JPS60177061A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having small linear expansion coefficient of the molded article, high resistance to thermal deformation, excellent physical properties such as impact resistance, and extremely excellent moldability and appearance of the molded article, and suitable for rainwater guttering, etc., by compounding a vinyl chloride resin with short glass fibers, glass beads, a modifier, and a processing aid. CONSTITUTION:(A) 100pts.(wt.) of a vinyl chloride resin is compounded with (B) 5-30pts. of short glass fibers (e.g. chopped glass fibers of 0.05-3mm. long, preferably surface-treated with coupling agent), (C) 5-30pts. of glass beads (having particle diameter of 50-100mu and preferably surface-treated with a coupling agent), (D) 5-20pts. of a modifier selected from chlorinated polyethylene, ethylene-vinyl acetate copolymer, ABS and MBS, and preferably, (E) 1-5pts. of a processing aid selected from MAS and polymethyl methacrylate.

Description

[Detailed Description of the Invention] (Field of Industrial Application) The present invention is suitable for molded products with a small linear expansion coefficient and excellent physical properties and appearance, particularly thin-walled molded products such as rain gutters, decking materials, and window frames. The present invention relates to a vinyl chloride resin composition.

(Prior art) In recent years, molded products made of vinyl chloride resin, such as rain gutters made of hard vinyl chloride, have been increasingly used.
Rigid PVC rain gutters have a higher coefficient of linear expansion than metal rain gutters, and during use, changes in temperature may cause changes in longitudinal length, causing deformation or breakage at connections or fasteners. They also had the disadvantage that the parts that were directly exposed to sunlight were prone to thermal expansion and bending or waving.

Conventionally, as described in Japanese Patent Publication No. 55-30639, 100 parts by weight of a vinyl resin having a viscosity index of 50 to 180 and 10 to 10 parts of an inorganic filler whose individual particles have an average diameter of 0.05 to 50 μm are used. 60 parts by weight, 1.5 to 5 parts by weight of a lubricant, and 5 to 40 parts by weight of glass fiber with a length of 4 to 6 lengths.
Extrusion molding compositions containing 15 to 25 parts by weight of glass have been proposed, but the glass fibers are difficult to disperse uniformly in the resin, and the adhesion between the mixed glass fibers and the vinyl resin is poor. Large voids are created around the fibers, which makes the vinyl resin
The physical properties of the molded product (such as impact resistance) are significantly reduced.
In addition, moldability is not sufficient, and the surface condition of the molded product is poor, and due to this, it has the disadvantage of whitening (chalking) within a short time when used outdoors.

(Object of the present invention) In view of the above facts, as a result of intensive study, the inventor has determined that:
It was discovered that the above-mentioned conventional drawbacks can be overcome by shortening the length of the short glass fibers and adding a modifier that improves the adhesion between the short glass fibers and the resin, and the present invention has been made. The present invention has a small coefficient of linear expansion, is difficult to cause thermal deformation, has excellent physical properties such as single impact resistance, has excellent moldability, and can be molded with a smooth surface. The object of the present invention is to provide a vinyl chloride resin composition suitable for products, particularly thin-walled molded products such as rain gutters, decking materials, and window frames.

(Summary of the Invention) The summary of the present invention is as follows: 1. Vinyl chloride resin 100 ffi
4 parts by weight: 5 to 30 parts by weight of short glass fibers, 5 to 30 parts by weight of glass beads, chlorinated polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate. - A vinyl chloride resin composition containing 5 to 20 parts by weight of at least one modifier selected from butadiene-styrene copolymers (hereinafter referred to as "composition I of the present invention")
, and 2. Vinyl chloride resin 100! For Okibe,
5 to 30 parts by weight of short glass fibers and 1. glass beads 5 to 3
and at least one modification selected from chlorinated polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene copolymer. A vinyl chloride resin prepared by adding 5 to 20 parts by weight of an agent and 1 to 5 parts by weight of at least one processing aid selected from methyl methacrylate-acrylonitrile-styrene copolymer and methyl methacrylate. composition (hereinafter referred to as "composition 2J of the present invention").

