JPS60179444A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:The titled resin composition having a low coefficient of linear expansion, giving a molded article with excellent physical properties and appearance, etc., suitable as rainwater gutter etc., obtained by incorporating short glass fibers, mica, calcium carbonate, a plasticizer, and a specified modifier and a processing aid into a PVC resin. CONSTITUTION:100pts.wt. vinyl chloride resin is incorporated with 5-30pts.wt. short glass fibers; 5-30pts.wt. mica; 10-50pts.wt. calcium carbonate; 5-20pts.wt. modifier such as chlorinated polyethylene, an ethylene-vinyl acetate copolymer, an acrylonitrile-butadiene-styrene copolymer or a methyl methacrylate-butadiene- styrene copolymer; 1-5pts.wt. processing aid such as a methyl methacrylate- acrylonitrile-styrene copolymer or polymethyl methacrylate; and 0.1-5pts.wt. plasticizer (e.g. dioctyl phthalate).

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 walls, 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 the longitudinal length, causing deformation or breakage at connections or fasteners. The problem was that the exposed part of the bone L exposed directly to sunlight expanded thermally and became bent and wavy.

Conventionally, as described in Japanese Patent Publication No. 53-21891, vinyl resin 100 with a viscosity index of 50 to 180 has been used.
J, the average diameter of the individual particles is 0.05-50μ, Q machine filler 10-60 parts by weight, lubricant 1.5 parts by weight.
An extrusion molding composition containing ~5 parts by weight and 5 to 40 parts by weight of glass fiber has been proposed, but the adhesion between the mixed glass fiber and vinyl resin is poor, and a large amount of inorganic filler is mixed. Because of this, the physical properties of the molded product such as impact resistance are low, the moldability is poor, the surface condition of the molded product is not smooth, and the appearance is poor. It has the disadvantage of whitening (chalking) within a short period of time when exposed to water.

Furthermore, as described in Japanese Patent Application Laid-Open No. 57-34147, a mixture of 100 parts by weight of vinyl chloride resin with 3 to 20 parts by weight of mica and 15 to 50 parts by weight of calcium carbonate has been proposed; It has poor adhesion with vinyl chloride resin, and because it contains a large amount of calcium carbonate, the surface of the molded product is not smooth, and not only does it have a poor appearance, but this also makes it difficult to use it outdoors. It sometimes has the disadvantage of whitening (chalking) within a short period of time.

(Purpose of the Invention) In view of the above facts, the inventor has made a thorough examination and found that
The length of the short glass fibers is made extremely short, a modifier is added to improve the adhesion between the short glass fibers and mica, and the resin is added, and a processing aid is added to improve kneading during molding. By adding a plasticizer to smooth the surface of the resin, the inventors have discovered that the above-mentioned conventional drawbacks can be overcome and the present invention has been completed.The gist of the present invention is to Glass short tJN fiber 5 to 3
0 parts by weight, 5 to 30 parts by weight of mica, 10 to 50 parts by weight of calcium carbonate, chlorinated polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate-butadiene- 5 to 20 parts by weight of at least one modifier selected from styrene copolymers; at least 5 to 20 parts by weight of at least one modifier selected from methyl methacrylate-acrylonitrile-styrene copolymers and methyl methacrylate-1 1 to 5 parts by weight of one type of processing aid and 0.1 to 5 parts by weight of a plasticizer
A vinyl chloride resin composition comprising parts by weight.

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

Examples of short glass fibers used in the present invention include chopped glass fibers having strands cut into lengths of 0.05 to 3II11 (when present in the molded product), and short glass fibers having lengths of 0.05 to 3
Glass chops cut to a length of 0.05 to 3 mm (when present in a molded product) are preferably used. Particularly preferably used are those that have been surface-treated with a camping treatment agent such as epoxy silane.

For example, the mica used in the present invention has a diameter of 20 mm.
Those around μ are preferably used, and those whose surfaces have been treated with a compensating agent such as epoxy silane are preferably used.

As the calcium carbonate used in the present invention, for example, precipitated calcium carbonate, slight rhusium carbonate, ultrafine carbonate calcium, etc. are preferably used, and among them, ultrafine calcium carbonate is particularly preferably used. Those whose surfaces have been surface-treated with fatty acid ester or the like are preferably used.

When added to the system, the modifying agent used in the present invention improves the adhesion between the short glass fibers and mica and the vinyl chloride resin, and eliminates the voids that occur around the short glass fibers. It is made of chlorinated polyethylene (chlorinated PE
), ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), and methyl methacrylate-butadiene-styrene copolymer (M
At least one type selected from BS) is used.

The processing aid used in the present invention is methyl methacrylate-acrylonitrile-styrene copolymer (MA
At least one selected from S) and methyl methacrylate (MMA) is used.

