JP2003277631A - Molding resin composition and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a molding resin composition compounding an organic filler material at a high concentration and having excellent mechanical strengths, surface smoothness and flexibility. <P>SOLUTION: The molding resin composition comprises 20-79 wt.% of the organic filler material (A), 70-20 wt.% of a thermoplastic resin or elastomer (B) having 3-60 MPa flexural rigidity (Olsen stiffness according to ASTMD790A) and 1-20 wt.% of an unsaturated carboxylic acid-modified resin (C). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a molding resin composition, and more particularly to a molding resin composition containing a high concentration of an organic filler material, which is excellent in mechanical strength, surface smoothness and flexibility. And a molded article comprising the molding resin composition.

[0002]

2. Description of the Related Art In a resin composition for molding, there has not been much study on blending an olefin resin with an organic filling material obtained by crushing vegetation, etc. There is a problem that the mechanical strength is lowered due to its poor affinity with the olefin resin.

As a method for solving such a problem, a modified polyolefin resin and an organic peroxide are blended with the olefin resin and the organic filler. For example, a resin composition containing polypropylene resin, wood powder (or rice husk), modified polypropylene resin, organic peroxide and inorganic filler (Japanese Patent Publication No. 62-5186).
Japanese Patent Publication No. 5-60502).

[0004]

However, according to the above prior art, the polyolefin resin composition containing the organic filler can be molded to some extent, and the mechanical strength of the obtained molded product is improved. However, even by these methods, the interfacial bondability between the organic filler and the olefin resin in the molten state is insufficient, and the organic filler is not incorporated into the polyolefin resin. For this reason,
The mechanical strength of the obtained sheet-shaped molded product is not yet satisfactory, and there is also a problem that resin breakage easily occurs at the edge portion during extrusion molding. This tendency was more remarkable as the blending ratio of the organic filling material increased.

Therefore, an object of the present invention is to provide a molding resin composition which can contain an organic filler in a high concentration and which is excellent in mechanical strength, surface smoothness and flexibility. is there.

[0006]

According to the present invention, the organic filling material (A) is 20 to 79% by weight, and the bending rigidity (ASTM) is
D790A Olsen stiffness) is 3-60M
Thermoplastic resin of Pa or elastomer (B) 70 to 20
% By weight, and unsaturated carboxylic acid modified resin (C) 1 to 20
There is provided a molding resin composition, which is composed of wt%. In the molding resin composition of the present invention, (1) the organic filler (A) is vegetation, particularly vegetation obtained by weeding and felling, and crushed to an average length of 0.01 to 20 mm. (2) The thermoplastic resin or elastomer (B) is an ethylene polymer (B-1) or an olefin thermoplastic elastomer (B-2). (3) The ethylene polymer (B) -1) is a copolymer containing 50 to 98% by weight of ethylene and 2 to 50% by weight of an unsaturated carboxylic acid ester or vinyl ester, (4) the ethylene-based polymer (B-1) is An ethylene / unsaturated carboxylic acid copolymer or an ionomer thereof, (5) the ethylene polymer (B-1)
But the density 0.900~0.940g / cm ³ of ethylene / alpha-olefin random copolymer and / or amorphous or low-crystalline density 0.860~0.900g / cm ³ Ethylene / alpha-olefin It is preferably a random copolymer, and (6) the unsaturated carboxylic acid modified resin (C) is an unsaturated carboxylic acid graft modified resin.

The present invention further provides a molded product obtained by molding the above-mentioned molding resin composition. The molded product of the present invention is particularly preferably molded into a sheet.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition for molding of the present invention has an organic filling material (A) of 20 to 79% by weight and a flexural rigidity (AST).
MD790A Olsen-type stiffness) is 3 to 60
70 to 2 thermoplastic resin or elastomer (B) of MPa
0% by weight, and unsaturated carboxylic acid modified resin (C) 1-2
An important feature is that it consists of 0% by weight. It is not clear why the molding resin composition having the above-mentioned constitution has excellent mechanical strength, surface smoothness and flexibility while containing the organic filler (A) at a high concentration, but the bending rigidity (ASTM D790A Olsen type stiffness) of 3 to 60 MPa thermoplastic resin or elastomer (B)
Is flexible and has low crystallinity and excellent filler loading, and the unsaturated carboxylic acid graft-modified resin (C) exhibits excellent affinity for the organic filler even in the molten state during molding, It is considered that the mechanical strength, the surface smoothness, and the flexibility are improved because the organic filler flows into the molten resin in a state of being taken in.
Moreover, in the molding resin composition of the present invention, since resin breakage is unlikely to occur, it is possible to obtain a molded article having excellent surface smoothness without exposing the organic filling material to the surface of the molded article. is there.

