JPS6264840A - Polymer composition containing high-molecular cellulosic material - Google Patents

Abstract

PURPOSE:To improve processability, flexibility, tensile strength, etc., by blending a cellulosic graft copolymer, rubber and a plasticizer with a vinyl chloride 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) is mixed with 10-60wt% vinyl chloride polymer (B) (e.g., polyvinyl chloride) and 5-60wt% cellulosic graft copolymer (C) 5-30pts.wt. rubber and 20-100pts.wt. plasticizer (e.g., dioctyl phthalate) are blended with 100pts.wt. resulting polymer mixture to obtain the titled polymer compsn. By blending component C, the compatibility of component A with component B can be improved. By adding rubber, tensile strength can be improved. By adding the plasticizer, flexibility can be improved.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polymer containing a cellulose polymer, a vinyl chloride polymer, a cellulose graft copolymer, a rubber, and a plasticizer. Regarding the composition.

[Prior art] Conventionally, cellulose polymers such as this powder are blended with thermoplastic polymers, and cellulose polymers are impregnated with monomers that form thermosetting polymers or thermoplastic polymers. A method of obtaining a molded article by polymerizing and polymerizing is known.

[Problems to be solved by the invention] However, the blending method described above cannot increase the amount of cellulose-based polymer added, and the method of impregnating and polymerizing a monomer does not require extrusion processing or roll processing. It is difficult to mold it through processing and other methods, and it is also difficult to scale molded products that are flexible and have tensile strength.

The present invention was made in order to provide a polymer composition containing a cellulose-based polymer in which a large amount of cellulose-based polymer is added and which has excellent processability, tensile strength, and flexibility.

[Means for Solving the Problems] The present invention provides cellulosic polymers containing 30 to 70% (wt%)
(same below), 100 parts (by weight, same below) of a polymer mixture consisting of 10-60% vinyl chloride polymer and 5-60% cellulose graft copolymer, 5-30 parts of rubber, and 20-100 parts of plasticizer. The present invention relates to a polymer composition containing a cellulose-based polymer consisting of parts.

[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 50 to 200 mesh pass from the viewpoint of product appearance and strength.

Examples of the vinyl chloride polymer used in the present invention include polyvinyl chloride, chlorinated polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-allyl chloride copolymer, vinyl chloride-ethylene copolymer, and chlorinated polyvinyl chloride. vinyl
Examples include known copolymers such as propylene copolymers containing 50% or more of vinyl chloride, and mixtures thereof.

The cellulose-based graft copolymer used in the present invention is obtained by impregnating the cellulose-based polymer with a monomer and producing a
200 H7, ultrasonic waves with an intensity of about 100 to 1000 W, X-rays, γ-rays, etc. of 1 to 10 HeV) In the presence of usual suspending agents and polymerization initiators,
It may be produced by suspension polymerization under normal conditions, 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, it is preferable to use vinyl chloride, methyl methacrylate, monomers containing methyl methacrylate, or mixtures thereof because they are easily suspension polymerized and have good compatibility with thermoplastic polymers. In particular, it is preferable to copolymerize a mixture of methyl methacrylate and methyl acrylate or butyl acrylate because the processability and thermal stability of the composition are improved.
Preference is given to using a mixture of 100 parts of methyl methacrylate and 50 to 150 parts of methyl acrylate or butyl acrylate. In addition to the above-mentioned methyl acrylate and butyl acrylate, other monomer components when using a monomer containing methyl methacrylate include 2
- Ethylhexyl acrylate, hydroxyethyl methacrylate, etc., and the content of methyl methacrylate is 50% in the monomer containing methyl methacrylate.
% or more.

The amount of the 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 as a copolymer will not be exhibited, and 5
If it exceeds 0.00 parts, the grafting efficiency tends to decrease.

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

In the present invention, a polymer mixture is prepared from a cellulose polymer, a thermoplastic polymer, and a cellulose graft copolymer. 35-60%, thermoplastic polymer 10-60%, preferably 20-45%,
The cellulose graft copolymer content is 5 to 60%, preferably 10 to 30%.

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

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, you will not be able to obtain the feel of wood texture and good appearance that are characteristic of using wood flour.

Furthermore, 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, resulting in a cost disadvantage.

The composition of the present invention comprises 100 parts of the above polymer mixture and 5 to 5 parts of rubber.
30 parts, preferably 10-20 parts and 20-100 parts of plasticizer
parts, preferably 30 to 90 parts, and if necessary, processing aids may be used in amounts up to about 20 parts.

Examples of the rubber include natural rubber and SBR.

Known rubbers such as chlorinated polyethylene, acrylonitrile-butadiene rubber, ABS resin, and HBS resin can be mentioned.

If the proportion of rubber is less than 5 parts per 100 parts of the polymer mixture, the tensile strength of the resulting molded article will not be improved;
If the amount exceeds 50 parts, it becomes difficult to change the rigidity and surface appearance, which are characteristics of using cellulose polymers.

Examples of the plasticizer include commonly used plasticizers such as nistyl phthalate plasticizers, epoxy plasticizers, polyester plasticizers, and linear aliphatic plasticizers.

The proportion of plasticizer is 20 parts per 100 parts of the polymer mixture.
If the amount is less than 100 parts, the resulting molded product will not have the flexibility of a soft molded product, and if it exceeds 100 parts, it will be difficult to obtain the rigidity and surface beauty that are characteristic of cellulose polymers. .