(Structure of the Invention) As the vinyl chloride resin used in the composition 1.2 of the present invention, for example, polyvinyl chloride (PVC), polyvinylidene chloride, chlorinated polyvinyl chloride (chlorinated PVC), etc. are preferably used. used, especially polyvinyl chloride (PVC)
) is particularly preferably used.

Examples of short glass fibers used in compositions 1 and 2 of the present invention include chopped glass fibers in which the strands are cut into 0.05 to 3 fins (when present in the molded product), or glass fibers with a length of 0.0
Pile-shaped materials cut into 5-3 m (when present in the molded product) are preferably used, especially those with a length of 0.05-3 mm.
Glass chops that have been cut (when present in the molded product) are particularly preferably used, and those that have been surface-treated with a camplining agent such as epoxy silane are also preferably used.

As the glass beads used in the composition 1.2 of the present invention, for example, those having a particle size of 50 to 100 μ and whose surfaces have been treated with a cambling treatment agent such as epoxy silane are preferably used. .

The modifier used in Composition 1.2 of the present invention improves the adhesion between the short glass fibers and the vinyl chloride resin by being added to the system, and improves the adhesion between the short glass fibers and the vinyl chloride resin. It suppresses the voids that occur and improves the impact resistance of molded products.
Ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer (ABS) and methyl methacrylate-butadiene-styrene copolymer (MBS)
) is used.

As the processing aid used in the composition 2 of the present invention, a few (both one) selected from methyl methacrylate-acrylonitrile-styrene copolymer (MAS) and methyl methacrylate (MMA) are used. used.

In the present invention, in addition to the above, stabilizers and pigments may be used in combination as necessary.

In composition 1.2 of the present invention, short glass fibers are added to 100 parts by weight of vinyl chloride resin along with other components.
By adding 5 to 30 parts by weight, the coefficient of linear expansion of the molded product is decreased, the rigidity is increased, and the molded product is resistant to thermal deformation due to temperature changes without deteriorating moldability, impact resistance, etc. No short glass fibers are added or the amount added is 5 parts by weight per 100 parts by weight of vinyl chloride resin.
If a small amount (less than 30 parts by weight) is added, a sufficient effect cannot be expected, and if a large amount (more than 30 parts by weight) is added, moldability will be poor (and the appearance of the molded product will not be smooth). Also, impact resistance and weather resistance deteriorate.

In composition 1.2 of the present invention, 5 to 30 parts by weight of glass beads are added to 100 parts by weight of vinyl chloride resin together with other components, thereby reducing the impact resistance (47) of the molded product. Improving moldability without adding glass beads.If glass beads are not added at all or if they are added in a small amount of less than 5 parts by weight, a sufficient effect cannot be expected; if glass beads are added in a large amount exceeding 30 parts by weight, In this case, the resin is not sufficiently kneaded in the special molding machine, resulting in not only poor moldability but also poor impact resistance.

In the composition 1.2 of the present invention, 5 parts by weight of the modifier is added to 100 parts by weight of the vinyl chloride resin along with other components.
By adding 20 to 20 parts by weight, physical properties such as impact resistance and rigidity of the molded product can be improved without increasing the coefficient of linear expansion. If no modifier is added at all or only a small amount of less than 5 parts by weight is added, sufficient effects cannot be expected;
Furthermore, if a large amount exceeding 20 parts by weight is added, the coefficient of linear expansion will increase.

In Composition 2 of the present invention, the above-mentioned auxiliary agent is added to 100 parts by weight of vinyl chloride resin along with other components.
By adding 1 to 5 parts by weight, together with the modifier, the physical properties such as impact resistance and rigidity of the molded article are further improved without increasing the coefficient of linear expansion. If a processing aid is not added at all or if it is added in a small amount of less than 1 part by weight, sufficient lino-fruit cannot be expected, and if it is added in a large amount exceeding 5 parts by weight, the line of the molded product may be The expansion rate will increase.