Further, in the present invention, it is particularly preferable to contain an ethylene / unsaturated carboxylic acid copolymer or an ionomer thereof. Since ethylene and unsaturated carboxylic acid copolymers or ionomers thereof have an excellent affinity for organic fillers, the inclusion of them makes it possible to further improve the above properties.

(A) Organic Filling Material It is important that the organic filling material to be blended in the resin composition in the present invention is blended in an amount of 20 to 79% by weight, particularly 30 to 68% by weight. That is, when the amount of the organic filler is less than the above range, not only the linear expansion coefficient of the molded product obtained by molding the resin composition is large, but also the natural texture is poor, while When the amount of the organic filler is larger than the range, the molding itself becomes difficult and the obtained molded product becomes brittle, which is not preferable. Examples of the organic filling material used in the present invention include vegetation such as grass and wood (for example, vegetation obtained by weeding and felling), partially or completely baked vegetation or esterified wood-based material. Can be mentioned,
Among these, vegetation is preferable, and grass obtained by weeding is particularly preferable. The organic filling material used in the present invention is
What is dried and then crushed to a certain length is preferable because it has excellent affinity with the resin and molding flow. Suitably, the average length is 0.01 to 20 mm, especially 0.02 to 10 mm.
It is desirable to have an average length in the range of mm.

When the partially or completely burned plant or wood (A ') is used as the organic filling material, the compounding composition of the present invention is 20 to 79% by weight of the filling material (A'), 70 to 20% by weight of a thermoplastic resin or elastomer (B) having a flexural modulus (ASTM D790A Olsen type stiffness) of 3 to 60 MPa, and an unsaturated carboxylic acid modified resin (C) (preferably unsaturated carboxylic acid graft modified resin) The resin composition consisting of 1 to 20% by weight, as well as the filling material (A ′) of 20 to 80% by weight and the flexural rigidity (ASTM
D790A Olsen stiffness) is 3-60M
Thermoplastic resin of Pa or elastomer (B) 80 to 20
Resin composition consisting of wt% or filler material (A ′) 20
The resin composition consisting of 80 to 80% by weight of ethylene and an unsaturated carboxylic acid copolymer or 80 to 20% by weight of its ionomer (D) also has mechanical strength, surface smoothness and flexibility. The resin composition is also provided as a useful molding resin composition, like the molding resin composition of the present invention.

(B) Flexural rigidity (ASTM D790A
Thermoplastic resin or elastomer having an Olsen type stiffness of 3 to 60 MPa, and the thermoplastic resin or elastomer used in the present invention is
It is important that the flexural rigidity (ASTMD790A Olsen type stiffness) is 3 to 60 MPa, particularly 3 to 40 MPa. This bending rigidity (ASTM
D790A Olsen-type stiffness) is a test piece that is cut to a prescribed size, and is fixed to one side, and the other side is bent to a predetermined angle, and indicates the bending hardness,
A thermoplastic resin or elastomer having a flexural rigidity within the above range is flexible and has excellent filler loading. As a thermoplastic resin or elastomer having a flexural rigidity (ASTM D790A Olsen type stiffness) of 3 to 60 MPa, an ethylene polymer (B-
1) and the olefinic thermoplastic elastomer (B-2) can be preferably used. Further, as the component (B) that can be used in the present invention, as long as the flexural rigidity after blending satisfies the above range, the component (B-1) and / or the component (B-2) can be used depending on the required properties. 2) selected from
It is also possible to use more than one type of polymer. In the present invention, (B) a thermoplastic resin or elastomer having a flexural rigidity (ASTM D790A Olsen type stiffness) of 3 to 60 MPa is mixed in the resin composition in an amount of 70 to 20% by weight, particularly preferably 60 to 40% by weight. To do.

(B-1) Ethylene Copolymer The ethylene copolymer is a copolymer (B of ethylene and unsaturated carboxylic acid ester or vinyl ester).
-1-1), ethylene / unsaturated carboxylic acid copolymer or its ionomer (B-1-2), density 0.900 to
0.940 g / cm ³ ethylene / α-olefin random copolymer and / or amorphous or low crystalline density of 0.
860 to 0.900 g / cm ³ of ethylene / α-olefin random copolymer (B-1-3) can be preferably used, and particularly, a copolymer of ethylene and an unsaturated carboxylic acid ester or vinyl ester. Is preferred.

