JPH09104010A - Ligneous resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide ligneous resin composition which is filled with ligneous feeling and covalently has the characteristic of lumber and resin and is capable of easily obtaining flame retardancy. SOLUTION: This ligneous resin composition consists of 1-99 pts.wt. powdery or fibrous ligneous material (A), 99-1 pts.wt. thermoplastic resin (B) and an aqueous film-formable inorganic compound (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wood-based resin composition which has wood-like texture, combines the characteristics of wood and resin, and can be easily imparted with flame retardancy.

[0002]

2. Description of the Related Art A wood-based resin composition obtained by mixing relatively fine wood powder as a molding aggregate with a thermoplastic resin such as polystyrene, ABS, or polyvinyl chloride and performing press molding, extrusion molding, injection molding, or the like. Is known (for example, Japanese Patent Publication No. 3-16970).

A molded article made of such a wood-based resin composition is used as a building member, for example, as a door frame material, a window frame material,
In addition to building materials such as flooring and wall materials, it is expected to be used for furniture, automobiles, ships, home appliances, etc.

However, the molded product having such a structure is not sufficiently flame-retardant for use in high-rise building members and some automobile parts where flame retardancy is required. And its use is limited.

In order to solve these problems, addition of an organic halogen-based flame retardant, an antimony-based flame retardant auxiliary agent, etc. has been tried, but it is not so effective. Further, if a large amount of flame retardant is used, problems such as generation of harmful gas during combustion occur.

[0006]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a wood-based resin composition which is full of wood texture, combines the characteristics of wood and resin, and can easily impart flame retardancy. To do.

[0007]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems, and by adding an aqueous film-forming inorganic compound together with wood powder to be added to a thermoplastic resin, It has been found that excellent characteristics can be obtained, and the present invention has been completed. That is, the present invention is a wood material having (A) 1 to 99 parts by weight of a powdery or fibrous wood material, (B) 99 to 1 parts by weight of a thermoplastic resin, and (C) an aqueous film-forming inorganic compound. It is a resin composition.

Hereinafter, the present invention will be described in detail. The powdery or fibrous woody material of component (A) used in the present invention is made from crushed chips, pulp, waste materials produced from wood processing steps, sawdust, or the like. These materials usually contain about 10 to 20% by weight of water.

The material is heated (for example, 100 to 150).
C.), preferably 20 to 3
It can be powdered to 00 mesh. Alternatively, a strong shearing force may be applied at this time to defibrate the wood-based material into a fibrous state. The wood material (A) thus obtained preferably has a water content of 6% by weight or less, especially 3% by weight or less.

The component (B) thermoplastic resin used in the present invention may be any general thermoplastic resin, such as polystyrene, HIPS (high impact polystyrene), ABS (acrylonitrile butadiene styrene), Examples thereof include polyvinyl chloride, polyethylene, polypropylene, polyamide, polyester, polycarbonate, polyphenylene ether, and polyetherimide. These resins may be used alone or as a blend of two or more. In particular, modified polystyrene, which is an alloy of polystyrene or HIPS and polyphenylene ether, is preferable.

The weight ratio of the component (A) wood material and the component (B) thermoplastic resin can be varied within a wide range, and when a molded article is obtained by compression molding, the component (A): component (B). Is (1-99) :( 99-1), preferably (3
0 to 80): (70 to 20). When a molded article is obtained by extrusion or injection molding, component (A): component (B) is (1 to 99) :( 99 to 1), preferably (1
0-90): (90-10), preferably (30-7)
0): (70 to 30).

The component (C) aqueous film-forming inorganic compound used in the present invention is composed of a mineral acid or a sub-mineral acid compound which is hydrated with a metal to form boric acid or hydrofluoric acid, and an alkali metal. [A _a B _b ] _r C _c D _d or [A _a B _b C _c D _d ] _s C _p D _q where A: Si, Al B: FH, H, BH ₃ , B ₂ O ₃ C: Na, K, Li D: H ₂ O, OH (where a, b, c, d, p, q, r, s in the formula are the number of moles).

This aqueous film-forming inorganic compound is used as a surface coating material or an adhesive material, and the inorganic coating film is not destroyed even when exposed to a flame, and heat conduction is prevented by dehydration of crystal water. Furthermore, it becomes a heat-resistant coating film and shows the effect of preventing the inflow of radiant heat. Examples of such an aqueous film-forming inorganic compound include Likit Ceramics PHN (trade name) manufactured by Comix Corporation.

