JPS59189150A - Molding composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent compatibility and gives transparent moldings, by mixing a methyl methacrylate (co)polymer with a specified alternating chlorofluorocopolymer. CONSTITUTION:An alternating copolymer obtd. by polymerizing 100pts.wt. mixture of chlorotrifluoroethylene and 2,2,3,3-tetrafluoropropyl vinyl ether in a molar ratio of 40/60-60/40 in the presence of 0.05-5pts.wt. catalyst such as azobisisobutyronitrile and in the absence of oxygen at 0-100 deg.C, is used. A (co)polymer composed of 100pts.wt. methyl methacrylate and 0-50pts.wt. other monomer such as ethyl acrylate and said alternating copolymer are mixed together in a weight ratio of 1/9-9/1.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a molding composition containing a methyl methacrylate polymer containing methyl methacrylate as a main component.

Methyl methacrylate polymers have long been used in lighting equipment, home appliances, instrument display boards, and other products due to their excellent translucency.
It is used in many products for decorative and transparent purposes such as automobile parts and containers. However, methyl methacrylate polymers have the disadvantage that they do not have sufficient stain resistance and that their light transmittance tends to decrease due to stains.

Various studies have been conducted to improve the stain resistance and lower the refractive index while maintaining the excellent translucency of the methyl methacrylate polymer. No other method has been found other than using vinylidene chloride resin.

The present inventors have conducted extensive research to solve the above-mentioned drawbacks, and have found that chlorotrifluoroethylene and 2.2, 3.3
- By using a molding composition containing an alternating copolymer with tetrafluoropropyl vinyl ether and a methyl methacrylate polymer containing methyl methacrylate as a main component (hereinafter referred to as the methyl methacrylate polymer used in the present invention), the above-mentioned conditions can be obtained. The inventors have discovered that the drawbacks can be overcome and have completed the present invention.

That is, in the present invention, by using the above-mentioned alternating copolymer as one component of the molding composition, coating films, films, molded articles, etc. produced using the composition have excellent stain resistance and light transmittance, and have low It has the remarkable effect of having a high refractive index and excellent workability during the production of coatings, films, molded articles, etc.

The alternating copolymer of the present invention is a copolymer made from chlorotrifluoroethylene and 2,2,3,3-tetrafluoropropyl vinyl ether, and is
(hereinafter referred to as DSO) glass transition temperature of approximately 63°C
1 Thermal decomposition temperature (weight loss start temperature) approximately 266°0, refractive index (
nD) about 1.400, critical surface tension about 25 ayn/cm
It has a light transmittance of about 93.5% in the wavelength range of 400 to 800 parts m for a sheet of % thickness imm. This alternating copolymer is a non-grade polymer, has excellent translucency and is transparent, and can be used in solvents in which the methyl methacrylate polymer is dissolved, such as methyl ethyl ketone, acetone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, and phtyl acetate. It dissolves in solvents such as , ethyl cellosolve, dimethylformamide, dimethylacetamide, and other ketones and esters.

The alternating copolymer of the present invention contains chlorotrifluoroethylene and 2.2,3.3-tetrafluoropropyl vinyl ether in a molar ratio of 40,760 to 60/40, preferably 4
5155 to 55/45 and polymerization in the absence of 0 to 100°01 oxygen. A solvent may be used in the polymerization reaction, and preferred solvents include trichlorotrifluoroethane, 1,1,2.2-tetrachloro-1,2-difluoroethane, methyl ethyl ketone, ethyl acetate, etc. that dissolve the alternating copolymer. can give.

The amount of solvent used varies depending on the type, but is usually 1 part by weight (parts by weight, same hereinafter) of this alternating copolymer.
00 to 400 parts is preferable. Also used in the polymerization reaction are commonly used polymerization catalysts such as azobisisobutyronitrile, diimpropyl peroxydicarbonate, isobutyol peroxide, benzoyl peroxide, tert-butyl peroxyisobutyrate, and the like. The amount of polymerization catalyst used is preferably 0.05 to 5 parts per 100 parts of the alternating copolymer. The alternating copolymer of the present invention may contain a third comonomer component within a range that does not significantly change its properties, and such comonomers include alkyl vinyl ether, Fluoroal bovine rubinyl ether (2,2,3,3
- Tetrafluoropropyl vinyl ether (<), etc.

The methyl methacrylate polymer used in the present invention is a homopolymer of methyl methacrylate or a copolymerizable monomer of methyl methacrylate and other monomers, such as ethyl methacrylate, methyl acrylate, ethyl acrylate, and other methacrylic esters and acrylic esters. It includes copolymers with etc. The content of these other copolymerizable monomer components is 0 to 50 parts, preferably 0 to 30 parts, based on 100 parts of methyl methacrylate.