(B-1-1) Copolymer Composed of Ethylene and Unsaturated Carboxylic Acid Ester or Vinyl Ester The ethylene / unsaturated carboxylic acid ester or vinyl ester copolymer used in the present invention is ethylene-containing. It is preferable that the amount is 50 to 98% by weight and the content of unsaturated carboxylic acid ester or vinyl ester is in the range of 2 to 50% by weight, and the melt flow rate (MFR) is 0.1 to 10% from the viewpoint of filler loading. 50 g /
It is preferably in the range of 10 minutes (2160 g load, 190 ° C.).

Examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate. , Isobutyl methacrylate, dimethyl maleate, diethyl maleate and the like. Among them, especially methyl acrylate, ethyl acrylate, methyl methacrylate,
Ethyl methacrylate is preferred. Examples of vinyl ester include vinyl acetate and vinyl propionate. Of these, vinyl acetate is particularly preferable.

Specific examples of the copolymer composed of ethylene and unsaturated carboxylic acid ester or vinyl ester include ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer. And ethylene- (meth) acrylic acid alkyl ester copolymers such as ethylene-ethyl methacrylate copolymer and ethylene-vinyl acetate copolymer. For example, when an ethylene-vinyl acetate copolymer is used, the vinyl acetate content is 5 to 49% by weight, preferably 25 to 33% by weight, and the melt flow rate (MF) is
An ethylene-vinyl acetate copolymer having R) of 1 to 200 g / 10 minutes, preferably 10 g / 10 minutes or less (2160 g load, 190 ° C.) can be preferably used.

(B-1-2) Ethylene / unsaturated carboxylic acid copolymer or ionomer thereof As the ethylene / unsaturated carboxylic acid copolymer or ionomer thereof which can be preferably used as the component (B) of the present invention, The ethylene / unsaturated carboxylic acid copolymer or its metal salt having an unsaturated carboxylic acid copolymerization amount of 5 to 30% by weight, preferably 6 to 25% by weight. Acrylic acid and methacrylic acid are preferable as the unsaturated carboxylic acid. The ethylene / unsaturated carboxylic acid copolymer used in the present invention is a copolymer of other unsaturated monomers such as unsaturated carboxylic acid esters such as acrylic acid ester and methacrylic acid ester, vinyl ester such as vinyl acetate, and the like. It may be polymerized. When such other unsaturated monomer is copolymerized, it may be blended in a proportion of, for example, 30% by weight or less, preferably 25% by weight or less, but the total amount of unsaturated carboxylic acid is 45% by weight or less, especially 4
The weight ratio is preferably 0% by weight or less.

When the metal salt (ionomer) of the above copolymer is used, for example, lithium, sodium, potassium,
A salt of a metal ion such as calcium, magnesium or zinc can be used. The degree of neutralization with these metal ions is 1 to 100%, preferably 5 to 80%. The ethylene and unsaturated carboxylic acid copolymers or ionomers thereof have an ethylene content of 70 to 98% by weight, particularly 75
It is preferably a random copolymer having a content of ˜95% by weight and an unsaturated carboxylic acid content of 2 to 30% by weight, particularly 5 to 25% by weight. The ethylene and unsaturated carboxylic acid copolymers or ionomers thereof have a melt flow rate (MFR) of 0.1 to 100 g / 10 minutes, particularly 0.5 to 50 g / 10 minutes (2160 g load, 190 ° C.).
It is preferably in the range of.

(B-1-3) Density 0.900 to 0.94
0 g / cm ³ of ethylene / α-olefin random copolymer The ethylene / α-olefin random copolymer used as the component (B) of the present invention has a density (ASTM D1).
505) is in the range of 0.900 to 0.940 g / cm ³ and the melt flow rate (ASTM D1238, 1
90 ° C., load 2.16 Kg) is 0.01 to 200 g / 1
The range of 0 minutes, preferably 0.03 to 100 g / 10 minutes, and particularly preferably 0.05 to 50 g / 10 minutes is desirable. Density (ASTM D1505) is 190 ° C
Flow rate of 2.16 Kg load (MF
R) The strand obtained at the time of measurement is heat-treated at 100 to 125 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and then measured by a density gradient tube. The ethylene / α-olefin random copolymer used in the present invention may be a copolymer of ethylene and α-olefin, but is preferably an ethylene homopolymer, and particularly, a metallocene olefin polymerization catalyst is used. It is preferably polyethylene prepared by using. That is, in the ethylene / α-olefin random copolymer used in the present invention, the structural unit derived from ethylene is 50 to 100% by weight, preferably 70 to 100% by weight, more preferably 80 to 100% by weight.
The constituent units present in an amount of 100% by weight and derived from α-olefins are 0 to 50% by weight, in particular 0 to 30% by weight,
It is particularly preferably present in an amount of 0 to 20% by weight.
The α-olefin used in the present invention preferably has 3 to 20 carbon atoms, and examples thereof include propylene and 1-.
Butene, 1-pentene, 1-hexene, 4-methyl-1
-Pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-exicocene and the like can be mentioned. α-
The olefins can be used alone or in combination of two or more.

