JPH0222352A - Method for producing vinylidene fluoride resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition capable of blending pigment and filler at large amounts without promoting thermal decomposition by blending a vinylidene fluoride with an acrylic resin, pigment and/or filler. CONSTITUTION:The aimed composition obtained by blending 100 pts.wt. vinylidene fluoride with 0. 5-50 pts.wt. acrylic resin and 10-50 pts.wt. pigment and/or filler capable of promoting thermal decomposition of vinylidene fluoride.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a vinylidene fluoride resin composition, and more particularly to a vinylidene fluoride resin composition containing a relatively large amount of pigment and/or filler.

(Prior art) Conventionally, vinylidene fluoride resin has a relatively low molding temperature of 200 to 260°C among fluorine-based resins, which is close to the molding temperature of general-purpose plastics, so it has excellent moldability and has been used in various applications. It started to happen.

When molding these vinylidene fluoride resins, they are colored depending on the purpose of use, and various fillers such as glass fibers are blended. For example, when blending colorants,
In many cases, a masterbatch is prepared by blending a colorant at a higher concentration than the final concentration of the molded article, and this masterbatch is used for final coloring. A similar masterbatch method may also be used in blending various inorganic fillers.

(Problems to be Solved by the Invention) In the masterbatch method as described above, depending on the type of pigment and/or filler, these additives may be mixed with the vinylidene fluoride resin and the pigment and/or filler. It may accelerate thermal decomposition of vinylidene fluoride resin.

For example, in the case of pigments such as titanium oxide and cobalt oxide blue, and silicon-containing fillers such as glass fiber, these pigments and/or fillers are melted at a ratio of 10 parts by weight or more per 100 parts by weight of vinylidene fluoride resin. When kneaded, the vinylidene fluoride resin is rapidly decomposed and a satisfactory high concentration product cannot be obtained.

Accordingly, an object of the present invention is to provide a vinylidene fluoride resin composition containing a high concentration of pigments and/or fillers that may promote thermal decomposition of the vinylidene fluoride resin.

(Means for solving problems) The above objects are achieved by the present invention as described below.

That is, the present invention provides 0.5 to 50 parts by weight of an acrylic resin per 100 parts by weight of vinylidene fluoride resin and 1 part of a pigment and/or filler that promotes thermal decomposition of the vinylidene fluoride resin.
A vinylidene fluoride resin composition containing 0 to 50 parts by weight.

(Function) When blending pigments and/or fillers that may accelerate the thermal decomposition of vinylidene fluoride resin with vinylidene fluoride resin, the vinylidene fluoride resin is decomposed by using acrylic resin together. Pigments and/or fillers can be blended in high concentrations without any problems.

(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments.

The vinylidene fluoride resin used in the present invention is a fluorine-based resin known per se, including Kynar (Pennwald),
It is commercially available under the trade name of KF Polymer (Kureha Chemical Co., Ltd.), and any known vinylidene fluoride resin can be used in the present invention.

The pigment and/or filler added to the vinylidene fluoride resin has a tendency to promote thermal decomposition of the vinylidene fluoride resin.For example, the pigments include titanium oxide white, titanium oxide yellow, cobalt oxide blue, etc. Examples of the inorganic filler include glass fiber,
Examples include glass beads and silicon oxide. These pigments and/or fillers can be used individually or as a mixture.

When the above pigments and/or fillers are mixed in a small proportion, for example, when the amount is less than 10 parts by weight per 100 parts by weight of vinylidene fluoride resin, the effect of promoting thermal decomposition of vinylidene fluoride resin is not significant. However, if the blending amount of these pigments and/or fillers exceeds 10 parts by weight per 100 parts by weight of vinylidene fluoride resin, the vinylidene fluoride resin will be violently thermally decomposed during melt-kneading for compounding, and conventionally It has been difficult to provide concentrated compounds.

In the present invention, when blending pigments and/or fillers in a high concentration with vinylidene fluoride resin, by using an acrylic resin together during melt-kneading, the vinylidene fluoride resin can be absorbed by the pigments and/or fillers. It has been found that thermal decomposition can be significantly suppressed.

