JPH09286880A - Resin composition containing wood flour - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition containing wood flour and suitable for a building interior material by blending a specified ethylene/α-olefin copolymer and wood flour and produce a molded article therefrom. SOLUTION: This composition contains 100 pts.wt. polyolefin resin (A) and 40-250 pts.wt. wood flour (B). The component A comprises an ethylene/3-12C α-olefin copolymer obtained by polymerization in the presence of a metallocene catalyst and having a density of 0.86-0.88g/cm<3> , a melt index of 0.5 to 40, and a ratio of weight-average molecular weight to number-average molecular weight of (1.5 to 5):1. The component B has a mean particle diameter of 10-200μm. This composition is formed into a sheet of 0.15-15mm in thickness, and a skin material and a backing material respectively laminated on the surface and the rear thereof to give a flooring material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyolefin resin composition containing wood flour. Among them, it relates to a polyolefin resin composition suitable for a floor material for interiors of buildings, a wall material, and the like, a molded product based thereon, and a floor material using the molded product.

[0002]

2. Description of the Related Art Floor materials used as an alternative to natural materials
In the field of synthetic resin-based building materials for wall materials, products that use vinyl chloride-based resin are easy to manufacture and process molded products, and have excellent flame retardancy, and are inexpensive. And is widely used. However, for building materials using the above vinyl chloride resin, use an acid-resistant incinerator to incinerate scraps such as scraps generated during construction and waste generated when the building is demolished. However, there is a problem in that it takes time and money for sorting and processing.

In order to solve such a problem, studies have been made to replace the vinyl chloride resin with a polyolefin resin, but it is still insufficient as a building material member for the above-mentioned applications. It was of performance. For example, Japanese Unexamined Patent Publication (Kokai) No. 6-322187 discloses a wood-flour-filled resin molded plate formed by using a mixture of polypropylene and high-density polyethylene as a polyolefin-based resin and mixing a specific amount of wood flour with the mixture. ing. However, the molded plate obtained here has a high rigidity, and when used as a floor material, the workability is significantly inferior to that of a vinyl chloride resin floor material, and the price is the same as that of existing plywood or medium quality plywood. It was hard to say that it was cheaper than materials such as fiberboard (MDF).

[0004]

A wood-powder-containing polyolefin resin composition for building materials such as flooring and wall materials, and excellent moldability using the same, and adhesiveness when laminated with plywood and the like. A resin molded product containing wood powder with good quality and a flooring material based on the same.

[0005]

The gist of the present invention is to provide a polyolefin resin and 4 parts wood powder per 100 parts by weight of the resin.
A wood powder-containing resin composition containing 0 to 250 parts by weight, wherein (a) ethylene and 3 to 1 carbon atoms obtained by polymerizing the polyolefin resin using a metallocene catalyst.
2 is a copolymer with an α-olefin, wherein (b) the density is 0.86 to 0.88 g / cm ³ , (c) the melt index is 0.5 to 40, and (d) the weight average molecular weight ( M
w) and the number average molecular weight (Mn) (hereinafter referred to as “Mw / M
n ") is from 1.5 to 5.
An olefin copolymer (hereinafter, referred to as a “polyolefin copolymer”), and an average particle size of the wood powder is 10 to 20.
A wood powder-containing resin composition having a diameter of 0 μm.

Further, the gist of the present invention is to provide a wood powder-containing resin molded product obtained by molding the above composition into a sheet having a thickness of 0.15 to 15 mm, and a skin material on one surface of the wood powder containing resin molded product. Is also laminated, and a flooring in which a wood board, cloth, or paper is laminated on the other surface, is also present.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The polyolefin resin used in the present invention is a specific ethylene-α obtained by polymerization using a metallocene catalyst.
-Olefin copolymer. The metallocene catalyst (also referred to as a single-site catalyst or Kaminsky catalyst) is described in JP-A-3-163088 or JP-A-7-118431.
It is a catalyst composed of a metallocene-based transition metal complex and an organoaluminum compound as disclosed in JP-A-7-148895 and the like, and may be used by being supported on an inorganic substance.

As the metallocene type transition metal complex, for example, a transition metal selected from Group IVB (titanium, zirconium, hafnium) is added to a cyclopentadienyl group, a substituted cyclopentadienyl group, a dicyclopentadienyl group, a substituted dicyclohexyl group. A pentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is coordinated as one or two ligands, or among these Coordination of two groups bridged by a covalent bond, in addition to those having a ligand such as a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an acetylacetonate group. can give.