(B-1-4) Amorphous or low crystalline ethylene-α-olefin random copolymer having a density of 0.850 to 0.900 g / cm ³ Amorphous or used as the component (B) of the present invention. Low crystalline density 0.860-0.900 g / cm ³ ethylene-α
The -olefin random copolymer is a copolymer of ethylene and α-olefin and has a density (ASTM D1
505) is 0.850 g / cm ³ or more and 0.900 g / c
less than m ³ , preferably 0.855 g / cm ³ or more and 0.8
It is preferably in the range of 95 g / cm ³ or less. Also, melt flow rate (ASTM D1238, 190
C., load 2.16 Kg) is preferably in the range of 0.5 to 50 g / 10 minutes, particularly 0.2 to 20 g / 10 minutes. As the α-olefin used in the present invention, the above-mentioned α-olefin having 3 to 20 carbon atoms can be used, preferably 4 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms. It is desirable to use α-olefins.
The α-olefin can be used alone or in combination of two or more.

Ethylene-α which can be used in the present invention
-The olefin random copolymer has a constitutional unit derived from ethylene of 30 to 95 mol%, particularly 40 to 95.
It is preferably in the range of mol%. Further, it has an amorphous or low crystallinity, a crystallinity by X-ray diffraction method of 40% or less, particularly 30% or less, and its melting point (ASTM D3
418) is usually 100 ° C. or lower. The amorphous or low crystalline ethylene / α-olefin random copolymer having a density of 0.860 to 0.900 g / cm ^{3 can be} prepared by a conventionally known method, for example, using a Ziegler-based olefin polymerization catalyst under medium and low pressure. Can be manufactured, and is also disclosed in
-9724, JP-A-6-136195, JP-A-6-136196, and JP-A-6-207057.
Including a metallocene catalyst component described in Japanese Patent Publication,
It can be produced by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms in the presence of a so-called metallocene olefin polymerization catalyst. The composition of the ethylene-α-olefin random copolymer is usually about 200 mg of polymer in 1 m in a 10 mmΦ sample tube.
of a sample uniformly dissolved in 1 liter of hexachlorobutadiene
^{The 13} C-NMR spectrum is measured at a measurement temperature of 120 ° C., a measurement frequency of 25.05 MHz, a spectrum width of 1500 Hz,
Pulse repetition time 4.2sec, pulse width 6μsec
It is determined by measuring under the measurement conditions of.

(B-2) Olefin-based thermoplastic elastomer The olefin-based thermoplastic elastomer that can be used as the component (B) of the present invention is a peroxide-decomposable polyolefin resin or contains at least a peroxide-decomposable polyolefin resin. Containing an ethylene / α-olefin copolymer rubber as an essential component, at least one of which is usually an ethylene / α-olefin copolymer rubber alone or both the rubber and the polyolefin resin are partially contained. Those which are cross-linked are preferred. Specifically, (a) ethylene / α-olefin copolymer rubber 100 to
20 parts by weight (b) 0 to 80 parts by weight of polyolefin resin (a + b is 1
(C) Peroxide non-crosslinking type hydrocarbon rubbery substance (d) Mixture consisting of 0 to 100 parts by weight of at least one component selected from mineral oil type softening agent 100 to 30 parts by weight of a partially crosslinked rubber composition (I) obtained by dynamically heat treating (kneading in a molten state) below and a polyolefin resin (II)
0-70 parts by weight (provided that 5 to 70 parts by weight per 100 parts by weight of the final mixture,
In addition, at least a part thereof contains a peroxide-decomposable polyolefin resin).

As the ethylene / α-olefin copolymer rubber (a) which is a raw material of the thermoplastic elastomer which can be used in the present invention, ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated diene ternary or multi-component Polymerized rubber, ethylene-butadiene copolymer rubber, ethylene / 1-butene copolymer rubber, ethylene / 1-butene non-conjugated diene multipolymer rubber, etc.
Is a substantially amorphous elastomer whose main component is α-olefin or a mixture thereof. Among them, ethylene / propylene polymer rubber and ethylene-propylene-non-conjugated diene terpolymer rubber are preferable. Here, the non-conjugated diene refers to dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, 5-ethylidene-2-norbornene and the like, and among them, dicyclopentadiene and 5-ethylidene-2-norbornene are included. A copolymer as the third component is preferred.