As such acrylic resin, any conventionally known acrylic resin can be used, but particularly preferred acrylic resins are available from the market under trade names such as Dianal, Metablane (Mitsubishi Rayon), and Paraloid (Kureha Chemical). Available methacrylic resins are preferred. It is preferable to use these acrylic resins in a proportion of 0.5 to 50 parts by weight per 100 parts by weight of vinylidene fluoride resin.If the amount used is less than this range, the effect of use will be insufficient. If the amount used exceeds the amount, the original performance of the vinylidene fluoride resin will deteriorate, which is not preferable.

The vinylidene fluoride resin of the present invention has the above-mentioned components as essential components, but may also contain other known additives such as other pigments, other fillers, plasticizers, lubricants, stabilizers, etc. within the range that does not interfere with the purpose of the present invention. Of course, they can be combined.

The vinylidene fluoride resin composition of the present invention can be obtained by simply mixing the above-mentioned components or by melt-kneading them at the same time, but a particularly preferred method is as follows: It is preferable to melt and knead the pigment and/or filler particles in advance so that the pigment and/or filler particles are sufficiently coated with the acrylic resin, and then mix this with the vinylidene fluoride resin, which more preferably achieves the object of the present invention. be done.

(Example) Next, the present invention will be explained in more detail by giving examples and comparative examples. In the text, parts or percentages are based on weight unless otherwise specified.

Example 1 Methacrylic resin (Dyanal BR resin, manufactured by Mitsubishi Rayon) 40 parts Titanium oxide (R-
820, manufactured by Ishihara Sangyo) 60 parts The above-mentioned material was melted and kneaded for 5 minutes in a Pan Bali mixer (70! capacity), then rolled with two 18-inch rolls to form a sheet, and this was made into a 4X4X4ma+ with a pelletizer. It was granulated into square pellets. This square pellet is crushed with a turbo mill crusher,
It was made into a granular coloring agent of 20 to 30 meshes.

This coloring agent was added at a ratio of 50 parts to 100 parts of vinylidene fluoride resin (Kynar 721, manufactured by Pennwalt) and mixed uniformly with a Henschel mixer. The vinylidene fluoride resin composition of the present invention was kneaded and extruded using a 45 parts mm twin-screw extruder set at 230° C. to obtain a pellet-shaped vinylidene fluoride resin composition of the present invention with excellent pigment dispersibility, a smooth surface, and vivid color development.

Example 2 50 parts of the acrylic resin in Example 1 and cobalt oxide blue (#1024, manufactured by Asahi Sangyo) 5 as a pigment.
Pigment dispersibility,
A pellet-shaped vinylidene fluoride resin composition of the present invention having excellent surface condition and color development was obtained.

Example 3 100 parts of vinylidene fluoride resin (Kynar 721) 20 parts of methacrylic resin (Dianallo R Resin) 30 parts of titanium oxide (R-820') After uniformly mixing the above tableware with a Henschel mixer, part of the cylinder A pellet-shaped vinylidene fluoride resin composition of the present invention was obtained by kneading and extrusion using a twin-screw extrusion machine with a temperature of 210°C to 210°C and a die part set to 230°C.

Example 4 In Example 3, the vinylidene fluoride resin composition of the present invention was prepared in the same manner as in Example 3, except that 25 parts of Diernal BR resin and 25 parts of cobalt oxide blue (#1024) were used as the pigment. Obtained.

Comparative Example 1 100 parts of vinylidene fluoride resin (Kynar 721) 30 parts of titanium oxide (R-820) The above ingredients were mixed uniformly in a Henschel mixer, and then molded in a twin-screw extrusion molding machine under exactly the same conditions as in Example 1. A pellet-shaped vinylidene fluoride resin composition of a comparative example was obtained.

The appearance of this pellet was a little foamy, and the coloring on the surface was unclear.

Furthermore, 5 minutes after starting the extruder operation, a foaming phenomenon accompanied by an odor was observed from the die, so the rapid operation was stopped. Comparative Example 2: 125 parts of vinylidene fluoride resin (Kynar 721), 25 parts of cobalt oxide blue (#1024), using the first Jul as a sample. A pellet-shaped vinylidene fluoride resin composition of a comparative example was obtained using a twin-screw extrusion molding machine under the following conditions.

The appearance of this pellet was a little foamy, and the coloring on the surface was unclear.