The mixing ratio of the alternating copolymer of the present invention and the methyl methacrylate polymer used in the present invention is 179 to 9/1 by weight;
Preferably it is 377 to 7/3.

When the amount of this alternating copolymer decreases, the critical surface tension, which is a measure of stain resistance, of coating films, films, molded articles, etc. produced using the molding composition of the present invention increases, and the translucency also decreases. However, if the blending ratio is less than 179, the effect of using the alternating copolymer of the present invention cannot be improved. On the other hand, when the amount of this alternating copolymer increases, the glass transition temperature of coating films, films, molded articles, etc. produced using the molding composition of the present invention becomes low, and when the blending ratio exceeds 971, it is difficult to Undesirable.

The compatibility between the alternating copolymer of the present invention and the methyl methacrylate polymer used in the present invention is particularly good, resulting in a transparent molding composition.

That is, one component of this alternating copolymer, 2.2,
3. Copolymers in which 3-tetrafluoropropyl vinyl ether is replaced with other similar components, such as alternating copolymers of chlorotrifluoroethylene and hydrocarbon vinyl ethers such as methyl vinyl ether or butyl vinyl ether, are methyl methacrylate polymers. The compositions are cloudy due to their poor compatibility. Chlorotrifluoroethylene and 2.2,3,3,4,4,5.5-octafluoropentyl vinyl ether or 2°2.3,
Alternating copolymers with fluorine-containing vinyl ethers other than 2,2,3,3-tetrafluoropropyl vinyl ether such as 3,4,4,5,5,6,6,7,7-dozocafluorohebutyl vinyl ether are also applicable. Compatibility with the methyl methacrylate polymer used in the invention is poor, and their compositions also become cloudy. In contrast, the molding compositions of the present invention are transparent and specific.

The refractive index of the methyl methacrylate polymer used in the present invention is about 1.490, and the refractive index of the alternating copolymer of the present invention is about 1.
．． 400, and the difference is about 0.090. Approximately 0.
．． The difference in refractive index of 090 is comparable to the difference between the core material and sheath material of an optical fiber. Despite the large difference in refractive index, the molding composition of the present invention is transparent, and from this point as well, it can be seen that the molding composition is unique.

The molding composition of the present invention is prepared by mixing a solution of the alternating copolymer of the present invention with a solution of the methyl methacrylate polymer used in the present invention, or by hot rolling the alternating copolymer and the methyl methacrylate polymer used in the present invention. It can be obtained by a method such as kneading.

The molding composition of the present invention can be used for stain-resistant paints, sheath materials for optical fibers that utilize the difference in refractive index, etc. Objects have excellent translucency.

Next, the composition of the present invention will be explained in detail with reference to Production Examples, Examples, Comparative Production Examples, and Comparative Examples.

Production example 1 1000 ml! A glass autoclave was charged with 350 ml of ion-exchanged water and 1 g of sodium carbonate, and after the space was sufficiently replaced with nitrogen gas to remove oxygen, 180 ml of trichlorotrifluoroethane was charged, and then 2, 2, 3.3 - 34.5 g of tetrafluoropropyl vinyl ether, 25 g of chlorotrifluoroethylene.
I prepared 4y. Heat the mixture with stirring to 65
After heating at °ay, azobisisobutyronitrile 0.
3 g was added and polymerized at the same temperature for 8 hours. The pressure at the start of polymerization was 2.1' kg/am G, and the pressure when polymerization was carried out for 8 hours was 0.2 kg/cm G.

The polymer was dissolved in trichlorotrifluoroethane, and this solution was added to petroleum ether with stirring to cause reprecipitation. The polymer was then dried under reduced pressure and
．． A colorless and transparent polymer was obtained.

The obtained monopolymer was subjected to elemental analysis S and FNMR analysis. From the results of elemental analysis, the molar specific force between chlorotrifluoroethylene and 2.2.3.3-tetrafluoroethylene was 1/1, and from the results of NMR analysis, the bonds between vinyl ether units and between chlorotrifluoroethylene units were determined. It turned out to be an alternating copolymer in which substantially no copolymer was present. In addition, this alternating copolymer has a thermal decomposition temperature (temperature at which weight loss starts in air at a heating rate of 10'o/min) of 263°a, and a glass transition temperature of :osa (temperature at which temperature increases at a heating rate of 10°C and 7 min at 33°C1). Refractive index (
Relaxation) 1.40 [1, critical surface tension 25 ayn/am
It has a light transmittance of 96.5% in the wavelength range of 400 to soo nm for a sheet with a thickness of i mm, and is dissolved in methyl ethyl ketone and trichlorotrifluoroethane.