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

In the present invention, along with other components, glass f:li
11 to 100 parts of vinyl chloride resin, 5 parts
By adding 30 to 30 parts by weight, the coefficient of linear expansion of the molded product is reduced, the rigidity is increased, and the molded product is resistant to thermal deformation due to temperature changes, without deteriorating moldability, repulsion 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 deteriorate and the appearance of the molded product will not be clear. Moreover, impact resistance and weather resistance deteriorate.

In the present invention, by adding 5 to 50 parts by weight of mica to 100 parts by weight of vinyl chloride resin along with other components, linear expansion of the molded product can be achieved without deteriorating moldability and impact resistance. Reduce the ratio and make it less likely to be thermally deformed due to temperature changes. If mica is not added at all or if the amount added is less than 5 parts by weight per 100 parts by weight of vinyl chloride resin, a sufficient effect cannot be expected; If added, moldability will deteriorate, the appearance of the molded product will not be smooth, and impact resistance will deteriorate.

In the present invention, together with other components, calcium carbonate is added in an amount of 10 to 5 parts by weight based on 100 parts by weight of vinyl chloride resin.
By adding 0 parts by weight, the rigidity of the molded article is improved and it becomes less susceptible to thermal deformation due to temperature changes without deteriorating the weather resistance and impact resistance. If calcium carbonate is not added at all or if the amount added is less than 10 parts by weight per 100 parts by weight of vinyl chloride resin, sufficient effects cannot be expected, and if calcium carbonate is added in excess of 50 parts by weight. If a large amount is added, impact resistance and weather resistance will deteriorate.

In the present invention, by adding 5 to 20 parts by weight of the modifier together with other components to 100 parts by weight of the vinyl chloride resin, the impact resistance of the molded product can be improved without increasing the coefficient of linear expansion. Improve physical properties such as strength and rigidity. 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 the present invention, the processing aid, along with other ingredients,
By adding 1 to 5 parts by weight to 100 parts by weight of vinyl chloride resin, it can improve the resistance (φi impact resistance, rigidity, etc.) of molded products together with the modifier without increasing the coefficient of linear expansion. To further improve the physical properties.If no processing aid is added at all or if it is added in a small amount of less than 1 part by weight, a sufficient effect cannot be expected, and if it is added in a large amount exceeding 5 parts by weight. In this case, the coefficient of linear expansion of the molded product becomes large.

In the present invention, by adding 0.1 to 5 parts by weight of a plasticizer to 100 parts by weight of vinyl chloride resin together with other components, the linear expansion coefficient can be increased or the rigidity can be decreased. To smoothen the surface condition of a molded product, improve its appearance, and improve its weather resistance.

(Effects of the present invention) The vinyl chloride resin composition of the present invention contains 5 to 30 parts by weight of short glass fibers, 5 to 50 parts by weight of mica, and 10 to 10 parts by weight of calcium carbonate to 100 parts by weight of vinyl chloride resin. 50 parts by weight, and at least one modifier selected from chlorinated polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene copolymer 5 1 to 20 parts by weight, 1 to 5 parts by weight of at least one processing aid selected from methyl methacrylate acryloni]-lyrous styrene copolymer and methyl methacrylate, and 0.1 to 5 parts by weight of a plasticizer. Since it is made by adding a 5-fold Q part, the linear expansion coefficient of the molded product is small and thermal deformation due to temperature changes does not occur, and it has excellent physical properties such as tensile strength and impact resistance. The moldability is extremely good, the surface condition of the molded product is smooth and there is a J slope, and the appearance is good.As a result of this, it does not whiten (chalking) within a short time when used outdoors and is weather resistant. It has excellent properties.

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

(Example 1.2)) The composition shown in Table 1 (short glass fibers with a length of 2 to 5 cm and whose surface was treated with epoxy silane was used) was heated in a mixer at 120°C for 6 minutes. Heat and mix, knead this mixture in a roll kneader at 160"C for 5 minutes to make a sheet with a thickness of 1.2 mm, and crush this sheet to give 311 mm.
A 1-square crushed piece is made, and this crushed piece is extruded using an extruder and a mold at a resin temperature of 180 to 185°C to a thickness of 1.2+
A thin-walled profiled article of I++ was extruded.

A test piece was cut out from the molded product, and the coefficient of linear expansion, tensile strength, elongation, impact strength, heat shrinkage rate, weather resistance, and length of short glass fibers in the molded product were measured. The adhesion between the fiber and resin was observed. The results are shown in Example 1.
．． 2 are shown in Table 1.

(Comparative Examples 1 and 3) The formulations of Comparative Examples 1 and 3 in Table 1 were mixed well in a mixture, and the mixture was heated in an extruder and mold at a resin temperature of 180 to 1.
The extrusion was removed at 85° C., and a thin profiled product having a thickness of 1.21111 mm was extruded. The test pieces were cut out, and the coefficient of linear expansion, tensile strength, and elongation were measured. The results are also shown in Table 1 as Comparative Examples 1 and 3.

