JPH0148293B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a synthetic resin composition comprising a synthetic resin and modified wood flour obtained by impregnating and curing wood flour with a specific compound. Traditionally, wood flour has been generated in large quantities in the wood industry, but it has little utility and most of it is discarded as waste, so it is hoped that it can be used more effectively in the future from the perspective of resource conservation. It can be used as a filler or a modification material for synthetic resins, but untreated wood flour has no affinity with synthetic resins, so even if mixed with it, the properties of the composite material will deteriorate.
It is only used as a filler for some phenolic resins. The present inventors have discovered that treating wood flour with a specific compound improves its affinity with synthetic resins, and that when this is mixed with synthetic resins, the physical properties of composite materials are significantly improved. reached. The present invention is a synthetic resin composition comprising 100 parts by weight of a synthetic resin and 5 to 150 parts by weight of modified wood flour obtained by impregnating and curing wood flour with polyoxyalkylene (meth)acrylate represented by the following general formula (). It is. (Here, A is hydrogen or an active hydrogen residue of an alcohol, phenol, amine compound, or carboxylic acid compound having 1 to 8 carbon atoms and 1 to 24 carbon atoms, and R is Hydrogen or methyl group, m is an integer of 2 to 4, n is 2 to 100, x and y are each integers of 1 to 8, y
-x is 0 or an integer from 1 to 7; ) The compound represented by the general formula () used in the present invention is a compound having 1 to 8 active hydrogen atoms, such as alcohols, phenols, amine compounds, or carboxylic acid compounds having 1 to 24 carbon atoms, and the presence of a catalyst. It is obtained by subjecting the polyoxyalkylene compound obtained by addition polymerization of alkylene oxides described below to an esterification reaction with acrylic acid or methacrylic acid. Examples of the above alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, dodecanol, tridecanol, tetradecanol, hexadecanol,
Single group alcohols such as octadecanol, 2-ethylhexanol, isostearyl alcohol, oleyl alcohol; ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, polyglycerin, sugars, etc. of polyhydric alcohols are available. In addition, as phenols, phenol,
Cresol, butylphenol, octylphenol, nonylphenol, etc. can be used, and amine compounds include methylamine, dimethylamine, ethylamine, diethylamine, propylamine,
Monovalent amines such as dipropylamine, butylamine, dibutylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, docosylamine, oleylamine; ethylenediamine,
Polyvalent amines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine can be used. Furthermore, carboxylic acid compounds include acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid,
1 such as palmitic acid, stearic acid, oleic acid, etc.
Divalent fatty acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, etc. is available. As addition polymerization catalysts for alkylene oxides, alkali catalysts such as sodium hydroxide, potassium hydroxide, and sodium methoxy or acid catalysts such as Lewis acids such as boron trifluoride and tin tetrachloride can be used. Examples of alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran. Other compounds represented by the general formula () include acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, or 2-hydroxypropyl methacrylate with boron trifluoride, It can also be obtained by addition polymerizing the above alkylene oxides in the presence of a Lewis acid catalyst such as tin tetrachloride. The wood flour used in the present invention is made of coniferous wood,
Any broad-leaved tree may be used, but coniferous trees such as pine, Japanese pine, cedar, hemlock, Japanese hemlock, and spruce are more preferable. Regarding the particle size, sawdust generated in the wood industry may be used as is, but a fine powder finer than 28 mesh is preferable in order to increase the affinity with the synthetic resin and further improve the properties of the resulting composite material. In addition, the moisture content of wood flour is 25% or less, preferably 15% or less; too much moisture will worsen the miscibility and compatibility with synthetic resins, and the tensile strength of the composite material.
Physical properties such as hardness and impact resistance deteriorate. The modified wood flour used in the present invention can be obtained by impregnating and hardening 100 parts by weight of wood flour with 10 to 100 parts by weight of polyoxyalkylene (meth)acrylate represented by the general formula (). That is, when wood flour is placed in a container equipped with a stirrer and stirred while gradually adding the compound of general formula (), the treatment agent is absorbed and impregnated into the gaps of the wood flour. In order to carry out the impregnation more completely, it is also possible to operate under reduced or pressurized conditions in airtight containers. Although the treatment temperature may be room temperature, compounds of general formula () whose melting point is higher than room temperature are melted by heating to a temperature of about 80°C. It is preferable to impregnate the compound of general formula () into wood flour in the form of a undiluted solution, as it is easier to work with, but if necessary, lower alcohols, polyhydric alcohols, etc.
It may be used by dissolving or dispersing it in a solvent such as glycol ethers, esters, ketones, or water, and in this case, after impregnation, the solvent is removed by heating or heating under reduced pressure. To cure a compound of general formula () impregnated in wood flour, 50% of the treated wood flour is
It is also possible to perform thermal polymerization by treatment at a temperature of 0.degree. C. or higher, or to initiate and cure polymerization with ionizing radiation, electron beams, ultraviolet rays, etc., but it is usually preferable to carry out polymerization using a polymerization initiator. Examples of the polymerization initiator used in this case include peroxides, azo compounds, and redox polymerization initiators that are a combination of peroxides and reducing agents that have the ability to polymerize vinyl groups. Further, depending on the nature of the wood flour to be treated, if necessary, it is possible to add a known polymerization accelerator such as an amine, a metal soap, a metal halide, etc. for curing. Modified wood flour that has been treated as described above has improved compatibility with synthetic resins and has good compatibility.
It is extremely useful as a filler and modifier for synthetic resins. In the present invention, the modified wood flour is mixed in an amount of 5 to 15 parts by weight with respect to 100 parts by weight of the synthetic resin. The synthetic resins covered here include thermosetting resins such as phenolic resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, and epoxy resins, and thermoplastic resins such as polyethylene, polypropylene, polystyrene,
Examples include poly(meth)acrylate, polyvinyl chloride, polyvinyl acetate, polycarbonate, polyester, polyurethane, etc., but it is particularly effective against phenolic resin, urea resin, melamine resin, polyethylene, polypropylene, polystyrene, and polyvinyl chloride. . The synthetic resin composition mixed with the modified wood flour of the present invention has improved tensile strength and impact resistance as a composite material, improved cushioning properties, and has a lower surface resistivity and antistatic ability. is also granted,
It can be used effectively in a wide range of applications, including building materials such as flooring materials, wall materials, sealing materials, various packaging materials, electrical component materials, and industrial component materials. The present invention will be explained below with reference to Examples. Example 1 Production of modified wood flour Test wood flour S shown in Table 1 was placed in a container equipped with a stirrer.
Take 100 parts by weight, and add 2 parts by weight of a mixture of 50 parts by weight of impregnating agent A shown in Table 2, 0.05 parts by weight of polymerization initiator benzoyl peroxide, and 0.02 parts by weight of polymerization accelerator dimethylaniline while maintaining the temperature at 40 to 60°C and stirring.
It was gradually added to the wood flour S over a period of time, and stirring was continued for an additional 2 hours to ensure uniform impregnation. After that, the temperature was raised to 90℃ to 100℃ and heated for 4 hours to make wood flour S.
The impregnating agent impregnated inside was cured, and 139 parts of Table 3
Modified wood flour No. 1 shown in (yield 92.7%) was obtained. Thereafter, similar treatments were carried out using the impregnating agents shown in Table 2 to obtain modified wood flours No. 2 to No. 19 and Ratio-1 to Ratio-9 shown in Table 3. ● Test wood powder Cellulosin (trade name of Sanshin Kogyo Co., Ltd.) was used. The wood is mainly composed of conifers such as hemlock, Japanese hemlock, Japanese pine, and spruce, with approximately 5% by weight of hardwoods such as lauan mixed in. The particle size and moisture content are shown in Table 1.