The polyolefin resin (b) mixed with the ethylene / α-olefin copolymer rubber during the dynamic treatment includes ethylene, propylene, butene-1,
A homopolymer of 1-olefin such as hexene-1,4-methyl-1-pentene, a copolymer of two or more kinds thereof, or a copolymer of α-olefin and 15 mol% or less of another polymerizable monomer. Polymer, for example, ethylene / vinyl acetate copolymer,
Ethylene / acrylic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / methacrylic acid copolymer, ethylene / methyl methacrylate copolymer, etc. Examples include molecular substances. A particularly preferable polyolefin resin is melt flow rate (ASTM D1238).
Is 0.1 to 50 g / 10 minutes, and the degree of crystallinity by X-ray diffraction measurement is 40% or more. Peroxide decomposition type polyolefin resin (mixed with peroxide and kneaded under heating to thermally decompose to reduce the molecular weight, Polyolefin resin in which the fluidity of the resin is increased), specifically, isotactic polypropylene, or a copolymer of propylene and 15% or less of other α-olefin, such as propylene-ethylene copolymer, propylene- 1-butene copolymer, propylene-1-hexene copolymer, propylene-
4-methyl-1-pentene copolymer can be exemplified. Further, the above-mentioned peroxide-decomposable polyolefin resin and peroxide-crosslinkable polyolefin resin (a polyolefin resin in which the fluidity of the resin is crosslinked and reduced by mixing with peroxide and kneading under heating), for example, a density of 0.910 to 0. A mixture with low and medium density polyethylene of 0.940 g / cm ³ can be preferably used as the polyolefin resin.

Non-crosslinking hydrocarbon type rubber-like substances (c) are, for example, polyisobutylene, butyl rubber,
Propylene 70% by mole or more of propylene-ethylene copolymer rubber, propylene-1-butene copolymer rubber, atactic polypropylene, etc. Hydrocarbons that do not crosslink even when mixed with peroxide and kneaded under heating, and do not deteriorate fluidity Refers to the rubbery substance of the system. Among these, polyisobutylene and propylene-1-butene copolymer rubber can be preferably used.

The mineral oil-based softening agent (d) weakens the intermolecular action force of the rubber to facilitate the processing when the rubber is usually rolled, and reduces the hardness of the vulcanized rubber to reduce the flexibility and elasticity. It is a high boiling point petroleum fraction used for the purpose of increasing
They are classified into paraffinic type, naphthene type, aromatic type and the like. In the preparation of the thermoplastic elastomer, the peroxide non-crosslinking hydrocarbon rubber-like substance (c) and / or the mineral oil-based softening agent (d) do not necessarily have to be blended, but the flow characteristics and thus the moldability are not required. In order to further improve the amount, (c) and / or (d) is added to 10 parts with respect to 100 parts by weight of the total amount of the ethylene / α-olefin copolymer rubber (a) and the polyolefin resin (b).
It is preferred to add up to 0 parts by weight, especially 5 to 100 parts by weight.

As the polyolefin resin (II) optionally mixed after the dynamic treatment, the same resin as the polyolefin resin (b) added during the dynamic heat treatment can be used. Alternatively, α-olefin and another polymerizable monomer of 15 mol% or less, for example, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer Examples thereof include a polymer, an ethylene-methacrylic acid copolymer, an ethylene-methyl methacrylate copolymer, and the like, which is a resinous polymer substance.

As the cross-linking agent used for partial cross-linking, organic peroxides such as dicumyl peroxide, di-tert-butyl peroxide, 1,3-bis (tert-butylperoxyisopropyl) benzene, sulfur,
Examples thereof include phenolic vulcanizing agents such as alkylphenol formaldehyde resins and triazine-formaldehyde resins, oximes, polyamines and the like. Among these, organic peroxides and phenolic vulcanizing agents are preferable crosslinking agents.

