JPS60177057A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having small linear expansion coefficient, high resistance to thermal deformation, excellent physical properties such as impact resistance, and extremely excellent moldability, giving a molded article having good surface state, and suitable for rainwater guttering, etc., by compounding a vinyl chloride resin with short glass fibers, a thermosetting resin, 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) 5-20pts. 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 coefficient of linear expansion and excellent physical properties and appearance, particularly thin-walled molded products such as rain gutters, deck + A, window frames, etc. 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 when used, the longitudinal length changes due to changes in temperature, causing deformation or breakage at 91% of the connections or fasteners. The drawbacks were that the parts directly exposed to solar radiation were prone to thermal expansion and bending or waving.

Therefore, conventionally, as described in Japanese Patent Publication No. 53/21891, 61 resin 10
0 vehicle weight part and the average diameter of individual particles is 0.05 to 50μ
10 to 60 parts by weight of an inorganic filler, and 1.5 to 60 parts by weight of a lubricant.
Extrusion molding compositions have been proposed having 5 parts by weight and 5 to 40 parts by weight of glass fibers of 4 to 6 lengths; The adhesion between the glass fiber and the vinyl resin is poor, and large voids occur around the glass fiber, resulting in poor physical properties such as impact resistance of the molded product compared to the vinyl resin before the glass fiber was added. In addition, the moldability deteriorates significantly, the surface condition of the molded product is not smooth, the appearance is poor, and due to this, it whitens within a short time when used outdoors. There was a drawback called (chalking).

(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 modifier and thermosetting resin that improve the adhesion between the short glass fibers and the resin, we have overcome the above-mentioned drawbacks of the conventional method. This is what led to the present invention.
The present invention has a small coefficient of linear expansion and is difficult to cause thermal deformation.
In addition, molded products with excellent physical properties such as impact resistance, excellent moldability, and excellent surface condition, especially for rain gutters, decks, etc.
The object of the present invention is to provide a vinyl chloride resin composition suitable for thin-walled molded products such as window frames.

(Summary of the present invention) The summary of the present invention is that 100 parts by weight of vinyl chloride resin, 5 to 30 parts by weight of short glass fibers, 50 parts by weight of thermosetting resin IO, chlorinated polyethylene, ethylene-vinyl acetate, etc. Vinyl chloride prepared by adding 5 to 20 parts by weight of at least one modifier selected from copolymers, acrylonitrile-butadicone-styrene copolymers, and methyl methacrylate-butadiene-styrene copolymers. based resin composition (hereinafter referred to as the composition 1 of the present invention), 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, 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 - A vinyl chloride resin composition (hereinafter referred to as composition 2 of the present invention) containing 1 to 5 parts by weight of at least one processing aid selected from acrylonitrile-styrene copolymer and methyl methacrylate.
).

(Structure of the present invention) As the vinyl chloride resin used in the compositions 1 and 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 the composition 1.2 of the present invention °C
For example, if the strand has a length of 0.05 to 31 (
Glass chips cut into pieces (when present in a molded product), pile-shaped ones cut into a length of 0.05 to 3 mm (when present in a molded product), etc. are preferably used, among others, Taste 0.05
~3 (When present in the molded product) Glass tygosop is particularly preferably used, and those surface-treated with a coupling treatment agent such as epoxy silane are also preferably 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.

The modifier used in compositions 1 and 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, acrylic nitrile-butadiene-styrene copolymer (ABS), and methylmethacrylate-butadiene-styrene copolymer (M
At least one type selected from BS) 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. In addition, impact resistance and temporary resistance deteriorate.

In composition 1.2 of the present invention, the thermosetting resin is added in an amount of IO to 50 parts by weight per 100 weight arit+ of the vinyl chloride resin without increasing the linear expansion coefficient. , the f resistance of the molded product? Improve physical properties such as impact resistance and rigidity. If no thermosetting resin is added or only a small amount of less than 10 parts by weight is added,
A sufficient effect cannot be expected, and if a large amount exceeding 50 parts by weight is added, the coefficient of linear expansion will increase.

In compositions 1 and 2 of the present invention, the above-mentioned modifier is added to 100 parts by weight of vinyl chloride resin along with other components.
By adding 5 to 20 parts by weight, physical properties such as F4 impact resistance and rigidity of the molded product can be improved without increasing the coefficient of linear expansion. If the modifier is not added at all or if it is added in a small amount of less than 5 parts by weight, sufficient effects cannot be expected, and if it is added in a large amount exceeding 20 parts by weight, the coefficient of linear expansion will be large. turn into.

In Composition 2 of the present invention, by adding C, 1 to 5 parts by weight of the processing aid together with other components to 100 parts by weight of the vinyl chloride resin, it is possible to improve the quality and quality 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 no processing aid is 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.

(Effects of the present invention) The composition (2) of the present invention contains 100 parts by weight of vinyl chloride resin.
5 to 30 parts by weight of short glass fibers, 10 to 50 M parts of thermosetting resin, chlorinated polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene. A molded article containing 5 to 20 parts by weight of at least one modifier selected from copolymers,
The coefficient of linear expansion is small, so thermal deformation due to temperature changes does not occur.
Moreover, it has excellent physical properties such as tensile strength and impact resistance, and has good moldability, and the surface condition of the molded product is good and the appearance is good.

Composition 2 of the present invention, 10 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, chlorinated polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene. 5 to 20 parts by weight of at least one modifier selected from copolymers and at least one processing aid selected from methyl methacrylate-acrylonitrile-styrene copolymers and methyl methacrylate. 1 to 5 parts by weight of the agent is added, so the molded product has a small coefficient of linear expansion, is less prone to thermal deformation due to temperature changes, and has excellent physical properties such as tensile strength and impact resistance. It has extremely good moldability, and the surface condition of the molded product is smooth and uniform.

