JPS60177062A - 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, extremely excellent moldability and good appearance of the molded article, and suitable for rainwater guttering, etc., by compounding a vinyl chloride resin with short glass fibers, a thermosetting resin, 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) 10-50pts. of a thermosetting resin (e.g. polyester resin), (D) 5-30pts. of glass beads (having particle diameter of 50-100mu and preferably surface-treated with a coupling agent), (E) 5-20pts. of a modifier selected from chlorinated polyethylene, ethylene-vinyl acetate copolymer, ABS and MBS, and preferably, (F) 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, vinyl resin 100 with a viscosity index of 50 to 180 has been used.
parts by weight, 10 to 60 parts by weight of an inorganic filler whose individual particles have an average diameter of 0.05 to 50μ, and 1.5 to 5 parts by weight of a lubricant.
Extrusion molding compositions have been proposed having 5 to 40 parts by weight of glass fibers of 4 to 6 lengths, and 5 to 25 parts by weight of glass beads, but the glass fibers are uniformly dispersed in the resin. Also, the adhesion between the mixed glass fiber and the vinyl resin is poor, creating large voids around the glass fiber, which causes the molded product to be weaker than the vinyl resin before the glass fiber is added. Physical properties such as impact resistance deteriorate significantly,
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:
By minimizing the length of the short glass fibers and adding a thermoplastic resin and a modifier that improve the adhesion between the short glass fibers and the resin, the above-mentioned conventional drawbacks can be overcome. This discovery led to the creation of the present invention, which has a small coefficient of linear expansion, is less prone to thermal deformation, has excellent physical properties such as impact resistance, and has excellent moldability.
The object of the present invention is to provide a vinyl chloride resin composition suitable for molded products with good surface conditions, particularly thin molded products such as rain gutters, deck sheds, and window frames.

(Summary of the Invention) The summary of the present invention is as follows: 1. For 100 parts by weight of vinyl chloride resin, 5 to 30 parts by weight of short glass fibers, 10 to 50 parts by weight of thermosetting resin, 5 to 30 parts by weight of glass beads, chlorinated polyethylene, ethylene-vinyl acetate, etc. A vinyl chloride resin prepared by adding 5 to 20 parts by weight of at least one modifier selected from acrylonitrile-butadiene-styrene copolymer and methyl methacrylate-butadiene-styrene copolymer. composition (hereinafter referred to as "composition I of the present invention"); and 2. 5 to 30 parts by weight of short glass fibers, 10 to 50 parts by weight of thermosetting resin, and 100 parts by weight of vinyl chloride resin; 5 to 30 parts by weight of beads, chlorinated polyethylene, ethylene
Vinyl acetate copolymer, acrylonitrile-butadiene-
5 to 20 parts by weight of at least one modifier selected from styrene copolymer and methyl methacrylate-butadiene-styrene copolymer, and methyl methacrylate-acrylonitrile-styrene copolymer and methyl methacrylate. 1 to 5 parts by weight of at least one processing aid selected from the following.

(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. Polyvinyl chloride (PVC) is particularly preferably used.

The short glass fibers used in composition 1.2 of the present invention are °ζ
For example, glass chops in which the strands are cut into lengths of 0.05 to 3 mm (when present in the molded product), and
A pile-shaped material cut at 0.05 to 3 S (when present in the molded product) is preferably used, especially one with a length of 0.05 to 3
Glass chops cut into diamonds (when present in the molded product) are particularly preferably used, and those whose surface has been surface-treated with a compacting agent such as epoxy silane are also suitably used.

As the thermosetting resin used in the composition 1.2 of the present invention, for example, polyester resin, epoxy resin, phenol resin, etc. are 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 100μ and whose surfaces have been treated with a coupling 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 caused by molding and improves the impact strength etc. of molded products.
Ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer (ABS) and methyl methacrylate-butadiene-styrene copolymer (MBS)
) is used.

The processing aid used in the composition 2 of the present invention is at least one selected from methyl methacrylate-acrylonitrile-styrene copolymer (MAS) and methyl methacrylate (MMA). Ru.

