JPS6264837A - Polymer composition containing high-molecular cellulosic material - Google Patents

Abstract

PURPOSE:To improve processability, thermal stability, etc., by blending a cellulosic graft copolymer with a thermoplastic polymer compsn. contg. a relatively large quantity of a high-molecular cellulosic material for the production of building materials. CONSTITUTION:30-70wt% high-molecular cellulosic material (A) (e.g., woodmeal or pulp) is mixed with 10-60wt% thermoplastic polymer (B) (e.g., polyvinyl chloride or chlorinated polyvinyl chloride) and 5-60wt% cellulosic graft copolymer (C) to obtain the desired polymer compsn. contg. a high-molecular cellulosic material. As component C, a copolymer composed of a high-molecular cellulosic material and vinyl chloride and/or a copolymer composed of a high-molecular cellulosic material and methyl methacrylate are/is preferred. By blending component C, the compatibility of component A with component B can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a cellulose polymer-containing polymer composition comprising a cellulose polymer, a thermoplastic polymer, and a cellulose graft copolymer.

[Conventional technology] Conventionally, cellulose polymers such as wood flour are blended with thermoplastic polymers, and cellulose polymers are impregnated with monomers that form thermosetting polymers or thermoplastic polymers. A method is known in which a molded product is hung by polymerizing the molded product.

[Problems to be Solved by the Invention] However, the blending method described above cannot increase the amount of cellulose polymer added, and the method of impregnating monomers and polymerizing them requires extrusion processing, roll processing, etc. It is difficult to mold it by processing or other methods.

The present invention has been made in order to provide a cellulose-based polymer-containing polymer composition that has a large amount of cellulose-based polymer added and has good processability.

[Means for Solving the Problems] The present invention provides cellulosic polymers containing 30 to 70% (wt%)
The present invention relates to a cellulose-based polymer-containing polymer composition comprising 10 to 60% of a thermoplastic polymer and 5 to 60% of a cellulose-based graft copolymer for improving the compatibility of the two.

[Example] Examples of cellulosic polymers used in the present invention include natural polymers such as wood flour, straw, bulb, and rice husk, purified cellulose, and chemically modified cellulose. Among these, it is particularly advantageous to use wood flour of about 60 to 200 mesh pass from the viewpoint of product appearance and strength.

Examples of thermoplastic polymers used in the present invention include polyvinyl chloride, chlorinated polyvinyl chloride, polystyrene, polyacrylic acid, polyacrylates from acrylates with alcohols having 1 to 12 carbon atoms, polymethacrylic acid, and polymethacrylic acid having 1 to 12 carbon atoms. Polymethacrylates, ABS-based polymers, HBS-based polymers from methacrylates with ~12 alcohols,
Polymers and copolymers such as polyethylene, polypropylene, and polyacrylonitrile, or copolymers produced from monomers used in the production of these polymers and copolymers,
Examples include various mixtures of the above polymers and copolymers.

Among these, it is particularly advantageous to use polyvinyl chloride, chlorinated polyvinyl chloride, or a mixture thereof since they are flame retardant.

The cellulose-based graft copolymer used in the present invention is obtained by impregnating the cellulose-based polymer with a monomer and producing a
200KH21 may be produced by irradiation with ultrasonic waves with an intensity of about 100 to 1000 W or radiation such as X-rays or gamma rays with a strength of 1 to 10 HeV. It may be produced by suspension polymerization under normal conditions in the presence of a polymerization initiator, and the production method is not particularly limited.

Examples of the monomer include vinyl chloride, vinylidene chloride, vinyl acetate, methacrylic acid, methacrylate with an alcohol having 1 to 12 carbon atoms, acrylic acid, and acrylic acid having 1 to 12 carbon atoms.
Examples include acrylates with 12 alcohols, acrylonitrile, butadiene, styrene, α-methylstyrene, allyl chloride, allyl glycidyl ether, and these may be used alone or in combination of two or more. Among these monomers, monomers containing vinyl chloride, methyl methacrylate, methyl methacrylate, or mixtures thereof are easily used for suspension polymerization.
It is preferable because it has good compatibility with thermoplastic polymers.

Particularly when using a mixture of methyl methacrylate and methyl acrylate or butyl acrylate,
It is preferable to use a mixture of 100 parts (by weight, hereinafter the same) of methyl methacrylate and 50 to 150 parts of methyl acrylate or butyl acrylate because the processability and thermal stability of the composition of the present invention are improved. In addition, when using a monomer containing methyl methacrylate, examples of monomer components other than those mentioned above include 2-ethylhexyl acrylate, hydroxyethyl methacrylate, etc. It is preferable that the content is 50% or more in the mass.

The amount of monomer to be graft-polymerized to 100 parts of cellulose-based polymer when producing a cellulose-based graft copolymer is preferably 10 to 500 parts, and 50 to 200 parts. It is even more preferable. If the weight is less than 10 parts, the characteristics of the copolymer will not be exhibited, and if it exceeds 500 parts, the grafting efficiency will tend to decrease.

The cellulose-based graft copolymers may be used alone or in combination of two or more.

In the present invention, the composition of the present invention is prepared from a cellulose polymer, a thermoplastic polymer, and a cellulose graft copolymer. Preferably 35-60%,
Thermoplastic polymer 10-60%, preferably 20-45%
, 5 to 60%, preferably 10 to 30% of the cellulose-based graft copolymer.

When the proportion of the cellulose polymer is less than 30%,
If, for example, wood flour is used as the cellulose-based polymer, the characteristics such as wood texture, good appearance, and high strength cannot be changed, and this is disadvantageous in terms of cost. If it exceeds 70%, it will be difficult to mix the composition uniformly, and the processability will not be good.