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

(Examples 1 to 7) Compounds shown in Table 1 (short glass fibers had a length of 2 to 5 mm)
(used) whose surface 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 kneader for 5 minutes at 160°C to obtain a thickness of 1.21 mm.
Make 11 sheet-like materials, crush this sheet-like material, and make 3
■Create pulverized pieces with a bending angle, extrude the pulverized pieces using an extruder and mold at a resin temperature of 180 to 185°C to a thickness of 1.2
- A thin-walled irregular shaped product was extrusion molded.

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. Adhesion was observed. The results are shown in Table 1 as Examples 1 to 7.

(Comparative Example 1) The formulation of Comparative Example 1 in Table 2 was well mixed in a mixture, and the mixture was heated in an extruder and mold at a resin temperature of 1)) 0 to 18.
Extrusion was carried out at 5° C. to obtain a thin, irregularly shaped article with a thickness of 1.2 s. The test piece was cut out, and the coefficient of linear expansion, tensile strength, elongation, and impact resistance were measured. The results are shown in Table 2 as Comparative Example 1.

(Comparative Example 2) The formulation of Comparative Example 2 in Table 2 (short glass fibers had a length of 4 to
I attempted to mold a 5 mm-sized piece (surface treated with epoxy silane) in the same manner as in Comparative Example 1, but the moldability was poor and molding was not possible. Mix at room temperature, and mix this mixture in a 1:I-ru kneader.
Knead at 90℃ for 5 minutes (make a sheet with a thickness of 1.2 mm, cut out this sheet, and preheat with a hand press at 190℃ for 2 minutes at 50 kg / cJ,
1.3 by pressing for 1 minute at 0℃100 kg/c+J
A sheet of m@ was prepared, a test piece was cut out from this sheet, and the same measurements and observations as in the example were performed. The results are also shown in Table 2 as Comparative Example 2.

The coefficient of linear expansion was measured using ASTM: D696. 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 observing the cross section of the test piece under an electron microscope and observing the formation of voids around the short glass fibers.

As is clear from Table 1, in the cases of Examples 1 to 4, the coefficient of linear expansion is small, and the physical properties such as surface impact resistance are the same as those of Comparative Example 1, where short glass fibers are dispersed and the temperature is not The moldability was improved to the extent that it was comparable to the above, and the moldability was able to be molded into a thin-walled irregularly shaped product with 1.2 fins, and the surface condition of the molded product was also good.

In addition, it was observed that there was good adhesion between the short glass fibers and the resin, with only very small voids partially visible around the short glass fibers. Moreover, in the cases of Examples 5 to 7, the moldability was also extremely good, and the surface condition of the molded products was smooth and uniform.

As is clear from Table 2, Comparative Example 1 has a significantly large coefficient of linear expansion 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. (hereinafter referred to as my own) Table 2 Procedure Nei City Authorized Letter (spontaneous) April 26, 1980 1. Indication of the case 1982 Patent Application No. 31790 2. Name of the invention Vinyl chloride resin composition 3 , Relationship to the case of the person making the amendment Patent applicant postal code 530 Address 2-4-4 Nishitenma, Kita-ku, Osaka Table Subject of amendment (1) Column for claims and detailed description of the invention in the specification .

Correct content (1) Amend the claims of the specification by adding a separate sheet.

(2) Page 5, line 9 to line 10 of the specification, page 7, line 7 to
In the 8th line and the 5th line from the bottom of page 10, 1 "Methyl methacrylate" is corrected to "Polymethyl methacrylate".

(3) Page 7, line 8 of the specification and wcXS page, table 1 (line 9)
``MMA'' is corrected to ``[PMMAJ''.

Statement @ 1 on the 6th line from the bottom of page 11 "Tension strength" There is a certain thing, "tensile strength" and correct it.

6. List of attached documents (1) One or more documents stating the amended scope of claims Claim 1: 100 parts by weight of vinyl chloride resin, 5 parts by weight of short glass fibers
30 parts by weight of a thermosetting resin, 10 to 50 parts by weight of a thermosetting resin, chlorinated polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene copolymer. A vinyl chloride resin composition containing 5 to 20 parts by weight of at least one modifier selected from among the above.

100 parts by weight of vinyl dichloride resin, 5 to 30 parts by weight of short glass fibers, and 50 parts by weight of thermosetting resin IO,
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 at least one processing aid selected from methyl methacrylate-acrylonitrile-styrene copolymer and polymethyl methacrylate 1 to 5
A vinyl chloride-based $I III composition comprising parts by weight.

Claims (1)

[Claims] 1. 100 parts by weight of vinyl chloride resin, 5 parts by weight of short glass fibers
30 parts by weight, 10 to 50 parts by weight of a thermosetting resin, chlorinated polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene copolymer. A vinyl chloride resin composition containing 5 to 20 parts by weight of at least one modifier selected from among the above. 2. Add 5 parts of short glass fiber to 100 parts by weight of vinyl chloride resin.
30 parts by weight of thermosetting resin IO to 50 parts by weight, chlorinated polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer and methyl methacrylate-butadiene-styrene copolymer. 5 to 20 parts by weight of at least one modifier selected from among 1 to 5 parts by weight of at least one processing aid selected from methyl methacrylate-acrylonitrile-styrene copolymer and methyl methacrylate. A vinyl chloride resin composition comprising parts by weight.