composition according to any one of the above (1) to (3), which contains 70 to 30 parts by weight of a cellulose-based powder, and (5) a (C) functional group-containing polyolefin-based resin composition. The woody resin composition according to any one of the above (1) to (4), which contains the polymer in an amount of 3 to 10 parts by weight based on 100 parts by weight of the total of (A) and (B). Can be.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The polyolefin resin (A) used in the present invention includes, for example, ethylene, propylene, butene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, and the like. And α-olefin homopolymers or copolymers thereof, or copolymers thereof with unsaturated monomers copolymerizable therewith. Preferably, polyethylenes such as high density, medium density or low density polyethylene, linear low density polyethylene, ultra high molecular weight polyethylene, ethylene-vinyl acetate copolymer or ethylene-ethyl acrylate copolymer, atactic, syndical Otactic or isotactic polypropylene, or polypropylenes such as a propylene-ethylene block copolymer or a random copolymer, or poly-4-methylpentene-1 or the like can be used.

(B) The cellulosic powder is not particularly limited, and for example, sawdust powder, pulp powder and the like can be used. Preferably, sawdust such as pine, cedar, cypress, hemlock and the like generated in the sawing process is used.

(C) The functional group-containing polyolefin polymer is preferably an olefin polymer having at least one functional group selected from the group consisting of an epoxy group, a carboxyl group, an acid anhydride, a hydroxyl group, and a nitrogen-containing base. It is united. For example, glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, those modified with an unsaturated epoxide such as allyl glycidyl ether or the like, or those added with a liquid rubber such as terminal hydroxylated polybutadiene during such graft modification are used. be able to. Further, the polyolefin is treated with an organic peroxide such as benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, t-butyl hydroperoxide to form a carboxyl group,
Unsaturated organic acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid; anhydrides of unsaturated organic acids such as maleic anhydride, itaconic anhydride and citraconic anhydride; and unsaturated acids such as methyl acrylate and monomethyl maleate It is obtained by graft-polymerizing an unsaturated carboxylic acid such as an amide of an unsaturated organic acid such as an ester of an organic acid, an amide of acrylic acid, and a monoamide of fumaric acid, and an imide of an unsaturated organic acid such as itaconamide. The functional group-containing polyolefin polymer may be used alone or in combination of two or more.

The styrenic resin used as (D) in the present invention is, for example, a homopolymer such as styrene or α-methylstyrene, a copolymer thereof, or a copolymer of an unsaturated monomer copolymerizable therewith. Polymers. Preferably, general-purpose polystyrene, impact-resistant polystyrene,
Heat-resistant polystyrene (α-methylstyrene polymer), acrylonitrile-butadiene-styrene copolymer (ABS
), Acrylonitrile-styrene copolymer (AS), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES), acrylic rubber-acrylonitrile-styrene copolymer ( AAS).

(D) Polyphenylene ether (PPE)
Known resins can be used as the system resin. For example, a blend of PPE and the above-mentioned various styrene-based resins, a copolymer in which a styrene-based compound is grafted on PPE, or a PPE homopolymer as described below can be used. Among them, a blend of PPE and a styrene-based resin is preferable. At this time, the mixing ratio of the styrene-based resin to the PPE is not particularly limited as long as the excellent characteristics of the PPE are not impaired.

The polyphenylene ether has, for example, the general formula:

[0015]

Embedded image (Wherein Q ¹ , Q ² , Q ³ and Q ⁴ each independently have a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group and at least two carbon atoms between the halogen atom and the phenyl ring A haloalkyl group or a haloalkoxy group;
Represents a monovalent substituent selected from those which do not contain a class α-carbon, and q is an integer representing the degree of polymerization.) And is a kind of polymer represented by the above general formula The copolymer may be used alone or in combination of two or more.

The method for producing PPE is not particularly limited. For example, US Pat. No. 3,306,874 and US Pat.
It can be prepared by the reaction of phenols according to the procedures described in 257,357 and 3,257,358. These phenols include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dibutylphenol, 2,6-dilaurylphenol, 2,6-dipropylphenol, 2,6-diphenylphenol, 2-methyl-6-
Ethylphenol, 2-methyl-6-cyclohexylphenol, 2-methyl-6-tolylphenol, 2-methyl-6-methoxyphenol, 2-methyl-6-butylphenol, 2,
This includes, but is not limited to, 6-dimethoxyphenol, 2,3,6-trimethylphenol, 2,3,5,6-tetramethylphenol and 2,6-diethoxyphenol. Each of these may be reacted alone to the corresponding homopolymer, or reacted with another phenol to the corresponding copolymer having different units encompassed by the above formula.