The total solid content of the component (C) aqueous film-forming inorganic compound is 0.05 to 100 relative to the component (A) wood material.
%, Preferably 0.1 to 50%. If the total amount of the solid content of the component (C) is less than the above range, the effects of the present invention will not be sufficiently exhibited, and if it is more than the above range, various physical properties will deteriorate.

The method of adding the component (C) aqueous film-forming inorganic compound to the component (A) wood material is not particularly limited, but the water-based film-forming inorganic compound is added to and impregnated into the wood material, and this is heated and dried. The method of crushing is mentioned.

The component (C) aqueous film-forming inorganic compound is diluted with water or a mixed solvent of water and alcohol so as to facilitate the impregnation of the component (A) wood material, and the solution concentration is from 0.05 to
It may be 50%. When the concentration of the component (C) is lower than the above range, workability is deteriorated, and when it is more than the above range, it becomes difficult to dissolve.

The component (C) flame retardant used in the present invention is used for making the component (B) thermoplastic resin flame-retardant, and contains phosphorus, nitrogen, halogen and the like depending on the type of the component (B). Any organic and inorganic flame retardants, halogen-containing polymers, metal hydroxides such as aluminum and magnesium, boron compounds, metal oxides, sprayed silica, etc. can be selected as long as they can impart flame retardancy. You can

Of the phosphorus-based flame retardants, phosphoric acid ester-based compounds are particularly preferable. As the phosphate compound,
The following (Chemical formula 1),

[0019]

Embedded image

(Here, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group.
Except when ¹ = R ² = R ³ = R ⁴ = H. X ⁻ represents a divalent or higher valent organic group, p is 0 or 1, q is 1 or more,
For example, an integer of 30 or less and r is an integer of 0 or more. )
A phosphoric acid ester compound represented by However, it is not limited to these.

In the above formula, examples of the organic group include an alkyl group which may be substituted or not, a cycloalkyl group and an aryl group. When substituted, examples of the substituent include an alkyl group, an alkoxy, an alkylthio group, a halogen, an aryl group, an aryloxy group, an arylthio group, a halogenated aryl group, and the like, and a combination of these substituents. Groups (for example, arylalkoxy groups, etc.) or groups in which these substituents are bonded by oxygen atom, sulfur atom, nitrogen atom, etc. (for example, arylsulfonylaryl group, etc.)
May be used as a substituent.

The term "divalent or higher valent organic group" means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to carbon atoms from the above-mentioned organic groups.

Examples include alkylene groups, and preferably (substituted) phenylene groups, derived from polynuclear phenols such as bisphenols, and the relative positions of two or more free valences are arbitrary.

Particularly preferred are hydroquinone,
Resorcinol, diphenylol methane, diphenylol dimethyl methane, dihydroxydiphenyl, P, P'-
Examples include dihydroxydiphenylsulfone and dihydroxynaphthalene.

Specific examples of phosphoric acid ester compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisopropylphenyl phosphate, Tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl)-
2,3-dichloropropyl phosphate, tris (2,3-
Dibromopropyl) phosphate and bis (chloropropyl) monooctyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bis, wherein R ¹ -R ⁴ are alkoxy such as methoxy, ethoxy and propoxy, or preferably (substituted) phenoxy. Examples thereof include polyphosphates such as phosphate and trioxybenzene triphosphate, preferably triphenyl phosphate and various polyphosphates.

Among the halogen-based flame retardants, aromatic brominated compounds are particularly preferable. Specific examples thereof include low molecular weight organic halogen compounds of tetrabromobisphenol A, halogenated polycarbonates, halogenated epoxy compounds, brominated polystyrenes, brominated bisimide compounds, and the like.

The above flame retardant is added in an amount of 0.5 to 40% by weight, preferably 2 to 30% by weight, based on 100 parts by weight of the component (B). If the amount of the flame retardant is more than the above range, mechanical properties and heat resistance are impaired.

The halogen-based flame retardant is preferably used together with a flame retardant aid. Examples of the flame retardant auxiliary used here include metal oxides and hydroxides such as antimony trioxide, antimony tetroxide, antimony pentoxide, antimony halide, aluminum hydroxide, magnesium hydroxide and tin dioxide.

The amount of the flame retardant aid added is 0 to 15% by weight, preferably 0.5 to 10% by weight based on 100 parts by weight of the component (B).
% By weight.

The wood-based resin composition of the present invention may further contain an anti-dripping agent. Fluorinated polyolefin that can be used as such an anti-dripping agent,
It can be obtained commercially or can be produced by a known method.

