JPS61159428A - Modification of synthetic resin molding - Google Patents

Abstract

PURPOSE:To obtain an improved molding of good heat stability and low deformation, by irradiating a heterogeneous system consisting of a synthetic resin molding and a vinyl monomer with ultrasonic waves. CONSTITUTION:A heterogeneous system consisting of a synthetic resin molding and a vinyl monomer is irradiated with ultrasonic waves. Among the synthetic resins for producing the synthetic resin molding applied,polyvinyl chloride resin and polystyrene resin which have been used in various applications because of their particularly good moldability but have been somewhat lacking in functional property and durability are preferable since they are inexpensive, can be easily molded and are used generally. With respect to the shape of the synthetic resin molding applicable,sheets, films, plates, etc., are preferable since they can be uniformly irradiated with ultraviolet rays and can be produced continuously.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel method for modifying synthetic resin molded articles. More specifically, the present invention relates to a method of modifying a molded article by producing a copolymer by irradiating a synthetic resin molded article with ultrasonic waves in the coexistence of a vinyl monomer.

[Conventional technology] Conventionally, synthetic resin molded products have had problems such as staining due to static electricity, migration of compounding agents to the surface, and deterioration due to ultraviolet rays. Efforts have been made to solve these problems through processes such as

[Problems to be Solved by the Invention] If the above-mentioned problems of synthetic resin molded products are to be solved by the above-described method, the surface of the synthetic resin molded product and the coating film formed from the film or coating agent, etc. There are problems such as insufficient adhesion, and the process becomes complicated when attempting to plasma-treat the surface of a synthetic resin molded product or adhere a film to it.

Furthermore, the quality of the modified molded product is not necessarily satisfactory.

The present invention has been made to solve the above problems.

[Means for Solving the Problems] The present invention relates to a method for modifying a synthetic resin molded article by copolymerization carried out by irradiating ultrasonic waves in the coexistence of the synthetic resin molded article and a vinyl monomer. Because vinyl monomers are copolymerized by ultrasonic waves, there is no need to use a polymerization initiator, and therefore the modified molded product has good thermal stability, and there is no need to dissolve the modified molded product in the monomer. Because there is no molded product, there is less deformation of the molded product.

[Example] Examples of the synthetic resin for manufacturing the synthetic resin molded product used in the present invention include polyvinyl chloride resin, ABS
resin, HBS resin, AS resin, MHA resin, polystyrene resin, PE resin, PP resin, PAN
Commonly used thermoplastic resins such as (polyacrinitrile) resins and polyester resins, and commonly used thermosetting resins such as epoxy resins, urea resins, unsaturated polyester resins, and phenolic resins. Examples include synthetic resins consisting of a single resin or two or more resins. Among these, polyvinyl chloride resin and polystyrene resin have particularly good moldability and are used for various purposes, but are somewhat inferior in functionality and durability.
It is preferable because it is easy to make molded products and has been commonly used.

For example, stabilizers, processability improvers, plasticizers, and other compounding agents and additives may be added to the synthetic resin as appropriate.

The synthetic resin molded articles used in the present invention are those molded by commonly used molding methods such as extrusion molding, injection molding, calendar molding, and vacuum molding. There are no particular restrictions on the shape or size of the molded product, but from the viewpoints of uniform irradiation with ultrasonic waves and continuous production,
Preferably, the material is a sheet, film, or plate.

The vinyl monomer used in the present invention has the general formula: CH3-C-0-, B is a hydrogen atom or a halogen atom,
X is a hydrogen atom, a methyl group, -C-0-R (wherein, R is 0
1 to CI8 alkyl group) + C) 12 cHz
o) TH (in the formula, n represents 1 to 5) or a halogen atom, Y is a hydrogen atom, -C-OR (in the formula, R is the same as above), a phenyl group, -c=N.

-303Ha, C) 12 =CH- or a sulfonic acid residue) is a commonly used vinyl monomer. Among these vinyl monomers, especially when made into polymers, they have properties such as conductivity and
The polymer has functions such as hydrophilicity, ion adsorption, abrasion resistance, weather resistance, and gas selectivity, or by reacting a combination capable of imparting the above functions to the obtained polymer, the above-mentioned functions can be easily obtained. Monomers that can have functions are preferred. Specific examples of the vinyl monomer include methacrylic acid, methyl methacrylate, acrylonitrile, sodium allylsulfonate, and vinyl ether. These vinyl monomers may be used alone, or 2
More than one species may be used in combination.