Examples of the processing aids include commonly used heat stabilizers such as tin-based, metal soap-based, and phosphorus-based stabilizers, stabilizers such as commonly used antioxidants such as phenol-based and amine-based, and stearin. Examples include lubricants such as acids and fatty acid glycerides, fillers such as calcium carbonate and titanium oxide, and processing aids based on local molecules.

The proportion of processing aids is 2 parts per 100 parts of the polymer mixture.
If more than about 0 parts are used, bleeding tends to occur and it tends to be disadvantageous in terms of cost.

There are no particular limitations on the method for preparing the composition of the present invention, and a predetermined amount of a cellulose polymer, a thermoplastic polymer, and a cellulose graft copolymer are charged into a Henschel mixer or the like, mixed at about 60 to 120°C, and then polymerized. The composition of the present invention may be prepared by preparing a combined mixture and adding rubber, a plasticizer, and, if necessary, a processing aid to this, or by adding all of the above components and mixing at about 60 to 120°C. You may.

The composition of the present invention thus obtained can be molded under normal molding conditions by methods such as extrusion processing, roll processing, and press processing, and has a wood texture, impact resistance, and flexibility. It is possible to explore molded products with unique characteristics.

Next, the composition of the present invention will be explained based on Examples, but these are not intended to limit the present invention.

Examples 1 to 6 and Comparative Examples 1 to 3 Wood flour (200 mesh pass), polyvinyl chloride (manufactured by Kanekabuchi Chemical Co., Ltd., degree of polymerization 800), wood flour-vinyl chloride graft obtained by normal suspension polymerization method Copolymer (wood flour/vinyl chloride = 1/1 (weight ratio)), SBR (JSR-1500 manufactured by Japan Synthetic Rubber), plasticizer (dioctyl phthalate), and calcium-zinc stabilizer (Ca-Zn).
System stabilizer, MARK 5C-1 manufactured by Adeka Argus ■
2) were mixed in the proportions shown in Table 1 and kneaded with rolls at 150°C, and the winding time was examined as an evaluation of workability.

Conventional pressing method using the rolled composition, 140°C, 5
kQ/Cl1l, 1m thick under pressure for 5 minutes
A roll sheet of um was prepared, and the presence or absence of a wood grain feeling on the surface of the sheet was evaluated. 0 sheets with wood texture on the surface
Those without 1 were evaluated as ×.

The results are shown in Table 1.

Note that the term "wood texture" as used herein refers to a texture similar to that of a natural wood surface.

All of the sheets obtained were flexible and the wood powder did not come off even when bent.

From the results in Table 1, the roll winding time becomes faster when the wood flour-vinyl chloride graft copolymer is added (Example 1.
Comparison of Comparative Example 2 and Comparative Example 2), the feeling of wood texture can be obtained, but when the amount of wood flour is small as in Comparative Example 1, the winding time is fast but the feeling of wood texture cannot be obtained.

Examples 7 to 14 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 the suspension polymerization method.
Methyl methacrylate graft copolymer, barium
Zinc-based stabilizer (Ba-Zn-based stabilizer, MAR and AC-141 manufactured by Adeka Argus ■), acrylonide-butadiene rubber (JSRN220SH manufactured by Japan Synthetic Rubber ■)
) and a plasticizer (dioctyl phthalate) in the proportions shown in Table 2, the gel time and thermal decomposition time were examined using a Brabender plastograph at 150° C. and 50 rpm. Thermal decomposition time was determined by color change or decomposition.

Using the wound composition, a thickness of 0.0 mm was prepared in the same manner as in Example 1.
A flexible roll sheet of 2 mm was produced, and its tensile strength was measured according to JIS 6745.

The results are shown in Table 2.

In Table 2, 88^ represents methyl methacrylate, HA represents methyl acrylate, and BA represents butyl acrylate.

[Left below] From the results in Table 2, it can be seen that gelling properties, thermal stability, and tensile strength are improved by adding the wood flour-methyl methacrylate graft copolymer. Especially wood flour-
It can be seen that the effect is remarkable when methyl methacrylate-butyl acrylate graft copolymer and wood flour-methyl methacrylate-methyl acrylate graft copolymer are used.

E Effects of the present invention - The polymer composition of the present invention is: - Even if a larger amount of cellulose polymer is mixed than before, since the cellulose graft copolymer is used, the polymer composition of the present invention is not compatible with the vinyl chloride polymer. It is easy to process, and the molded product is flexible and has high tensile strength ■By selecting the composition of the cellulose-based graft copolymer,
It has characteristics such as being able to improve thermal stability and tensile strength.

Claims (1)

[Scope of Claims] 1. 100 parts by weight of a polymer mixture consisting of 30 to 70% by weight of a cellulose polymer, 10 to 60% by weight of a vinyl chloride polymer, and 5 to 60% by weight of a cellulose graft copolymer, and rubber 5 A polymer composition containing a cellulosic polymer consisting of ~30 parts by weight and 20 to 100 parts by weight of a plasticizer. 2. The composition according to claim 1, wherein the cellulosic polymer is wood flour. 3. The composition according to claim 1, wherein the vinyl chloride 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 graft copolymer consisting of a cellulose-based polymer and methyl methacrylate, methyl acrylate, or butyl acrylate.