Further, as the organoaluminum compound,
Alkyl aluminum and chain or cyclic aluminoxane can be mentioned, and as alkyl aluminum, triethyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, Diethyl aluminum hydride, ethyl aluminum sesquichloride, etc. can be exemplified, and the chain or cyclic aluminoxane can be produced by contacting the above alkylaluminum with water. Water is added, or water of crystallization of complex salts or water of adsorption of organic or inorganic compounds and It can be obtained by reacting aluminum.

Examples of the carrier for supporting the metallocene catalyst include silica gel, zeolite, diatomaceous earth and the like. As the α-olefin to be copolymerized with ethylene, one having 3 to 12 carbon atoms is used. For example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-
Pentene, 1-decene, etc. are mentioned, and the 1 type or the mixture of 2 or more types is used. The mixing ratio of α-olefin to ethylene is preferably 5 to 40% by weight.

Polymerized using the above metallocene catalyst,
Tylene-α-olefin copolymer (polyolefin-based copolymer
Polymer) using a Ziegler catalyst or a solid catalyst.
Compared to the combined polyolefin-based polymer,
Excellent mechanical strength. In the present invention, the above
Among the copolymers, the density is 0.86-0.88g / cm
^ThreeWith a melt index of 0.5-40, more preferred
Ku 0.8 to 30, and gel permeation chromatography
Weight average molecular weight determined by chromatography (GPC)
Ratio (Mw / M) of amount (Mw) and number average molecular weight (Mn)
ethylene in which n) ranges from 1.5 to 5, preferably from 2 to 4
-Α-olefin copolymer as a polyolefin resin
To use.

The composition of the present invention comprises the above polyolefin resin and 40 to 250 parts by weight of wood powder per 100 parts by weight of the resin. The average particle size of wood flour is 10
The one having a thickness of 200 μm, preferably 30 to 150 μm is used. The wood species used as the raw material of the wood flour used in the present invention is not particularly limited, and may be selected from conifers such as pine, fir and hemlock and broadleaf trees such as poplar. As the wood powder, it is preferable to use cutting powder as sawdust (saw dust) or the like, which is powdered with an average particle size of 10 to 200 μm by dry or wet pulverization or sieve powder.

When the average particle size of the wood powder exceeds 200 μm, heat generation due to frictional resistance during extrusion molding increases,
It is not preferable because foaming and coloring occur due to generation of gas due to decomposition of wood powder. In addition, the average particle size is 10μ.
With fine wood flour less than m, it takes time to grind and sieve flour,
In addition, dusting is likely to occur during mixing, which is not preferable.

The average particle size of the wood powder is expressed as the particle size at which the integrated value of the weight of each fraction measured by JIS sieve is 50% of the whole. Moreover, the average particle size of the wood flour is within the above-mentioned specific range, and 70% of the whole.
It is suitable that the wood powder content is not less than 80% by weight, preferably not less than 80% by weight, within the above range.

When the amount of wood powder to be added is less than 40 parts by weight with respect to 100 parts by weight of the polyolefin resin, for example, when a veneer or the like is laminated as a skin material on the surface of the molded product, or when it is combined with wood such as plywood. In the bonding process, the adhesiveness is reduced, which is not preferable. Conversely, if the amount of the wood flour exceeds 250 parts by weight, the viscosity increases when the wood flour and the resin are kneaded, and the surface of the sheet becomes rough during molding with an extruder or the like, This is also not preferable because the edge of the sheet tends to be cut off, thereby lowering the productivity and the physical properties of the sheet.

In addition to the above-mentioned components, an inorganic filler, a lubricant, a surfactant, a tackifier, a pigment, an antibacterial agent, etc. are added to the wood flour-containing resin composition of the present invention within a range not impairing the object of the present invention. You may. This wood flour-containing resin composition can be obtained, for example, by kneading a pellet of a polyolefin-based copolymer and a predetermined amount of the above-mentioned specific wood flour with a Banbury mixer. Further, for its molding, the composition can be molded into a sheet with a heating roll. Alternatively, the resin and the wood powder may be mixed and pelletized by using a twin-screw extruder kneader equipped with a hot-cut device, and then formed by an extruder equipped with a T-die.