Further, when the proportion of the thermoplastic polymer is less than 10%,
Processability is poor, making it impossible to produce a uniform product, and if it exceeds 60%, for example, the feel of wood texture and good appearance that are characteristic of using wood flour cannot be obtained.

The proportion of the cellulose-based graft copolymer is 5%
If it is less than 60%, the processability of the composition will be poor, and if it exceeds 60%, the amount of cellulose polymer added will be small, which will be disadvantageous in terms of cost.

When molding the composition of the present invention, a processing aid may be used in an amount of about 20 parts or less per 100 parts of the composition.

Examples of the processing aid include commonly used plasticizers such as phthalate plasticizers, epoxy plasticizers, polyester plasticizers, and linear aliphatic plasticizers; tin-based plasticizers, metal soap-based plasticizers, Generally used heat stabilizers such as phosphorus type; commonly used antioxidants such as phenol type and amine type; lubricants such as stearic acid and fatty acid glycerides; fillers such as calcium carbonate and titanium oxide; Examples include, but are not limited to, bird molecule-based processing aids.

If the proportion of the processing aid exceeds about 20 parts, bleeding tends to occur and it tends to be disadvantageous in terms of cost.

The method for preparing the composition of the present invention is not particularly limited, and is prepared by charging a predetermined amount of a cellulose polymer, a thermoplastic polymer, and a cellulose graft copolymer into a Henschel mixer, etc., and mixing at approximately 60 to 120°C. However, if necessary, processing aids etc. may be added to this, and all ingredients, including those used as necessary, are prepared from the beginning, and the 60 to 120
It may be prepared by mixing at about ℃.

The composition of the present invention obtained in this way can be molded under normal molding conditions by methods such as extrusion processing, roll processing, and press processing, and has a wood texture and an appearance similar to that of natural wood. You can explore molded products that have characteristics such as good quality.

Next, the composition of the present invention will be explained based on examples. 1　　　　　　− However, these are not intended to limit the invention.

Examples 1 to 5 and Comparative Examples 1 to 3 Wood flour (200 mesh pass), polyvinyl chloride (manufactured by Ifuchi Kagaku Kogyo, polymerization degree 80o), wood flour-vinyl chloride graft obtained by normal suspension polymerization method A mixture of copolymer (wood flour/vinyl chloride-171 (weight ratio)), tribasic lead sulfate (tribase), and lead stearate in the proportions shown in Table 1 was roll-kneaded at 195°C and processed. The winding time was examined as an evaluation of the properties. In addition, using the rolled composition, a sheet with a thickness of 2 mm was produced using the usual press processing method under the conditions of a temperature of 185 ° C. and a pressure of 5 k (J/c++?) for 10 minutes, and the presence or absence of a wood grain feeling on the sheet surface was evaluated. did.

A sheet with a wood grain feel on its surface was evaluated as ○, and a sheet without a wood texture was evaluated as ×. The results are shown in Table 1.

Note that the term "wood skin sensation" as used herein means that there is a touch sensation similar to that of a natural wood surface.

From the results in Table 1, the roll winding time becomes faster when wood flour-vinyl chloride copolymer is added (comparison of Example 4.5 and Comparative Example 3, comparison of Example 1 and Comparative Example 2); It can be seen that if there is too little powder, the feeling of wood texture cannot be obtained (Comparative Example 1).

Examples 6 to 12 and Comparative Examples 4 to 5 The same main flour used in Example 1, polyvinyl chloride, and wood flour with the composition (weight ratio) shown in Table 2 obtained by a normal suspension polymerization method. - Methyl methacrylate-based graft copolymer, tin-based stabilizer, and PA-20 (processing aid manufactured by Kanebuchi Kagaku Kogyo ■) in the proportions shown in Table 2 were mixed using a Brabender Plastograph to produce 195 The gelation time and thermal decomposition time were examined under the conditions of ℃ and 50 ppm. Thermal decomposition time was determined by color change or decomposition of the mixture.

The results are shown in Table 2.

In Table 2, HMA represents methyl methacrylate, HA represents methyl acrylate, and BA represents butyl acrylate.

The results in Table 2 show that addition of the wood flour-methyl methacrylate graft copolymer improves gelation time and thermal stability.

[Effects of the Invention] The cellulose-based polymer-containing polymer composition of the present invention has the following characteristics: ■ Even if a larger amount of cellulose-based polymer is mixed than before, since the cellulose-based graft copolymer is used, there is no phase interaction with the thermoplastic polymer. Good solubility and easy processing ■By selecting the composition of the cellulose-based graft copolymer,
It has characteristics such as being able to improve thermal stability.

Claims (1)

[Scope of Claims] 1. A cellulose polymer-containing polymer composition comprising 30 to 70% by weight of a cellulose polymer, 10 to 60% by weight of a thermoplastic polymer, and 5 to 60% by weight of a cellulose graft copolymer. 2. The composition according to claim 1, wherein the cellulosic polymer is wood flour. 3. The composition according to claim 1, wherein the thermoplastic polymer is polyvinyl chloride or chlorinated polyvinyl chloride. 4. The cellulose-based graft copolymer is a copolymer consisting of a cellulose-based polymer and vinyl chloride and/or a copolymer consisting of a cellulose-based polymer and methyl methacrylate or a monomer containing methyl methacrylate. A composition according to claim 1. 5. The composition according to claim 4, wherein the cellulose-based graft copolymer is a copolymer consisting of a cellulose-based polymer and methyl methacrylate, methyl acrylate, or butyl acrylate.