In a preferred embodiment, Q ¹ and Q ² are an alkyl group having 1 to 4 carbon atoms, and Q ³ and Q ⁴ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. For example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1, 4-phenylene) ether, poly (2-methyl-6-propyl-1,4
-Phenylene) ether, poly (2,6-dipropyl-1,4
-Phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether and the like. Further, as the PPE copolymer, an alkyl tri-substituted phenol in the above-mentioned polyphenylene ether repeating unit, for example,
Copolymers partially containing 2,3,6-trimethylphenol can be mentioned. Further, a copolymer in which a styrene-based compound is grafted on these PPEs may be used.
The styrene-based compound-grafted polyphenylene ether is a copolymer obtained by graft-polymerizing, for example, styrene, α-methylstyrene, vinyltoluene, chlorostyrene, or the like as the styrene-based compound on the PPE.

(D) The poly (methyl methacrylate) resin is not particularly limited, and known resins can be used. For example, a methyl methacrylate homopolymer or various copolymers containing methyl methacrylate as a main component can be used.

As the polycarbonate resin (D), known resins can be used.

[0020]

Embedded image (Where R and R ′ are each independently a halogen atom,
W is a monovalent hydrocarbon group or a hydrocarbon oxy group, and W is a divalent hydrocarbon group, -S-, -SS-, -O-, -S
(= O)-,-(O =) S (= O)-, or -C (=
O)-, n and n 'are each independently an integer of 0 to 4, and b is 0 or 1. ), And a diphenol component derived from the diphenol and a carbonate component. In the above formula, when R and R ′ are a halogen atom, examples thereof include a chlorine atom and a bromine atom. In the case of a monovalent hydrocarbon group, examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkaryl group. In the case of a hydrocarbon oxy group, examples of the hydrocarbon group include the aforementioned hydrocarbon groups.

When W is a divalent hydrocarbon group,
Alkylene group, alkylidene group, cycloalkylene group,
Or a cycloalkylidene group.

Specific examples of diphenols include, for example, diphenol; 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A); 2,2-bis (3,5-dibromo-4-hydroxyphenyl) Propane; 2,2-bis (3,
5-dimethyl-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (4 -Hydroxyphenyl) decane; 1,4-bis (4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclododecane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) Cyclododecane; 4,4-
Dihydroxydiphenyl ether; 4,4-thiodiphenol; 4,4-dihydroxy-3,3-dichlorodiphenyl ether; and 4,4-dihydroxy-2,5-dihydroxydiphenyl ether. Other US Patent Specification No.
Nos. 2,999,835, 3,028,365, 3,334,154 and
The diphenols described in 4,131,575 can be used. Such a polycarbonate can be produced, for example, by a known interfacial polymerization method using phosgene, a melt polymerization method (ester exchange method), or the like.

In the resin composition of the present invention, the component (A)
The mixing ratio of the polyolefin-based resin and the component (B) cellulose-based powder is (A) 20 to 80 parts by weight and (B)
80 to 20 parts by weight, preferably (A) 30 to 70 parts by weight, and (B) 70 to 30 parts by weight. Component (A)
If (B) exceeds the above upper limit and (B) exceeds the above upper limit, granulation into pellets becomes difficult, and if component (A) exceeds the above upper limit and (B) is below the above lower limit, a woody feeling cannot be obtained in the molded article. .

The lower limit of the compounding amount of the component (C) functional group-containing polyolefin polymer is 1 part by weight, preferably 3 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). The upper limit is 20 parts by weight, preferably 10 parts by weight.
Below the lower limit, sufficient compatibility cannot be obtained and the mechanical strength is low. Exceeding the above upper limit does not increase the effect and causes an increase in cost.

Component (D) The amount of one or more resins selected from the group consisting of a styrene resin, a polyphenylene ether resin, a polymethyl methacrylate resin, and a polycarbonate resin is as follows: components (A) and (B) A total of 1
The lower limit is 1 part by weight, preferably 3 parts by weight, particularly preferably 5 parts by weight, and the upper limit is 30 parts by weight, preferably 20 parts by weight, particularly preferably 10 parts by weight with respect to 00 parts by weight. Below the lower limit, the gloss of the surface of the molded article cannot be removed, and the woody feel does not improve. If the upper limit is exceeded, the compatibility decreases and the mechanical strength decreases.

In the resin composition of the present invention, in addition to the above components, various additives known to those skilled in the art, such as antioxidants, light stabilizers, antistatic agents, lubricants, dyes, pigments,
Additives such as plasticizers, release agents, glass fibers, metal fibers, metal flakes, flame retardants, ultraviolet absorbers, fillers, and reinforcing materials can be added.

In producing the woody resin composition of the present invention, the form (suspension, solution in an organic solvent, latex, powder, pellets, flakes, etc.) of each of the above-mentioned components and the order of blending are not limited. There is no limitation, and a conventionally known method can be used. All the components may be mixed and kneaded together, or any components may be previously mixed and kneaded, and then the remaining components may be added and kneaded. For example, pellets, powder, in a strip state, and the like, after dispersing and mixing with a high-speed mixer represented by a turnbull mixer or a Henschel mixer, a single-screw or multi-screw extruder,
A method of melt-kneading with a Banbury mixer, a roll, or the like is appropriately selected.