The wood powder to be added may be preliminarily dried by a dryer or a hopper dryer before kneading with the resin. When a twin screw extruder is used, the wood powder is added in-line using a device equipped with a hopper dryer. May be dried. The water content of the wood flour is preferably in the range of 3 to 7%. The molding temperature is preferably in the range of 120 to 190C. The thickness of the sheet to be molded is preferably in the range of 0.5 to 15 mm. If this thickness is less than 0.5 mm, composite molding with a skin material or wood tends to be difficult, while the thickness is 15 mm.
If it exceeds mm, the molding rate tends to be low, and the productivity of the sheet is significantly inferior. Further, when it is used as a flooring material, the workability and cutting workability tend to be inferior. The preferred sheet thickness is 1-5 mm.

The sheet-shaped resin product containing wood powder obtained as described above has a skin material on one side and a wood board, cloth on the other side.
Alternatively, a backing material such as paper may be laminated to form a laminated body, and the laminated body may be used as a flooring material. For laminating the skin material, a urea coater, a melamine resin, a vinyl acetate emulsion system, an ethylene-vinyl acetate emulsion system is applied to one side of this sheet with a coating device such as a roll coater, a blade coater, a curtain coater, and a spray coater. An acrylic emulsion-based, urethane emulsion-based, synthetic rubber-based, epoxy resin-based, or urethane resin-based adhesive may be applied, and the skin material may be bonded and laminated. A device such as a hot press, a cold press, or a vacuum press can be used for this adhesion.

The skin material used here preferably has a decorative surface, and examples thereof include a veneer or a veneer decorative plywood, a cork sheet, and a printing sheet. Examples of the backing material to be laminated on the other surface of the sheet-shaped molded article include, for example, a veneer, a plywood or a composite material in which paper or synthetic resin is laminated on the back surface of a wooden board,
Examples of the cloth include cotton, nylon, vinylon, polyester, woven cloth and non-woven cloth made of chemical fibers such as acrylic. Examples of the paper include high-quality printing paper, medium-quality paper, kraft paper, glassine paper, paperboard, Japanese paper, and a paper in which an olefin resin is laminated as a waterproof layer on one surface of these papers, or synthetic paper. .

In order to laminate the backing material, an adhesive may be applied to the sheet surface in the same manner as the skin material layer and then laminated with the backing material by a pressing device, or rolled into a roll. In the case of the lining material, the wood powder-containing resin molded product may be formed into a sheet shape and simultaneously laminated by heat bonding. The sheet thus prepared and obtained can be cut into desired dimensions to obtain the flooring material of the present invention.

[0021]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. <Evaluation of polyolefin-based (co) polymer> (1) Density: Measured by a density gradient tube method using a methanol / benzyl alcohol mixture according to ASTM D1505. (2) Melt Index (MI): ASTM D1
238 according to the measurement. (3) Mw / Mn: Mw and Mn were measured from a calibration curve (using standard polystyrene) using gel permeation chromatography (GPC) using trichlorobenzene as a solvent, and calculated from the measured values. <Evaluation of Sheet and Flooring Material> (1) Formability: Ease of forming was evaluated when a test sheet was prepared by an extruder. The evaluation criteria are as follows.

◯: A sheet could be prepared and rolled up without any problem. B: The sheet could be produced, but the appearance was inferior. X: The sheet could not be formed. (2) Bending stiffness: Measured according to JIS K7106. (3) Adhesive strength: An adhesive (CVC36 manufactured by Konishi Co., Ltd.) was applied to a plywood sheet having a thickness of 2 mm, the sheets were laminated, and then a load of 0.5 kg / cm ² was applied, and the sheets were left standing for 24 hours for lamination. A sample was prepared. For this sample, 180
By the peel adhesion test method, the adhesive strength was measured at a gripping speed of 200 mm / min and a sample width of 25 mm. (4) Workability: 30% by applying mortar to the concrete floor.
Epoxy adhesive (made by Cemedine Co., Ltd. E on the direct-bonding base for the test in which the height difference of 3 mm is sequentially provided at intervals of 3 cm.
P-331) was applied to a thickness of 1 mm, the laminated sheet prepared in the flooring production example was applied, and the workability and the followability to the stepped portion of the base were visually evaluated.

Criteria for evaluating workability ○: Good workability was obtained. Δ: The ability to follow the base is slightly inferior. X: The followability to the base was poor and defective adhesion occurred. <Example 1> EG815 manufactured by Dow Chemical Co., which is a polyolefin resin produced using a metallocene catalyst
0 added with wood powder in the composition ratio shown in the table, 65 mm manufactured by Mitsubishi Heavy Industries
φT die molding machine, temperature 190 ℃, sheet thickness 3m
A sheet was formed under the conditions of m and a take-up speed of 0.5 m / min.
The above-mentioned evaluation was performed about the obtained sheet. The results are shown in the table.