(Effects of the Invention) The composition 1 of the present invention contains 5 to 30 parts by weight of short glass fibers, 5 to 30 parts by weight of glass beads, and 5 to 20 parts by weight of the modifier, based on 100 parts by weight of the vinyl chloride resin. Since the molded product has a small coefficient of linear expansion and is less prone to thermal deformation due to temperature changes, it also has excellent physical properties such as tensile strength and impact resistance, and has good moldability. The surface condition of the product is good and the appearance is good.

Composition 2 of the present invention contains 5 to 30 parts by weight of short glass fibers and 5 parts by weight of glass beads based on 100 parts by weight of vinyl chloride resin.
Since it is made by adding 30 to 30 parts by weight, 5 to 20 parts by weight of the modifier, and 1 to 5 parts by weight of the processing aid,
The linear expansion coefficient of the molded product is small, so thermal deformation due to temperature changes does not occur.It also has excellent physical properties such as tensile strength and impact resistance, and has extremely good moldability, and the surface condition of the molded product is smooth. It is uniform and has an extremely good appearance.

The present invention will be explained below with reference to Examples.

(Example 1-15) The formulations shown in Tables 1 to 3 (short glass fibers had a length of 2 to 5
m-, whose surface has been treated with epoxy silane)
were heated and mixed in a mixer at 120°C for 6 minutes, and this mixture was kneaded in a roll kneader for 5 minutes at 160°C to a thickness of 1.
2 Make a sheet of fins, crush this sheet and make 3
Powder and crushed pieces of Tsurukaku are made, and the crushed pieces are extruded using an extruder and a mold at a resin temperature of 180 to 185°C to a thickness of 1.2 cm.
A thin-walled heteroplastic fin was extruded.

A test piece was cut out from the molded product, and the coefficient of linear expansion, tensile strength, elongation, impact strength, and length of the short glass fibers in the molded product were measured, and the adhesion between the short glass fibers in the molded product and the resin was measured. I observed the sex. The results were used as Examples 1 to 15.
Shown in the table.

(Comparative Example 1) The formulation of Comparative Example 1 in Table 4 was thoroughly mixed in a mixer, and the mixture was passed through an extruder and mold at a resin temperature of 180 to 185.
The mixture was extruded at a temperature of 0.degree. C. to form a thin, irregularly shaped article with a thickness of 1.2 mm. A test piece was cut out from the molded product, and the coefficient of linear expansion, tensile strength, elongation and impact strength were measured. The results are shown in Table 4 as Comparative Example 1.

(Comparative Example 2) The formulation of Comparative Example 2 in Table 4 (short glass fibers have a length of 2 to
I tried molding the same material as in Comparative Example 1, but the moldability was poor and molding was not possible. Mix at room temperature, knead this mixture for 5 minutes at 190°C with a roll kneader to make a sheet with a thickness of 1.2 mm, cut out this sheet, and mix with a hand press at 190°C.
After preheating at ℃50kg10J for 2 minutes, 190℃100k
A sheet with a thickness of 1.3 fins was prepared by pressing at g/cJ for 1 minute, and a test piece was cut from this sheet and the actual h(+!
The results of measurements and observations similar to those in the example are also shown in Table 4 as Comparative Example 2.

The surface and linear expansion coefficients were measured using ASTM: D696. Tensile strength and elongation were measured according to JISA5706. Regarding impact strength, it was measured according to JISA5400. The adhesion between the short glass fibers and the resin in the molded article was determined by viewing the cross section of the test piece under an electron microscope and observing the generation of voids around the short glass fibers.

As is clear from Tables 1 to 3, Examples 1 to 3.7 to 9
, 13 to 15, the coefficient of linear expansion is small, and the physical properties such as impact resistance are improved to the extent that they are comparable to those of Comparative Example 1 in which short glass fibers are not dispersed, and the moldability is also improved. is 1
．． It was possible to mold a thin-walled molded product of 21111, and the surface condition of the molded product was also good. In addition, it was observed that the short glass fibers and the resin were in close contact with each other, with only very small voids partially visible around the short glass fibers.