Furthermore, 5 minutes after starting the extruder operation, a foaming phenomenon accompanied by an odor was observed from the die, so the rapid operation was stopped. The initial version was used as a sample.

50 mg of each of the vinylidene fluoride resin compositions of the above Examples and Comparative Examples were sandwiched between two glass slides and heated to 280°C.
The film was rolled to a thickness of about 50 μm on a hot plate, and the state of the film after heating for 20 minutes was examined, and the results shown in Table 1 below were obtained.

Example 1: Retains clear white color.

Example 2: Maintains clear blue color.

Example 3: There was a slight change in yellowish white color.

Example 4: There was a slight change in the dull blue color.

Comparative Example 1: Turned black and gray and foamed.

Comparative Example 2: The color changed to black-blue and foamed.

Example 5 Acrylic resin (Balaroid K, manufactured by Kureha Chemical Co., Ltd.)
40 parts titanium oxide (C11-60,
(manufactured by Ishihara Sangyo) 60 parts The above blend was kneaded in a Banbury mixer in the same manner as in Example 1, and then ground to obtain a granular colorant.

Vinylidene fluoride resin (F Polymer #100O, manufactured by Kureha Chemical Co., Ltd.) 100 parts The above granular colorant 100 parts Lubricant (calcium stearate) 0.2 parts The above formulation was mixed uniformly with a Henschel mixer, and the temperature was set at 170°C. The mixture was kneaded for 5 minutes using two 10-inch mixing rolls with a clearance of 1 dragon, heated for 3 minutes in a press set at 230°C, and then kneaded at 150°C.
A pressure of g/cm was applied to obtain a sheet-like vinylidene fluoride resin composition of the present invention with a thickness of 0.5 mm and a vivid color.

Comparative Example 3 Vinylidene fluoride resin (F polymer #1000) 140
Part titanium oxide ((:R-60) 60 parts Lubricant (calcium stearate) 0.2 parts The above formulation was mixed uniformly with a Henschel mixer under the same conditions as in Example 5, and kneading with a mixing roll and press molding were attempted. However, during the mixing process described above, yellowish discoloration occurred, and a phenomenon of deterioration of peelability from the roll surface also occurred.Furthermore, the hue of the sheet after pressing was significantly inferior to that of Example 5. .

Example 6 Acrylic resin (Metablen P, manufactured by Mitsubishi Rayon)
60 parts glass fiber (C5-
06-M8-411, manufactured by Asahi Fiberglass)
200 cylinders of 40 parts of the above formulation
The mixture was kneaded in a 45φmm twin-screw extrusion machine set at 220° C. to obtain a pellet-shaped glass fiber masterbatch.

100 parts of vinylidene fluoride resin (Kynar 740) 100 parts of the above glass fiber masterbatch The above mixture was extruded using a 30φml 11 single-screw extruder with a cylinder set at 230°C and a die at 250°C to obtain a uniform appearance. A pellet-shaped vinylidene fluoride resin composition of the present invention was obtained.

Comparative Example 4 Vinylidene fluoride resin (Kynar 740) 160 parts Glass fiber (C5-06-M8-411)
40 parts of the above mixture was heated in a cylinder at 230°C and in a die at 25°C.
When we attempted kneading and granulation using a 30φmff1 single-screw extruder set at 0°C, the resin temperature rose rapidly immediately after the start of extrusion, and a foamed mixture with an odor was extruded from the die hole. , suddenly stopped J extrusion, and the pellet was 11
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(Effect) According to the present invention as described above, pigments and/or fillers that may accelerate the thermal decomposition of the vinylidene fluoride resin are added to the vinylidene fluoride resin without causing the vinylidene fluoride resin to thermally decompose. can be blended in a relatively large amount without thermally decomposing the vinylidene fluoride resin. Therefore, the vinylidene fluoride resin composition of the present invention is useful as a masterbatch for coloring vinylidene fluoride resin or as a molding material.

Claims (1)

[Claims] Acrylic resin 0 per 100 parts by weight of vinylidene fluoride resin
．． A vinylidene fluoride resin composition comprising 5 to 50 parts by weight of a pigment and/or filler that promotes thermal decomposition of the vinylidene fluoride resin.