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

In compositions 1 and 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 only 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 deteriorate and the appearance of the molded product will not be smooth. Moreover, impact resistance and weather resistance deteriorate.

In the present invention 1.2, by adding 10 to 50 parts by weight of thermosetting resin to 100 parts by weight of vinyl chloride resin together with other components, molded products can be produced without increasing the coefficient of linear expansion. Improve physical properties such as impact resistance and rigidity. If the thermosetting resin is not added at all or if it is added in a small amount (less than 10 parts by weight), a sufficient effect cannot be expected, and if it is added in a large amount exceeding 50 parts by weight, the coefficient of linear expansion will decrease. 6 In the present invention 1.2, by adding 5 to 30 parts by weight of glass beads to 100 parts by weight of vinyl chloride resin, the 1-hour impact resistance of the molded product can be improved. To improve moldability without making it worse. No glass beads added or 5
If only a small amount (less than 30 parts by weight) is added, a sufficient effect cannot be expected; if a large amount (more than 30 parts by weight) is added, the resin will not be kneaded sufficiently in the special molding machine.
Not only does the moldability become inefficient, but also the impact resistance deteriorates.

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, by adding 1 to 5 parts by weight of the processing aid to 100 parts by weight of the vinyl chloride resin, the processing aid can be modified without increasing the coefficient of linear expansion. Together with the agent, it further improves the physical properties of molded products, such as impact resistance and rigidity. If the processing aid is not added at all or if it is added in a small amount of less than 1 part by weight, sufficient effects cannot be expected, and if it is added in a large amount exceeding 5 parts by weight, linear expansion of the molded product may occur. The ratio becomes large.

Composition 1 of the present invention contains 5 to 30 parts by weight of short glass fibers, 10 to 50 parts by weight of thermosetting resin, and 5 to 30 parts by weight of glass beads, based on 100 parts by weight of vinyl chloride resin.
Since 5 to 20 parts by weight of the above-mentioned modifier is added, the linear expansion coefficient of the molded product is small and thermal deformation due to temperature changes occurs, and the physical properties such as tensile strength and impact resistance are It has excellent moldability, has a good surface condition, and has a good appearance.

Composition 2 of the present invention contains 5 to 30 parts by weight of short glass fibers, 10 to 50 parts by weight of thermosetting resin, 5 to 30 parts by weight of glass beads, and 100 parts by weight of vinyl chloride resin. Since it is made by adding 5 to 20 parts by weight of the modifier and 1 to 5 parts by weight of the processing aid, the coefficient of linear expansion of the molded product is small and thermal deformation due to temperature changes is less likely to occur. It has excellent physical properties such as tensile strength and impact resistance, and has extremely good moldability, and the molded product has a smooth surface and good appearance.

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

(Examples 1 to 12) The formulations shown in Table 1.2 (short glass fibers had lengths of 2 to 5
(Tsuru, the surface of which was treated with epoxy silane) was heated and mixed in a mixer at 120°C for 6 minutes, and this mixture was kneaded in a roll mixer at 160°C for 5 minutes to obtain a thickness of 1.2 cm.
Make a sheet of irises, crush this sheet, and
Pellet of fin angle is made, and this pellet is extruded with an extruder and mold at a resin temperature of 180 to 185°C to a thickness of 1°2.
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 are referred to as Example 1-12, and Section 1.2
Shown in the table.

(Comparative Example 1) The formulation of Comparative Example 1 in Table 3 was well mixed in a mixture, and the mixture was heated in an extruder and mold at a resin temperature of 180 to 185.
The mixture was extruded at a temperature of 0.degree. C. to obtain a thin, irregularly shaped article having a thickness of 1.2 mm. The test piece was cut out and its linear expansion coefficient, tensile strength, elongation, thermal shrinkage rate, and f6 resistance were measured. The results are shown in Table 3 as Comparative Example 1.