[Table] ● Impregnating agent Compound (A) with the general formula () having the structural formula shown in Table 2
~J) and comparative compounds (K~P) were used.

【table】

【table】

【table】

[Table] Example 2 Using the modified wood flour shown in Table 4 obtained in Example 1,
A polyvinyl chloride composite material was produced under the following formulation and conditions, and its performance tests were conducted. The results are shown in Table 4. 1 Compound composition Polyvinyl chloride (degree of polymerization 1100) ...100 parts by weight Dioctyl phthalate ...50 Dibutyltin dilaurate ...2.5 parts by weight Calcium stearate ...0.5 Zinc stearate ...0.5 Modified wood flour ...Table 4 2 Mixing conditions shown in 2 Using two calender rolls with an outer diameter of 6 inches,
At a temperature of 160 to 170°C, the above blended composition was gradually added and mixed for about 10 minutes to obtain a composite material.

[Table] From the test results in Table 4, the composite material obtained from the synthetic resin composition of the present invention has improved tensile strength and impact strength compared to the comparative product, and is softer in terms of hardness and has better cushioning properties. It's summery. Example 3 Using the modified wood flour shown in Table 5 obtained in Example 1,
A polypropylene composite material was produced under the following formulation and conditions, and the performance tests shown in Table 5 were conducted. The results are shown in Table 5. 1 Composition polypropylene (Mitsui Noblen JHH-G:
Mitsui Toatsu Co., Ltd.) ...100 parts by weight dibutyltin dilaurate ...0.5 Modified wood flour ...2 shown in Table 5 Mixing conditions Same as Example 2 except that the mixing temperature was changed to 170 to 180°C Kneaded.

[Table] From the test results in Table 5, the composite material obtained from the synthetic resin composition of the present invention has improved tensile strength and impact strength compared to the comparative product, and is softer in terms of hardness and has better cushioning properties. have characteristics. Example 4 Using the composite materials produced in Example 2 and Example 3, the surface resistivity was measured using JISK-
Measured according to 6705. The results are shown in Table 6. From Table 6, the composite material obtained from the synthetic resin composition of the present invention has a lower surface resistivity than the comparative product.
It can be seen that it has antistatic ability.

【table】

Claims (1)

[Scope of Claims] 1. 100 parts by weight of a synthetic resin and 5 to 150 parts by weight of modified wood flour obtained by impregnating and hardening wood flour with polyoxyalkylene acrylate or polyoxyalkylene methacrylate represented by the following general formula (). A synthetic resin composition consisting of. (Here, A is hydrogen or an active hydrogen residue of an alcohol, phenol, amine compound, or carboxylic acid compound having 1 to 8 carbon atoms and 1 to 24 carbon atoms, and R is Hydrogen or methyl group, m is an integer of 2 to 4, n is 2 to 100, x and y are each integers of 1 to 8, y
-x is 0 or an integer from 1 to 7; )