In the present invention, ultrasonic waves are irradiated to a system in which a synthetic resin molded article and a vinyl monomer coexist to modify the synthetic resin molded article.

The coexistence of synthetic resin molded products and vinyl monomers means that
The synthetic resin molded article may be immersed in the vinyl monomer, or the surface of the synthetic resin molded article may be coated with the vinyl monomer.

In short, it is sufficient that the synthetic resin molded article to be modified and the vinyl monomer are in contact with each other, and there are no particular limitations as long as they are in such a state.

When synthetic resin molded products and vinyl monomers coexist,
Although a solvent is not particularly necessary, a solvent may be used to adjust the viscosity of the vinyl monomer or adjust the compatibility between the synthetic resin molded product and the monomer. Examples of such solvents include methanol, n-hebutane, water, dioxane, etc., but some solvents do not completely dissolve the synthetic resin molded product used, and others are solvents that volatilize easily so that they can be easily removed after repulsion. Preferably, a solvent is used.

There are no particular limitations on the ultrasonic waves used in the present invention, and the frequency of
Ultrasonic waves with an output of 0.1 to 100 N/7 at N2 to 2,000 N2 can be used, but from the viewpoint of increasing reaction efficiency, ultrasonic waves of 0.51/cd or more are preferable. .

According to the method of the present invention, shape, strength, etc. are imparted using an easily moldable synthetic resin, and the copolymerized portion is then irradiated with ultrasonic waves to protect the synthetic resin molded product or impart various functions. becomes possible. Furthermore, a synthetic resin molded article modified by copolymerization may be treated with an appropriate solvent or heat to make the copolymer more uniform.

Next, the method of the present invention will be explained based on Examples, but the present invention is not limited thereto.

Example 1 A composition consisting of 100 parts of vinyl chloride resin (parts by weight, same hereinafter), 10 parts of plasticizer, 2 parts of stabilizer, and 0.2 parts of lubricant was molded to obtain a sheet with a thickness of 0.2 parts m. .

10 g of the sheet obtained in No. 31 was placed in a glass container, and in the presence of styrene monomer, N2 and 60
014 ultrasonic waves were irradiated at 60° C. for 3 hours.

After washing the resulting sheet with ethyl acetate to remove the polystyrene polymer, the weight had increased by 5.6%. A rough investigation using infrared absorption spectroscopy revealed that a styrene/vinyl chloride copolymer had formed.

The vinyl chloride resin is 3100 manufactured by Kanekabuchi Chemical Industry ■.
1 (degree of polymerization 1030), the plasticizer was dioctyl phthalate manufactured by Ohe Kagaku ■, the stabilizer was MARK AC-141 manufactured by Adeka Argus, and the lubricant was Rikemar manufactured by Riken Vitamin ■.

Example 2 and Comparative Example 1 In the same manner as in Example 1, the vinyl chloride resin sheet obtained in Example 1 was treated with 28% N2, in the presence of methacrylic acid.
Ultrasonic waves of 600 W were irradiated at 60° C. for 2 hours. The resulting sheet was washed with ethyl acetate to remove the polystyrene polymer, and its weight was measured, and it was found to have increased by 8.4%. When this sheet was analyzed by surface infrared absorption spectroscopy, the formation of a vinyl chloride/methacrylic acid copolymer was observed.

The obtained sheet was immersed in water, and after taking it out, the spread of water droplets on the sheet surface was observed to examine the hydrophilicity of the sheet surface. The results are shown in Table 1.

For comparison, the hydrophilicity of the sheet surface was also investigated for sheets that were not irradiated with ultrasound. The results are shown in Table 1.

Example 3 In the same manner as in Example 1, in the presence of a mixed solution of sodium allylsulfonate/methacrylic acid/water at a weight ratio of 1/1/2, N2 was added to the sheet obtained in Example 1. ,
Ultrasonic waves of 80011 were irradiated at 60° C. for 2 hours. When the weight of the sheet was measured after washing with water, a weight increase of 4.6% was observed. Furthermore, when examined using surface infrared absorption spectroscopy, it was found that vinyl chloride/allylsulfonic acid soda/
Formation of a methacrylic acid copolymer was observed.