(C) Unsaturated Carboxylic Acid Modified Resin In the present invention, the unsaturated carboxylic acid modified resin (C) may be added to the resin composition in an amount of 1 to 20% by weight, particularly 2 to 15% by weight. is important. The unsaturated carboxylic acid modified resin used in the present invention may be an unsaturated carboxylic acid graft modified resin or a resin modified by introducing an unsaturated carboxylic acid component into a main chain by copolymerization, In the present invention, an unsaturated carboxylic acid graft-modified resin is particularly preferable. The content of the modifier (unsaturated carboxylic acid) is preferably 0.01 to 10% by weight with respect to the base polymer component. The unsaturated carboxylic acid graft-modified resin used in the present invention is a resin in which a base polymer is graft-modified with an unsaturated carboxylic acid or a derivative thereof, and the graft amount of the unsaturated carboxylic acid or a derivative thereof is the base before modification (unmodified). 0.01 to 10% by weight, preferably 0.0
It is preferably 5 to 5% by weight of an unsaturated carboxylic acid graft-modified resin. Examples of the base polymer before graft modification of the unsaturated carboxylic acid-modified resin or before modification by copolymerization include olefin homopolymers or copolymers, and specific examples include high-pressure polyethylene and medium-high density. Polyethylene, linear low density polyethylene, ultra low density polyethylene, polyethylene such as metallocene ethylene polymer, polypropylene, poly-1-
Unsaturated carboxylic acids such as butene, poly-4-methyl-1-pentene, copolymers of ethylene and vinyl esters such as ethylene-vinyl acetate copolymers, ethylene and α, β-acrylic acid esters, methacrylic acid esters Esters such as methyl acrylate, ethyl acrylate,
Examples thereof include copolymers with isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, methacrylic acid ester, glycidyl methacrylate, dimethyl maleate and the like. Of these, polyethylene and a copolymer of ethylene and a vinyl ester (particularly vinyl acetate) are preferable in the present invention.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, monomethyl maleate, monoethyl maleate, and nadic acid (registered trademark). Among them, maleic acid, nadic acid (registered trademark) or acid anhydrides thereof can be preferably used. The unsaturated carboxylic acid graft-modified resin has a melt flow rate (MFR) of 0.1 to 50 g / 10 minutes (216
0 g load, 190 ° C.), preferably 0.2 to 30 g / 1
It is preferably in the range of 0 minutes.

In the molding resin composition of the present invention, the above-mentioned components (A) to (C) may be used in addition to the conventional components other than the components (A) to (C), if necessary, within a range not impairing the object of the present invention. It is also possible to mix known polyolefin resins, polyurethane resins, and polyester resins, or to mix various foaming agents for foam molding. In addition, talc, calcium carbonate, mica, inorganic fillers such as glass fiber,
It is also possible to add organic fillers such as polyester and polyamide fibers, flame retardants, various stabilizers, various additives such as lubricants, and colorants such as dyes and pigments.

As the lubricant, stearic acid amide,
Higher fatty acid amides such as oleic acid amide and mixed phosphoric acid esters such as polyoxyethylene alkyl ether phosphoric acid ester are preferable, and the addition amount thereof is 100% by weight of the resin composition.
It is preferably added in an amount of 0.05 to 10 parts by weight, particularly 0.1 to 5 parts by weight, based on the weight.

The molding resin composition of the present invention is produced by extrusion molding,
By molding using a usual molding means such as injection molding, various molded products such as sheets can be molded. As molding conditions, it is preferable to take care so that the temperature of the composition does not exceed 200 ° C. If it exceeds 200 ° C., the organic filler (A) may be decomposed, burnt, or the like, which is not preferable. In the present invention, (A) to (C)
It is of course possible to directly add components and other additives to a molding machine for molding, but previously use a heating device such as a blender, a kneader, a mixing roll, a Banbury mixer, a single-screw or twin-screw extruder. It is desirable to compound them. In particular, it is preferable to use a twin-screw extruder having a cooling control function for compounding, since handling in the subsequent molding process becomes easy.

The field of use of the molded product obtained from the molding resin composition of the present invention is not particularly limited, but it can be preferably used particularly in the fields of civil engineering, building materials and the like. For example, civil engineering film sheet, water-stop / water-blocking film sheet, architectural film sheet, curing film / sheet, weed growth prevention film / sheet, general miscellaneous goods film / sheet, stationery base material film / sheet, It can be suitably used for other industrial films and sheets. Among them, it can be particularly suitably used as a material for civil engineering and a raw material for members for housing water.

[0035]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to the following examples.

(Materials Used) (A) Organic Filling Material Generally, the plants discharged from weeding and felling operations are dried and crushed by a crushing machine such as a cutter, a ball mill or a crusher, and the average length is 5% by weight or less. 5
mm crushed product (A-1), average length 20 μm crushed product (A-2) organic filling material, (A-1) filling material obtained by baking part (A-3) (B ) A thermoplastic resin or elastomer having a flexural rigidity (ASTM D790A Olsen type stiffness) of 3 to 60 MPa, (C) unsaturated carboxylic acid graft modified resin, (D) ethylene unsaturated carboxylic acid copolymer or ionomer thereof, and ( E) The olefin resin is shown in Table 1 below. In Table 1, EVA is an ethylene vinyl acetate copolymer, VA is vinyl acetate, EMAA is an ethylene / methacrylic acid copolymer, MAA is methacrylic acid, and iB.
A is isobutyl acrylate, IO is an ionomer, LL
DPE stands for linear low density polyethylene, respectively.