<Example 2> A sheet was prepared and evaluated in the same manner as in Example 1 except that the sheet thickness was 18 mm. <Example 3> Wood powder was added to EG8100 manufactured by Dow Chemical Co., which was manufactured using a metallocene-based catalyst as a polyolefin-based resin, at a composition ratio shown in the table, and the temperature was changed in the same manner as in <Example 1>. 180 ℃, sheet thickness 0.8mm,
A sheet was prepared under a take-up speed of 10 m / min and evaluated. The results are shown in the table.

<Comparative Examples 1 to 3> Sheets were prepared and evaluated in the same manner as in Example 1 except that the polyolefin resin and the wood powder shown in the table were used. The results are shown in the table. <Floor material production example> A urethane-based emulsion adhesive (Konishi Co., Ltd.) was applied to one side of the wood powder-containing resin sheet prepared in Example 1.
CVC36) manufactured by Roll Coater with coating amount of 200 g /
It was applied at m ² and a veneer plate (white oak) having a thickness of 0.2 mm was superposed on this, and pressed for 3 minutes with a press molding machine at a temperature of 40 ° C. to bond the sheet and the veneer plate.

Next, an adhesive was applied to the back surface of the laminated sheets in the same manner as above, and a base cloth made of vinylon gauze was laminated as a backing material. The veneer surface of the obtained sheet is # 20
Clear paint after polishing with 0 sander (Urel Sanding Sealer No. 263L; Arakawa Paint Co., Ltd.)
Was manufactured by a roll coater (100 g / m ² ).
After coating, dry at room temperature, polish with a # 400 sander, and then apply a transparent coating (Polyurex Flat Clear; manufactured by Woshin Chemical Industry Co., Ltd.) with a roll coater (80 g / m ² ) at room temperature. Dried in. After drying, 30.3 cm
Edges were cut to obtain a flooring material having a size of 60.6 cm.

Mortar coating on the concrete floor, 3
Epoxy adhesive (EP-3 manufactured by Cemedine Co., Ltd.)
31) was applied in a thickness of 1 mm, and the floor material prepared above was applied. The conformability of the floor material to the base was good.

[0028]

[Table 1] Resin: ETY / AO ... Ethylene-α-olefin copolymer HDPE ・ ・ ・ High density polyethylene MI: Melt index Average particle size: Unit (μm) Bending stiffness: Unit (Kg / cm ² ) Adhesive strength: Unit ( (Kg / 2.5cm) * mark; measurement is impossible because the material is destroyed

[0029]

EFFECT OF THE INVENTION A wood powder-containing resin composition containing a specific amount of wood powder having a specific average particle diameter based on a specific polyolefin-based copolymer produced using a metallocene catalyst of the present invention, in the form of a sheet. The molded product and the flooring material based on the molded product have excellent flexibility and good workability and adhesiveness.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B32B 21/08 B32B 21/08 27/32 103 27/32 103 C08J 5/04 CES C08J 5/04 CES C08L 97/00 LSW C08L 97/00 LSW E04F 15/10 104 9232-2E E04F 15/10 104A (72) Inventor Miyuki Yamada 2 Oike, Iwazuka-cho, Nakamura-ku, Aichi Prefecture Mitsubishi Chemical MKB Co., Ltd. Nagoya Business Office

Claims (3)

[Claims] 1. A polyolefin-based resin and the resin 100
A wood powder-containing resin composition containing 40 to 250 parts by weight of wood powder per part by weight, wherein the polyolefin resin is obtained by polymerizing using a metallocene catalyst. 12 is a copolymer with α-olefin, and has a density (b) of 0.86 to 0.88 g / cm ³ ,
(C) Melt index is 0.5 to 40, and (d)
An ethylene-α-olefin copolymer having a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (hereinafter, referred to as “Mw / Mn”) of 1.5 to 5 (hereinafter, “polyolefin type”). And a wood flour-containing resin composition in which the mean particle size of wood flour is 10 to 200 μm. 2. The composition according to claim 1 in an amount of 0.15 to 1
A wood powder-containing resin molded product molded into a sheet with a thickness of 5 mm. 3. A flooring material in which a skin material is laminated on one surface of the wood powder-containing resin molded product according to claim 2 and a wooden board, cloth, or paper is laminated on the other surface.