JPS60179445A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:The titled 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, an ultraviolet absorber, 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; 5-50pts.wt. mica; 10-50pts.wt. calcium carbonate; 5-20pts.wt. modifier such as a 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 0.05-0.5pts.wt. ultraviolet absorber (G) (e.g. benzophenone).

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, 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. The disadvantage is that the parts that receive direct sunlight tend to expand thermally and become bent or 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.
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 1X parts by weight, 1.5 to 5 parts by weight of agent 11 and 5 to 5 parts of glass fiber with a length of 4 to 5 mm.
An extrusion molding composition with 40 parts by weight has been proposed, but the glass fibers are evenly distributed in the resin! 1 (4LJZ <
< , and f of mixed glass fiber and vinyl resin and '
Q Adhesiveness is poor, and large voids + V are generated around the glass fibers, resulting in a marked decline in physical properties such as impact resistance of the molded product compared to the vinyl resin before glass fibers are added. In addition, the moldability is extremely poor (the surface condition of the molded product is not smooth, and the appearance is not only bad, but also
Due to this, when used outdoors, it has the disadvantage of whitening (chalking) within a short period of time.

Furthermore, as described in JP-A No. 57-34147, a mixture of 3 to 20 parts by weight of mica and 15 to 50 parts by weight of calcium carbonate with 100 parts by weight of vinyl chloride resin has been proposed; The adhesion between mica and vinyl chloride resin is poor, and because a large amount of calcium carbonate is mixed in, 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 has the disadvantage of whitening (chalking) within a short period of time when exposed to water.

(Invention 1) In view of the fact of cooking, the misfired man conducted a thorough inspection J.1, and as a result, the length of the short glass fibers was extremely shortened, and the length of the short glass fibers, mica, and resin were reduced. Adding a modifier to improve the adhesion between
In addition, by adding an ultraviolet absorber that improves the weather resistance of molded products, conventional drawbacks such as those mentioned above can be overcome by 1N! erase j47
The present invention has been made based on the discovery that the coefficient of linear expansion is small, thermal deformation is difficult to occur, and physical properties such as impact resistance are excellent, as well as moldability and weather resistance are excellent. The object of the present invention is to provide a vinyl chloride resin composition suitable for molded products with smooth surfaces, particularly thin molded products such as rain gutters, decking materials, and window frames.

(Summary of the Invention) The gist of the present invention is to add 100 parts by weight of vinyl chloride resin, 5 to 30 parts by weight of short glass fibers, 5 to 50 parts by weight of mica, 1 to 50 parts by weight of calcium carbonate, and chlorinated polyethylene. , ethylene-11! i+: 5 to 20 parts by weight of at least one modifier selected from acid-hinyl copolymer, acrylonitrile-butadiene-styrene copolymer, and methylmethacrylate-1-butadiene-styrene copolymer , 1 to 5 parts by weight of at least one processing aid selected from methyl methacrylate acryl di-lyl-styrene copolymer and methyl methacrylate, and 0.05 to 0.5 parts by weight of an ultraviolet absorber. Parts by weight of the vinyl chloride resin composition.

(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. , polyvinyl chloride (PVC) is particularly preferably used.

Examples of short glass fibers used in composition 1.2 of the present invention include chopped glass fibers whose strands are cut into lengths of 0.05 to 3 m5 (when present in the molded product), and chopped glass fibers with lengths of 0.05 m to 3 m5 (when present in the molded product).
Pile-shaped materials cut into lengths of 0.05 to 3 mm (when present in the molded product) are preferably used, and in particular, piles cut to lengths of 0.05 to 3 mm (when present in the molded product) are preferably used. Glass chops are particularly preferably used, and those surface-treated with a coupling treatment agent such as epoxy silane are preferably used.

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 surface-treated with a coupling treatment agent such as aminosilane are preferably used.

As the calcium carbonate used in the present invention, for example, precipitated calcium carbonate, slight lucium carbonate, ultrafine calcium carbonate, etc. are preferably used, and among them, ultrafine calcium carbonate is particularly preferably used. The surface treated with fatty acid ester or the like is preferably used.

The modifier used in the present invention is added to the system to improve the adhesion between the short glass fibers and the vinyl chloride resin, and to reduce the voids that occur around the short glass fibers. , chlorinated polyethylene (chlorinated PE), ethylene-white, which improves the impact strength, etc. of molded products.

At least one selected from acid vinyl copolymer, acrylonitrile-butadicone-styrene copolymer (813S), and methyl methacrylate-butadiene-styrene copolymer (MBS) is used.

The auxiliary agent used in the present invention is methyl methacrylate-acrylonitrile-styrene copolymer (M
At least one selected from ΔS) and methyl methacrylate (MMA) is used.

As the ultraviolet ray absorbent used in the present invention, (column evaporator, salicylate conistere, hesoate ester, benzophenone type, benzotriazole type and acrylonitrile type) are preferably used.