(Comparative Example 2) The formulation of Comparative Example 2 in Table 3 (short glass fibers were
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+n, cut out this sheet, and mix with a hand press at 190°C.
After preheating for 2 minutes at ℃50kg/c+il, 190℃100
A sheet with a thickness of 1.3 mm was produced by pressing at kg/ci for 1 minute, and a test piece was cut out from this sheet and measured and observed in the same manner as in the example. The results were used as comparative example 2 and 3.
It is also shown in the table.

The coefficient of linear expansion was measured in accordance with ASTM:0696. Tensile strength and elongation were measured according to JISA5706. The impact strength 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 Table 1.2, Examples 1 to 3.7 to 9
In all cases, 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 formability is 1.2s+a. It was possible to form a thin-walled molded product, 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 4-6.1θ-
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 was possible to mold a thin-walled molded product with a moldability of 1 Jmm, 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.

As is clear from Table 3 (Comparative Example 1 has a significantly large coefficient of linear expansion and is easily deformed due to temperature changes, Comparative Example 2 has poor formability and is difficult to form into thin-walled irregularly shaped shapes). The product could not be molded, and its physical properties such as impact resistance and weather resistance were so poor that it could not be used for practical purposes. Also, there were large voids around the short glass fibers, and the relationship between the short glass fibers and the resin was poor. There was close contact between them.

-jE on Table 1, Table 2, Table 3? -1ff official document (spontaneous) April 26, 1980, Commissioner of the Japan Patent Office 1, Indication of the case, Patent Application No. 33012 of 1982, 2, Title of the invention: Vinyl chloride resin composition 3, Person making the amendment, and Relationship Patent applicant postal code 530 Address Patent Department 2-4-4 Nishitenma, Kita-ku, Osaka
(06) 365-2181 Subject of this amendment (1) The scope of claims and detailed description of the invention in the specification.

5. Contents of the amendment (1) The claims of the specification will be amended as shown in the attached sheet.

(2) Specification IF, page 5 # (in line ¥12 and lines 6 to l!c5 from the bottom of page 7, "methyl methacrylate" is corrected to "polymethyl methacrylate".

(3) In the specification, page 7, line 5 from the bottom, page 16, table 1 (line 9), and page 17, table 2 (line 9), replace “MMAJ” with “PMMA”. to correct.

(4 Specification, page 12, line 2, "Tension strength" There is a certain "Resistance tension" and correct it.

6 List of attached documents + 11 One or more documents stating the amended scope of claims Claims: 100 parts by weight of vinyl chloride resin, 5 to 30 overlapping parts of short glass fibers FA, and thermosetting Resin 10 to 50
M parts, 5 to 30 parts by weight of glass beads, and chlorinated polymethyl/, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene copolymer. A vinyl chloride-based m-fat composition comprising 5 to 203 parts of at least one selected modifier.

For 100Ji parts of vinyl dichloride resin, short glass fibers M15 to 30F [Jfk part, thermosetting fat 10 to 50M parts, glass beads 5 to 30 parts by weight, chlorinated polyethylene, ethylene- 5 to 20 parts by weight of at least one modifier selected from vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer and methyl methacrylate-butadiene-styrene copolymer, and methyl methacrylate- At least 1 m of processing aid selected from acrylonitrile-styrene copolymer and polymethyl methacrylate 1 to 5 ftf
A vinyl chloride resin composition obtained by adding fk part.

Claims (1)

[Claims] 1. For 100 parts by weight of vinyl chloride resin, 5 to 30 parts by weight of short glass fibers, 10 to 50 parts by weight of thermosetting resin, 5 to 30 parts by weight of glass beads, and chlorine. 5 to 20 parts by weight of at least one modifier selected from polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene copolymer; A vinyl chloride resin composition. 2. For 100 parts by weight of vinyl chloride resin, 5 to 30 parts by weight of short glass fibers, 10 to 50 parts by weight of thermosetting resin, 5 to 30 parts by weight of glass beads, chlorinated polyethylene, ethylene-acetic acid 5 to 20 parts by weight of at least one modifier selected from vinyl copolymer, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene copolymer, and methyl methacrylate-acrylic A vinyl chloride resin composition comprising 1 to 5 parts by weight of at least one processing aid selected from a nitrile-styrene copolymer and methyl methacrylate.