It is, for example, 100 to 10 in aqueous medium using a free-radical catalyst (for example sodium, potassium or ammonium peroxydisulfate).
00 psi pressure and 0-200 ° C, preferably 20-
It is a white solid obtained by polymerizing tetrafluoroethylene at a temperature of 100 ° C.

For more information, see Brubaker US Pat. No. 2,393,967. Although not essential, relatively large particles, such as average particle size 0.3 to 0.7
It is preferred to use a resin in the form of particles of mm (mainly 0.5 mm).

This is better than the usual polytetrafluoroethylene powder with a particle size of 0.05 to 0.5 mm. The reason that such relatively large particle size materials are particularly preferred is that they readily disperse in the polymer and tend to combine the polymers to form a fibrous material.

Such a suitable polytetrafluoroethylene is called Type 3 according to ASTM and is actually EIDupont de Nemours and Company.
From Teflon 6 (trademark: Teflon 6). Alternatively, it may be obtained commercially as Teflon 30J (trademark) from Mitsui DuPont Fluorochemicals.

The fluorinated polyolefin is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1.0, based on 100 parts by weight of the total of the components (A) and (B).
Use parts by weight.

In addition to the above-mentioned components, the wood-based resin composition of the present invention may have other conventional additives such as other components, for example, at the time of mixing the resin and at the time of molding, as long as the physical properties thereof are not impaired. Pigments, dyes, inorganic fillers (glass fiber, carbon fiber, glass flake, mica, talc, clay, carbon black, silica, titanium oxide, etc.), dispersants (silane coupling agents such as aminosilane and epoxysilane, titanate type) Coupling agents, etc., antibacterial agents (silver,
Copper, zinc-based inorganic antibacterial agents such as Zeomics), heat-resistant agents, antioxidants (hindered phenols, hindered amines, phosphites, etc.), UV absorbers (benzotriazole-based, benzophenone-based, etc.), lubricants, release agents A mold agent, a plasticizer, a fluidity improver, an antistatic agent, an elastomer, a foaming agent, and other stabilizers can be added.

The method for producing the wood-based resin composition of the present invention is not particularly limited, and a usual method can be used. Specific examples thereof include a method of dry blending using a mixer such as a Banbury mixer and a Henschel mixer, or a method of kneading while melting the resin using a mixer, a kneading extruder, or a roll, and these are batchwise. Or drive continuously. The mixing order of each component is not particularly limited.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below with reference to Examples. In the examples, the following components were used.

Component (A) powdery wood material: particle size 20 mesh or less, water content 0.9 wt% (after drying)

Component (B-1) Modified polyphenylene ether: Noryl 115 (trademark: manufactured by GE Plastics Co., Ltd.)

Component (B-2) Polyetherimide: Ultem 1000 (trademark: manufactured by GE Plastics Co., Ltd.)

Component (B-3) Polypropylene (PP): Hypol (trademark: manufactured by Mitsui Petrochemical Industry Co., Ltd.)

Component (B-4) Polyvinyl chloride (PVC): Denka Vinyl SS-13
0 (trademark: manufactured by Denki Kagaku Kogyo Co., Ltd.)

Component (C) Aqueous film-forming inorganic compound: Likit Ceramics PHN
(Trademark: manufactured by Comix), solid content 42-45%
(600 ° C)

Component (D-1) triphenylene phosphate: TPP (trademark: manufactured by Daihachi Chemical Co., Ltd.)

Component (D-2) Brominated bisphenol A oligomer (Br-BPA):
Fireguard 700 (trademark: Teijin Chemicals Ltd.)

Component (D-3) antimony trioxide (Sb ₂ O ₃ ): Phicat AT-3
(Trademark: manufactured by Suzuyu Chemical Co., Ltd.)

The compositions described in the examples were prepared as follows. First, Likit ceramics (hereinafter referred to as LC) is added to a wood material and mixed with a heater-equipped mixer 15
Coating was performed by stirring and drying at 0 ° C.

Subsequently, the respective components were mixed and kneaded by a twin-screw extruder to prepare chips, and 1/16 inch test pieces were prepared by an injection molding machine. Subsequently, each composition was evaluated as follows.

UL94 / V0, V1, V2 Test Five test rods were tested according to the test method given in Underwriters Laboratories, Inc. Bulletin 94 “Combustion Test for Material Classification” (hereinafter referred to as UL-94). Tested at a thickness of 1/16 inch. By this test method, the test material is U based on the results of 5 samples.
L-94 V-0, V-1, and V-2 were evaluated. The criteria for each V grade for UL-94 are outlined below.

V-0: The average flame holding time after removing the ignition flame is 5 seconds or less, and all the samples do not drop the fine flame that ignites the absorbent cotton.