The woody resin composition of the present invention is used for building materials, decorative materials for automobile parts or home appliances, structural members and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0030]

【Example】

[0031]

Examples 1 to 9 and Comparative Examples 1 to 4 Components The components used in each of the Examples and Comparative Examples are as follows. (A) Polyolefin resin: polypropylene (PP)
(K7010, trade name, manufactured by Chisso Corporation) (B) Cellulose-based powder: Rice pine sawdust generated in the sawing process (C) Functional group-containing polyolefin-based polymer: Maleic anhydride-modified polypropylene (modified PP) (Nobrene MP
E331, trademark, manufactured by Sumitomo Chemical Co., Ltd.) (D) Styrene resin: polystyrene (PS) (denkastyrol HRM-
2. Trade mark, manufactured by Denki Kagaku Kogyo Co., Ltd.) ABS (Techno ABS400, trade mark, manufactured by Techno Polymer Co., Ltd.) (D) Polyphenylene ether resin (PPE): Noryl SE90, trade mark, manufactured by Nippon GE Plastics Co., Ltd. (thermal deformation) (Temperature 90 ° C.) (D) Polymethyl methacrylate resin (PMMA): Acrypet VH, trademark, manufactured by Mitsubishi Rayon Co., Ltd. (D) Polycarbonate resin (PC): Panlite K
-1285 The kneading and molding components (A) to (D) manufactured by Teijin Chemicals Limited in amounts (parts by weight) shown in Table 1 or 2
The mixture was mixed by high-speed stirring in a molten state of the resin using a Kawata super mixer Z-1SP. Next, the mixture was transferred to a cooling mixer SMNC100 manufactured by Kawata Co., Ltd., and cooled to room temperature while further mixing to obtain a powdery mixture. This powdery mixture is twin-screw extruder (TEM-53 type, trademark, manufactured by Toshiba Machine Co., Ltd.)
The mixture was melt-kneaded and extruded to obtain pellets. The obtained pellets were extruded by a single screw extruder (FS65, trade name, manufactured by Ikegai Co., Ltd.) to form a molded product having a rectangular cross section of 75 mm width × 8 mm thickness.

Test <Surface Gloss> The gloss was evaluated based on the gloss of a 60 ° mirror surface (JIS).
Z8741). <Appearance> It was evaluated visually. The symbols in Tables 1 and 2 indicate the following.

A: The gloss disappears as a whole, there is no unevenness, and the grain pattern is excellent.

○: The gloss disappeared almost as a whole, and the grain pattern was good.

Δ: Partial unevenness of gloss is observed, and grain is not clear.

×: The overall appearance is high, the grain is not visible, and it looks like plastic. <Tactile sensation> Evaluation was made by the tactile sensation by hand. The symbols in Tables 1 and 2 indicate the following.

A: The feel of the wood is rough and the whole surface is excellent.

：: Good feeling with a rough wood-like texture.

△: There is a touch part like plastic that is partially slippery.

×: The entire surface is smooth and has a plastic touch. <Tensile strength> Measured according to ASTM D638.

Results The above results are shown in Tables 1 and 2.

[0042]

[Table 1]

[0043]

[Table 2] Examples 1 to 3 are resin compositions in which the amount of the component (D) PS was changed within the range of the present invention. The properties of the molded products were all good. In Examples 4 to 7, the component (D) was ABS, PPE, PMMA, and PC, respectively.
In each case, the same good molded product properties as those using PS (Example 1) were shown. Examples 8 and 9 vary the amounts of components (A) and (B) within the scope of the present invention. In each case, although the glossiness was slightly increased, the effects of the present invention could be sufficiently achieved.

Comparative Example 1 shows the result of a resin composition not containing the component (D). The glossiness was very high, and the appearance and touch were extremely poor. Comparative Example 2 shows that the component (D)
PS is blended in a large amount beyond the scope of the present invention. The tensile strength was remarkably reduced, and was not practical at all. In Comparative Examples 3 and 4, the amounts of the components (A) and (B) were out of the range of the present invention. The resin composition of Comparative Example 3 could not be formed into pellets and could not be molded, and the resin composition of Comparative Example 4 had extremely high glossiness, extremely poor appearance and tactile sensation, and significantly reduced tensile strength.

[0045]

According to the present invention, the texture (gloss,
The present invention provides a woody resin composition in which a molded article having significantly improved appearance and touch feeling and high mechanical strength is supplied at a low cost.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 71/12 C08L 71/12 97/02 97/02

Claims (2)

[Claims] 1. A polyolefin resin (A) 20 to 80.
(C) 1-20 parts by weight of a functional group-containing polyolefin-based polymer, (D) styrene-based resin, and polyphenylene ether, based on 100 parts by weight of the total weight of (B) the cellulosic powder and granules (80-20 parts by weight). A wood resin composition comprising 1 to 30 parts by weight of one or more resins selected from the group consisting of a base resin, a polymethyl methacrylate resin and a polycarbonate resin. 2. The method according to claim 1, wherein (D) 1 to 20 parts by weight of one or more resins selected from the group consisting of a styrene resin, a polyphenylene ether resin, a polymethyl methacrylate resin, and a polycarbonate resin. Woody resin composition.