Elemental analysis value; Actual value (%): o 30.6 al! 12.8
F 48.5 critical surface tension is determined by making the alternating copolymer into a methyl ethyl ketone solution, applying it on an aluminum plate to form a coating film, and thoroughly drying the solvent in the film in a vacuum for 4 days. The contact angle was measured using 2D00, and the critical surface tension was determined using Zisman plot.

The light transmittance was measured by kneading the alternating copolymer with a hot roll, producing a 1 mm thick film using a hot press at 200°0, and using a self-recording spectrophotometer manufactured by Hitachi, Ltd.

Production example 2 300 m+A! 47g of methyl methacrylate, 13f of ethyl methacrylate in a 4-glass flask,
60 g of methyl ethyl ketone as a solvent, 1.2 f of stearyl mercaptan as a chain transfer agent and heavy, 70°
It was heated to C. Polymerization was carried out at the same temperature for 7 hours, and the concentration was 48% (
A viscous polymer solution was obtained. The intrinsic viscosity [η] of the obtained polymer at 35°0 in methyl ethyl ketone is o, i6o (inches/9), the glass transition temperature is 7000, and the critical surface tension is 4 by the same method as in Production Example 1.
3 dyn/am Examples 1 to 5 The alternating copolymer of the present invention obtained in Production Example 1 was dissolved in methyl ethyl ketone to prepare a 20% solution. Also, production example 2
The resulting methyl methacrylate polymer solution used in the present invention was diluted with methyl ethyl ketone to prepare a 20% solution.

The above two types of solutions were mixed in the proportions shown in Table 1, and their compatibility was visually observed. Production example 1 using the obtained mixture
A coating film was prepared in the same manner as above, and the transparency of the coating film was observed with the naked eye. Further, the glass transition temperature and critical surface tension were measured in the same manner as in Production Example 1. The results are shown in Table 1.

In Table 1, O indicates good transparency, and × indicates poor transparency (white turbidity or two-phase separation).

Examples 6 to 10 The alternating copolymer of the present invention obtained in Production Example 1 and the commercially available Acrypera MP manufactured by Mitsubishi Rayon ■ were mixed in the proportions shown in Table 2, and heated on a hot roll at 160°C. After thorough kneading, a film was produced in the same manner as in Production Example 1, and the light transmittance was measured. The results are shown in Table 2.

Comparative Production Examples 1 to 7 The same molar amount of vinyl ether shown in Table 1 was used in place of 2,2,3.3-tetrafluoropropyl vinyl ether used in Production Example 1, and the same procedure was repeated as in Production Example 1. A polymer was prepared.

Comparative Examples 1 to 7 20 of the methyl methacrylate polymer obtained in Production Example 2
% methyl ethyl ketone solution and each of the 20% methyl ethyl ketone solutions of the alternating copolymers obtained in Comparative Production Examples 1 to 7 were mixed in the proportions shown in Table 1, and the mixture was evaluated for transparency and The transparency of the coating film produced using the mixture was measured. The results are shown in Table 1.

Procedural Amendment (Voluntary) November 28, 1980 Commissioner of the Patent Office Kazuo Wakasugi Representation of Case 1 1982 Patent Application No. 65iB '2 Name of Invention Molding Composition 3 Amendment to Case Related Patent Applicant Address New Hankyu Building, 1-12-69 Umeda, Kita-ku, Osaka Name (285) Representative of Daikin Industries, Ltd.
Mountain 1) Minoru 4 Agent 〒540 5 Subject of amendment (1) Contents of amendment in column 6 of “-Detailed description of the invention” of the specification (1) Contacted at 120°0 on page 10 lines 17-18 of the specification The angle is corrected as [contact angles of water, glycerin, diethylene glycol, methylene diiodide, and tetrachloroethylene at 20°0 using a contact angle measuring device manufactured by Kyowa Kagaku Co., Ltd.].

(2) 14 Due east 1 table glass transition #temperature (00)
' 56 40 743 45 in the column is corrected to 45.

347 that's all

Claims (1)

[Claims] 1. It is characterized by containing an alternating copolymer of chlorotrifluoroethylene and 2,2,3,3-tetrafluoropropyl vinyl ether and a methyl methacrylate polymer whose main component is methyl methacrylate. Molding composition. 2. Claims in which the alternating copolymer and the methyl methacrylate polymer are in a weight ratio of 179 to 9/1.
Composition according to item 1.