[0037]

[Table 1]

(Production of Compound and Sheet for Evaluation of Physical Properties of Organic Filling Material Composition) 140 ° C., 6 ° C. under nitrogen atmosphere
After kneading for 0 minutes using a Labo Plastomill (manufactured by Toyo Seiki Seisakusho), heat press at a temperature of 140 ° C. and 1 mm
It was formed into a thick sheet.

(Physical property evaluation method) The sheet obtained by the above method is measured by the following methods. Tensile strength: JIS K-6760 Tear strength: JIS K-6781 Bending rigidity: JIS K-7106 MFR: 190 ° C., 2160 g, 10 minutes bending whitening: Judged visually by 90 ° and 180 ° bending ○: No change Δ : Slightly changed X: Whitened XX:
Break

(Example 1 and Comparative Examples 1 to 4) An organic filler (A), a thermoplastic resin having a bending rigidity (ASTM D790A Olsen type stiffness) of 3 to 60 MPa or an ethylene / vinyl acetate copolymer (as an elastomer) B), and unsaturated carboxylic acid graft modified resin (C)
The molding resin composition (Example 1) in which the above was blended in the proportions shown in Table 2, and the molding resin in which the organic filler (A) and the ethylene / vinyl acetate copolymer (B) were blended in the proportions shown in Table 2. Molding resins (Comparative Examples 3 and 4) comprising the composition (Comparative Examples 1 and 2), the organic filler (A), the ethylene / unsaturated carboxylic acid copolymer or the ionomer (D) thereof,
The results of evaluation of strength and flexibility are also shown in Table 2. As is clear from Table 2, the resin composition according to Example 1 of the present invention has high strength, is flexible and is excellent without bending whitening, while the unsaturated carboxylic acid graft-modified resin (C) is used. The resin composition of Comparative Example 1 comprising the ethylene vinyl acetate copolymer (B) having a high vinyl acetate content, which is not blended, is excellent in flexibility, but the strength is remarkably lowered. Also,
The resin compositions of Comparative Examples 3 and 4 in which the ethylene / unsaturated carboxylic acid copolymer or its ionomer (D) was blended were excellent in strength but poor in flexibility, and bending whitening occurred.

[0041]

[Table 2]

(Examples 2 and 3, Comparative Examples 5 to 7) Organic filler (A), ethylene-vinyl acetate copolymer (B),
Unsaturated carboxylic acid graft modified resin (C), ethylene
Table 3 also shows the results of evaluating the strength and flexibility of the molding composition in which the unsaturated carboxylic acid copolymer or its ionomer (D) and the olefin resin (E) were mixed in the proportions shown in Table 3. As is clear from Table 3, the resin compositions according to Examples 2 and 3 of the present invention have higher strength than Example 1 and are flexible and excellent in terms of bending whitening. Modified resin (C)
Regarding the physical properties of the resin compositions according to Comparative Examples 5, 6, and 7 in which was not blended, the strength was low, the material became hard, and bending whitening easily occurred.

[0043]

[Table 3]

Reference Examples 1, 2, 3 Organic Filling Material (A-
Molding resin composition (Reference Example 1) in which the filler (A-3) obtained by baking at least part of 1) and the ethylene / vinyl acetate copolymer (B) are blended in a ratio shown in Table 4, and Organic filler (A-3), ethylene / vinyl acetate copolymer (B) and unsaturated carboxylic acid graft modified resin (C)
The strength of the molding resin composition (Reference Example 2) in which the above was blended in the ratio shown in Table 4, and the molding resin composition (Reference Example 3) in which the ethylene / unsaturated carboxylic acid (D) was further blended in the ratio, The results of evaluation of flexibility are also shown in Table 4. As is clear from Table 4, Reference Example 2 has higher strength, but has the same flexibility. on the other hand,
In Reference Example 3, as in the case of blending the organic filler (A-1), it has high strength, is flexible, and is excellent in that it does not bend and whiten.

[0045]

[Table 4]

(Examples 4 and 5, Comparative Examples 8 and 9) Organic filler (A), ethylene / α-olefin random copolymer and olefin thermoplastic elastomer (B), unsaturated carboxylic acid graft modified resin ( Table 5 also shows the results of evaluating the strength and flexibility of the molding composition containing C) in the proportion shown in Table 5. As is clear from Table 5, the resin compositions according to Examples 4 and 5 of the present invention are superior to Example 1 in flexural whitening, but are excellent in flexibility, while unsaturated carboxylic acid graft-modified resins are used. Comparative Examples 8 and 9 in which (C) was not blended were excellent in flexibility, but bending whitening was likely to occur.