As is clear from Table 1.2, Examples 4-6.10-
In all cases of No. 12, Comparative Example 1 has a small coefficient of linear expansion and physical properties such as impact resistance in which short glass fibers are not dispersed.
It has improved to the extent that it is comparable to the value of
It was possible to mold a thin-walled molded product, and the surface condition of the molded product was smooth and uniform, which was extremely good. In addition, it was observed that the short glass fibers and the resin were in close contact with each other, with only very small voids partially visible around the short glass fibers. Furthermore, the weather resistance was improved to the extent that it was comparable to that of Comparative Example 1 in which short glass fibers were not dispersed, and was extremely good.

As is clear from Table 4, Comparative Example 1 has a significantly large linear expansion coefficient and is easily deformed due to temperature changes. In the case of Comparative Example 2, the moldability was poor, making it impossible to mold a thin irregularly shaped article, and the physical properties such as impact resistance and weather resistance were so poor that they could not be put to practical use. Also, large voids were observed around the short glass fibers, and there was no close contact between the short glass fibers and the resin.

Table 1, Table 2, Table 3, 0; Can be molded into the shape of thin irregularly shaped products, and IMJf31
The surface state of the situation is the 1,000th table procedure. (Spontaneous) April 26, 1980] Mr. Commissioner of the Japan Patent Office ■, Indication of the case, 1982 Patent Application No. 33011 2, Name of the invention Vinyl Resin Composition 3, Relationship with the Amendment Person Case Patent Applicant Zip Code 530 Address Patent Department 2-4-4 Nishitenma, Kita-ku, Osaka
(06) 365-2181 Table subject to amendment (claims and detailed description of the invention column of 11 specifications)

& Contents of amendment (1) The scope of claims in the specification is amended as shown in the attached sheet.

(2) Statement #! On page 5, line 9 and page 7, lines 7-8, [
"Methyl methacrylate" should be corrected to "polymethyl methacrylate."

(3) Specification page 7, line 8, page 15, table 1 (line 8)
In Table 2 (line 8) on page 16 and Table 3 (line 7) on page 17, [MMAJ] is corrected to [PMMAJ.

(4) On page 11, line 5 of the specification, "Tension strength" There is a certain "tensile strength" and correct it.

& Attachment list + 1) At least one document stating the amended scope of the patent claims: 100 parts by weight of vinyl chloride resin, 5 to 30 Jifit parts of short glass fibers, and 5 glass beads 30 parts by weight, and at least one selected from chlorinated polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate-butadiene/-styrene copolymer. Modifier 5
20 parts by weight of a vinyl chloride resin composition.

For 100 parts by weight of vinyl dichloride resin, 5 to 30 parts by weight of short glass fibers, 5 to 30 parts by weight of glass beads,
Chlorinated polyethylene, ethylene-vinyl acetate copolymer,
At least one modifier selected from acrylonitrile-butadiene-styrene copolymer and methyl methacrylate-butadiene-styrene copolymer 5 to 2
0 parts by weight and 1 to 5 parts by weight of a processing aid of at least TFM selected from methyl methacrylate-acrylonitrile-styrene copolymer and polymethyl methacrylate.

Claims (1)

[Claims] 1. 100 parts by weight of vinyl chloride resin, 5 to 30 parts by weight of short glass fibers, 5 to 30 parts by weight of glass beads, chlorinated polyethylene, ethylene-vinyl acetate copolymer, A vinyl chloride resin composition comprising 5 to 20 parts by weight of at least one modifier selected from acrylonitrile-butadiene-styrene copolymer and methyl methacrylate-butadiene-styrene copolymer. 2. For 100 parts by weight of vinyl chloride resin, 5 to 30 parts by weight of short glass fibers, 5 to 30 parts by weight of glass beads, chlorinated polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene 5 to 20 parts by weight of at least one modifier selected from methyl methacrylate-butadiene-styrene copolymer and methyl methacrylate-butadiene-styrene copolymer; A vinyl chloride resin composition containing 1 to 5 parts by weight of at least one processing aid selected from among them.