(Comparative Example 2) The formulation of Comparative Example 2 in Table 1 (the short glass fibers had a length of 4 to
I tried molding the same material as in Comparative Example 1, but the moldability was poor and molding was not possible. This mixture was kneaded at 190°C for 5 minutes using a roll kneader to form a sheet with a thickness of 1.2 fins.The sheet was cut out and mixed at 190°C with a hand press.
After preheating for 2 minutes at C50kg/ct, 190℃100
kg/ctA for 1 minute to produce a 1.3 inch sheet, cut out a test piece from this sheet, and performed the same measurements and observations as in the example. The results were used as Comparative Example 2.
It is also shown in the table.

The coefficient of linear expansion was measured using ASTM: D696. Regarding tensile strength and elongation, JISA570
Measured at 6. Regarding impact strength, JISA540
Measured at 0. Regarding the heat shrinkage rate, cut out a test piece with a length of 200 + im in the longitudinal direction from the molded product, make lines at 100 tuna intervals in three places, heat the test piece in a gear oven at 100°C for 15 minutes, then take it out and let it cool to room temperature. After standing, the length between the lines was measured, and the degree of shrinkage (%) with respect to the original length was calculated. Regarding weather resistance, J+
Pressure 4゜5~5 kgf/ than the condition of 5A1j1s
Measurements were made under acceleration conditions raised to cm.

The adhesion between the short glass fibers and the resin in the molded product 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, Example 1. In case of 2,
In both 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 as thin as 1.2 ridges. The molded product could be molded and was stiff, and the surface condition of the molded product was smooth and uniform, which was extremely good.

As is clear from Table 1, 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 form a thin-walled molded product, and the physical properties such as impact resistance and weather resistance were so poor that they could not be put to practical use. Voids were observed, and there was no close contact between the short glass fibers and the resin. In the case of Comparative Example 3, the moldability was not very good, and although it was possible to mold a thin, irregularly shaped product, the surface condition was poor, and the physical properties such as impact resistance and weather resistance were too poor to be of practical use. It was bad. (Margin below)
Table 1 Procedural Official Letter (Spontaneous) April 26, 1980 Commissioner of the Patent Office 2 Name of the invention Vinyl chloride resin composition 3 Relationship with the person making the amendment Patent applicant postal code 530 Address: Patent Department, 2-4-4 Nishitenma, Yamakita-ku, Osaka
(06) 365-2181 Special Investigation Department Tokyo resident (Act 03)
434-95524, Subject of amendment (1) Field of claims and detailed description of the invention of Akira IIITIIF.

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

(2) "Methyl methacrylate" is replaced with "polymethyl methacrylate”.

(3) In the third line from the bottom of page 4 of the specification, "Composition." There is a certain thing, “It consists in the composition.” and correct it.

(4) Line 3 from the bottom of page 6 of the specification, table jl1 of page 15 (
(9th line) - Amend "MMA" to "PMMAJ" (5) Insert the following sentence between the 2nd line and the 1st line from the bottom of page 6 of the specification.

[Plasticizers used in the present invention include, for example, dibutyl heptatarate (DBP), dioctyl heptatalate (DOP)
), etc., 7-talic acid series, tricesilph 10-sulfate (TCP
Phosphate-based plasticizers such as ) and epoxy-based plasticizers such as epoxidized soybean oil are preferably used, especially dioctyl 7-thale).
(DOP) is particularly preferably used. (6) In the fourth line from the bottom of the first worker in the specification, the term ``Tensile strength'' shall be amended to ``Tensile strength.''

5 List of Attached Documents (1) One or more documents stating the amended scope of the claims The scope of the claims includes 100 parts by weight of vinyl chloride resin, 5 to 30 parts by weight of short glass fibers, and mica. 5 to 30 parts by weight, 10 to 50 parts by weight of calcium carbonate, 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 1 m of a modifier selected from 1 to 5 parts by weight of at least one processing aid selected from methyl methacrylate-acrylonitrile-styrene copolymer and polymethyl methacrylate. and 0.1 to 5 parts by weight of a plasticizer.

Claims (1)

[Claims] 1. For 100 parts by weight of vinyl chloride resin, 5 to 30 parts by weight of short glass fibers and 5 to 30 parts by weight of mica,
IO to 50 parts by weight of calcium carbonate, and at least one selected from chlorinated polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-cyclodiene-styrene copolymer, and methyl methacrylate-butadiene-styrene copolymer. 5 to 20 parts by weight of a seed modifier, 1 to 5 parts by weight of at least one processing aid selected from methyl methacrylate-acrylonitrile-styrene copolymer and methyl methacrylate, and 0 parts by weight of a plasticizer.
．． 1 to 5 parts by weight of a vinyl chloride resin composition.