V-1: The average flame holding time after removing the ignition flame is 25 seconds or less, and all the samples do not fall the fine flame igniting the absorbent cotton.

V-2: The average flame holding time after removing the ignition flame is 25 seconds or less, and these samples drop the fine flame igniting the absorbent cotton.

UL-94 specifies that all test rods must be classified in a particular V grade if they do not pass that grade. If this condition is not met, the five test rods will be given the grade of the worst performing one test rod. For example, if one test bar is classified as V-2, the rating for all five sample bars is V-2.

Examples 1 to 3 Noryl 115 (trademark: manufactured by Nippon GE Plastics Co., Ltd.) was used as the thermoplastic resin, and the addition amount (solid content) of LC coating the wood material was changed.

Comparative Example 1 The above Noryl 115 was compared with a composition comprising untreated wood.

From the evaluation of the component composition (% by weight) and the flame retardancy of each composition, it was found that the flame retardancy was remarkably improved.

[0058]

[Table 1] Component ratios and evaluation results of Examples and Comparative Examples

Examples 4 to 6 This example shows the test results of a flame-retardant resin composition using a numerical class of thermoplastic resins.

Table 2 shows the component composition (% by weight) of each composition and the evaluation of flame retardancy. From the results shown in Table 2, it was found that a wood-based resin composition having excellent flame retardancy can be obtained by using a wood material coated with LC.

[0061]

[Table 2] Component ratios of Examples and Comparative Examples and Examples

[0062]

According to the above description and examples, the wood-based resin composition containing the aqueous film-forming inorganic compound exhibits excellent flame retardancy in addition to the general characteristics of the wood-based resin. However, the molded product is expected to be applied to a wide range of applications such as door frame materials, flooring materials, wall materials, etc. as furniture materials for flame retardancy, furniture, automobiles, ships, home appliances, etc. .

Claims (11)

[Claims] 1. (A) Powdery or fibrous wood material 1
A wood-based resin composition comprising 99 parts by weight, (B) a thermoplastic resin 99 to 1 parts by weight, and (C) an aqueous film-forming inorganic compound. 2. The wood-based resin composition according to claim 1, wherein the wood material (A) is in the form of powder of 20 to 300 mesh or in the form of defibrated fibers. 3. The thermoplastic resin (B) is one or two selected from polystyrene, HIPS, ABS, polyvinyl chloride, polyethylene, polypropylene, polyamide, polyester, polycarbonate, polyphenylene ether, and polyetherimide. The wood-based resin composition according to claim 1, wherein the wood-based resin composition comprises a combination of two or more kinds. 4. The wood-based material according to claim 1, wherein the thermoplastic resin (B) is a modified polyphenylene ether which is an alloy resin of polystyrene or HIPS and polyphenylene ether. Resin composition. 5. The (C) aqueous film-forming inorganic compound comprises a mineral acid or a sub-mineral acid compound which is hydrated with a metal to form boric acid or hydrofluoric acid, and an alkali metal, and has the general formula [A _a B _b ] _R C _c D _d or [A _a B _b C _c D _d ] _s C _p D _q where A: Si, Al B: FH, H, BH ₃ , B ₂ O ₃ C: Na, K, Li. D: H ₂ O, OH (where a, b, c, d, p, q, r, s: represents the number of moles in the above formula).
The wood-based resin composition according to any one of 1. 6. The total solid content of the (C) aqueous film-forming inorganic compound is 0.05 to 100 relative to the (A) wood material.
%, And the wood-based resin composition according to any one of claims 1 to 4. 7. The wood resin composition according to claim 1, wherein the wood material (A) is coated with the aqueous film-forming inorganic compound (C). 8. The aqueous film-forming inorganic compound (C) for coating the wood material (A) is diluted with a solvent to a solution concentration of 0.05 to 50%. 7. The wood-based resin composition according to any of 7. 9. The wood-based resin composition according to claim 8, wherein the solvent for diluting the aqueous film-forming inorganic compound (C) is water or a mixed solution of water and alcohol. 10. The thermoplastic resin (B),
(D) Flame retardant The woody resin composition according to any one of claims 1 to 8, which contains an amount of 40% by weight or less. 11. The (D) flame retardant is an organic or inorganic flame retardant containing phosphorus, nitrogen, halogen, etc., a halogen-containing polymer, a metal hydroxide such as aluminum or magnesium, a boron compound, a metal oxide, The wood-based resin composition according to claim 9, which is composed of one kind or a combination of two or more kinds selected from sprayed silica and the like.