[0047]

[Table 5]

Example 6 Organic filler (A-2), ethylene / vinyl acetate copolymer (Bv), unsaturated carboxylic acid graft modified resin (C), and mixed phosphate ester as a lubricant (Toho) Phosphanol R made by Chemical Industry Co., Ltd.
L-210) was dry-blended in the ratio shown in Table 6 and kneaded using a 6-inch roll at a roll temperature of 140 ° C. and a roll rotation ratio of 1: 1 for 10 minutes, and then a sheet having a thickness of 1 mm was directly prepared. The roll releasing property of this composition was good, no smoke was generated, and the appearance of the sheet was smooth. The results of evaluating the strength and flexibility of the obtained molding composition are also shown in Table 6. It was found that in the case of the roll-formed sheet, the tear strength was almost the same as in Example 1, but the tensile strength was improved and the elongation was likely to occur.

Comparative Example 10 A 1 mm thick sheet was prepared from the formulation shown in Table 6 in the same manner as in Example 6 except that the unsaturated carboxylic acid graft-modified resin (C) was not used. The roll-releasing property of this composition was almost the same as that of Example 6. The results of evaluating the strength and flexibility of the obtained molding composition are also shown in Table 6. As is apparent from Table 6, when the unsaturated carboxylic acid graft-modified resin (C) is not blended, the tensile strength and tear strength become insufficient.

[0050]

[Table 6]

[0051]

INDUSTRIAL APPLICABILITY In the molding resin composition of the present invention,
Organic filling material (A) 20 to 79% by weight, flexural rigidity (A
STM D790A Olsen type stiffness) is 3 ~
60 MPa thermoplastic resin or elastomer (B) 70
-20% by weight and 1-20% by weight of the unsaturated carboxylic acid graft-modified resin (C), it becomes possible to mix the organic filler in a high concentration, and further, mechanical strength and surface smoothness, It has become possible to provide a molding resin composition having excellent flexibility.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F071 AA14 AA15 AA15X AA20X                       AA21X AA28X AA31X AA73                       AA78 AA82 AD06 AE17 AF14                       AF17Y AF26 AF27 AH03                       AH19 BC01                 4J002 AH00W BB05X BB06X BB07X                       BB08X BB10X BB12X BB14X                       BB15X BB17X BB213 BB23X                       BN053 BN073 FD01W FD010                       FD170 GC00 GL00

Claims (10)

[Claims] 1. An organic filling material (A) of 20 to 79% by weight,
Molding resin composition comprising 70 to 20 wt% of a thermoplastic resin or elastomer (B) having a flexural rigidity (ASTMD790A Olsen type stiffness) of 3 to 60 MPa, and 1 to 20 wt% of an unsaturated carboxylic acid modified resin (C). . 2. The molding resin composition according to claim 1, wherein the unsaturated carboxylic acid modified resin (C) is an unsaturated carboxylic acid graft modified resin. 3. The molding resin composition according to claim 1, wherein the organic filler (A) is a plant or tree. 4. The organic filler (A) is a plant or tree obtained by weeding and felling, and has an average length of 0.01 to 20 mm.
The resin composition for molding according to any one of claims 1 to 3, wherein the resin composition for molding is obtained by pulverizing into resin. 5. The thermoplastic resin or elastomer (B) is an ethylene polymer (B-1) or an olefin thermoplastic elastomer (B-2), according to any one of claims 1 to 4. The resin composition for molding according to claim 1. 6. The ethylene-based polymer (B-1) is a copolymer containing 50 to 98% by weight of ethylene and 2 to 50% by weight of an unsaturated carboxylic acid ester or vinyl ester. The molding resin composition according to claim 5. 7. The molding resin composition according to claim 5, wherein the ethylene polymer (B-1) is an ethylene / unsaturated carboxylic acid copolymer or an ionomer thereof. 8. The ethylene-based polymer (B-1) is ethylene / α-having a density of 0.900 to 0.940 g / cm ^3.
The molding resin composition according to claim 5, which is an olefin random copolymer and / or an amorphous or low crystalline ethylene / α-olefin random copolymer having a density of 0.860 to 0.900 g / cm ³ . 9. A molded product obtained by molding the molding resin composition according to claim 1. 10. The molded product according to claim 9, wherein the molding resin composition is molded into a sheet.