Example 4 Using the glass container of 3j, a plate-shaped injection-molded product 103 of polystyrene resin was irradiated with 600M ultrasonic waves at 60° C. in a N2 gas flow for 2 hours in the presence of methacrylic acid. After washing the molded body with hot hexanol to remove polymethyl methacrylate, the weight increase was 11.5%. A rough examination by surface infrared absorption spectroscopy revealed the formation of a styrene/methyl methacrylate copolymer on the surface of the molded product.

When the adhesive strength of the surface of the obtained copolymer was examined using a tensile tester, no peeling of the surface layer was observed, and the molded article was broken.

Example 5 In the same manner as in Example 4, a polystyrene resin molded product similar to that used in Example 4 was coated with 28
When the molded product was irradiated with N2 and 600°C ultrasonic waves for 2 hours at 60°C, the formation of a styrene/methacrylic copolymer was observed on the surface of the molded product, as in Example 4.

The thermal stability of the obtained molded article was examined in a gear oven at 190°C, and it was found to have better thermal stability than the original molded article.

Example 6 and Comparative Example 2 A plate-shaped molded product with a weight of 57 and a thickness of 2 Jll was made by injection molding a copolymer of acrylonitrile, styrene, and α-methylstyrene in the presence of methacrylic acid in the same manner as in Example 4. When the molded product was irradiated with 28 KHz, 600 W ultrasonic waves at 60° C. for 2 hours and washed with water and ethanol, a weight increase of 4.1% was observed. The formation of a copolymer of 7-acrylonitrile/styrene/α-methylstyrene/methacrylic acid was observed on the surface of the molded product.

The resulting molded product was immersed in water, and after taking it out, the spread of water droplets on the surface of the molded product was observed to determine the hydrophilicity of the surface of the molded product. The results are shown in Table 2.

For comparison, the hydrophilicity of the surface of a molded product that was not irradiated with ultrasonic waves was also investigated. The results are also shown in Table 2.

[Margins below] The heat resistance of the molded product obtained through roughening was measured in a gear oven at 190° C., and it was found to have the same heat resistance as the original molded product.

[Effects of the invention] Synthetic resin molded products modified by the method of the present invention: ■Since there is no need to use a polymerization initiator, the thermal stability of the modified molded product is good.■Films and coating agents The process is simpler than when modifying using materials such as molded products, and the copolymerized layer is less likely to peel off from the modified molded product ■Easy to mold synthetic resin gives shape, strength, etc. Since it can then be protected and added with various functions, it is possible to manufacture products with various functionalities at low cost.■It is possible to produce products with various functionalities at low cost. It has characteristics such as easy copolymerization with styrene, methyl methacrylate, etc.

April 2, 1985 1 Indication of the case 1985 Patent Application No. 720 2 Name of the invention Method for modifying synthetic resin molded products 3 Person making the amendment Relationship with the case Patent applicant Address: 3-2-4 Nakanoshima, Kita-ku, Osaka Name:
(094) Kanebuchi Chemical Industry Co., Ltd. Representative Masato Niino 4 Agent 540 5 Subject of amendment (1) Contents of amendment in column 6 of “Detailed Description of the Invention” of the specification (1) Page 3, line 19 of the specification [Polyacrinitrile]
Correct with "Polyacrylonitrile".

(2) "Polystyrene" on page 9, line 8 is corrected to "polymethacrylic acid."

(3) "Methacrylic acid" on page 11, line 12 is corrected to "methyl methacrylate."

that's all

Claims (1)

[Scope of Claims] 1. A method for modifying a synthetic resin molded article, which comprises irradiating an ultrasonic wave to a heterogeneous system in which a synthetic resin molded article and a vinyl monomer coexist. 2. The method according to claim 1, wherein the synthetic resin molded product is a polyvinyl chloride resin molded product or a polystyrene resin molded product. 3. The method according to claim 1, wherein the vinyl monomer forms a polymer having hydrophilicity, weather resistance, conductivity, or ion adsorption properties.