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

In the present invention, short glass fibers are used together with other components.
5 to 30 parts by weight of vinyl chloride resin
By adding more weight, the coefficient of linear expansion of the molded product is reduced, the rigidity is increased, and the molded product becomes less susceptible to thermal deformation due to temperature changes, without degrading moldability, ILJ impact resistance, etc. If short glass fibers are not added at all or only a small amount of less than 5 parts by weight is added, a sufficient effect cannot be expected, and if a large amount exceeding 30 parts by weight is added, The moldability deteriorates, the appearance of the molded product is not smooth, and the 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 it is added in a small amount (less than 5 parts by weight), a sufficient effect cannot be expected; if mica is added in a large amount (more than 50 parts by weight), moldability deteriorates and the molded product The appearance will not be smooth and the 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 product is improved and it becomes less susceptible to thermal deformation due to temperature changes without deteriorating the weather resistance and impact resistance. If the inorganic filler is not added at all or if it is added in a small amount (less than 10 parts by weight), sufficient effects cannot be expected, and if it is added in a large amount exceeding 50 parts by weight, the one-shot resistance and weather resistance deteriorates.

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 the vinyl chloride resin, together with the modifier, the physical properties such as impact resistance and rigidity of the molded product 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 (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, the linear expansion coefficient of the molded product will decrease. becomes large.

In the present invention, along with other components, a UV absorber is
0.0 to 80 to 100 parts by weight of vinyl chloride resin.
By adding 0.05 to 0.5 parts by weight, temperature rise during use of the molded product is prevented and weather resistance is improved. No UV absorber added or less than 0.05 parts by weight lSj
A sufficient effect cannot be expected if only a small amount is added, and even if it is added in a large amount exceeding 0.5 part by weight, it will not contribute effectively to improving weather resistance.

(Effect of the invention) The vinyl chloride resin composition of the present invention has a vinyl chloride resin composition of 8
0 to 100 parts by weight, 5 to 30 parts by weight of short glass fibers, 5 to 50 parts by weight of mica, 10 to 50 parts by weight of calcium carbonate, chlorinated polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene. - 5 to 20 parts of at least one modifier selected from styrene copolymer and methyl methacrylate-butadiene-styrene copolymer, and methyl methacrylate-acrylonitrile-styrene copolymer and methyl 1 to 5 parts by weight of at least one processing aid selected from methacrylates, and 0.05 to 0.0 parts by weight of an ultraviolet absorber.
5 parts by weight, the molded product has a small coefficient of linear expansion and is less prone to thermal deformation due to temperature changes, has excellent physical properties such as tensile strength and impact resistance, and has good moldability. The surface condition of the molded product is smooth and uniform, and the appearance is excellent.As a result, it does not whiten (chalking) within a short period of time when used outdoors.
Excellent weather resistance.

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

(Example 1.2) The formulation shown in Table 1 (short glass fibers were 2 to 5 long in length,
(Using one whose surface was treated with epoxy silane) was heat-mixed at 120°C for 6 minutes in a mixer, and this mixture was kneaded for 5 minutes at 160°C in a roll kneader to form sheets with a thickness of 1.2 mm. A product is made, this sheet-like material is crushed to make crushed pieces with 3 fin angles, and the crushed pieces are put into an extruder and a mold at a resin temperature of 1.
Extrusion was carried out at 80 to 185° C. to extrusion mold a thin profiled article with a thickness of 1.2 mm.

A test piece was cut out from the molded product, and the linear expansion coefficient, tensile strength, elongation, impact strength, heat shrinkage rate, weather resistance, and length of the short glass fibers in the molded product were measured. The adhesion between mica and resin was observed. The results are shown in Table 1 as Example 1.2.

(Comparative Examples 1 and 3) The formulations of Comparative Examples 1 and 3 in Table 1 were mixed well in a mixer, and the mixture was put into an extruder and a mold to form a resin'/! , 11□ degrees 18 (+ to 185°C) to extrude and mold a thin irregular shaped product with a thickness of 1.2 ridges. Test pieces were cut out from the molded product and measured for linear expansion coefficient, tensile strength, elongation, and heat The results of measuring shrinkage rate and weather resistance are also shown in Table 1 as Comparative Example 1.3.

(Comparative Example 2) The formulation of Comparative Example 2 in Table 1 (short glass fibers were:
I tried molding ~ (i all, surface treated with epoxy silane) in the same manner as in Comparative Example 1, but the moldability was poor and molding could not be done, so the mixture shown in Table 2 was used in a mixer. This mixture was kneaded at 190°C for 5 minutes using a 1:I-ru kneader to make a sheet with a thickness of 1.2 m, and this sheet was cut out and placed in a hand press. After preheating at 190℃ for 2 minutes at 50 kg/ca,
A 1.3 m long sheet was produced by pressing at 190·'cloo kg/cJ for 1 minute, and test pieces were 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. It is also shown in the table.

The coefficient of linear expansion was measured using ASTM D696. For tensile strength and elongation, JISA570
Measured at 6. (For h impact strength, JIS Δ54
Measured at 00. Regarding the heat shrinkage rate, cut out a test piece with a length of 200 mm in the longitudinal direction from the molded product, make lines at 100 mm intervals in 3 places, heat this 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, JISA1
Pressure 4゜5~5 kg f/a than the condition of 415
Measurements were carried out under accelerated conditions raised to 11 liters.

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, in both Examples 1 and 2, the coefficient of linear expansion is small, and the physical properties such as impact resistance are comparable to those of Comparative Example 1 in which short glass fibers are not dispersed. In addition, it was possible to form a thin-walled molded product with a moldability of 1.21, 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. In addition, the weather resistance was also improved compared to Comparative Example 1 in which short glass fibers were not dispersed.
The improvement was comparable to the value of , and was significantly better.

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 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. In the case of Comparative Example 3, although it was possible to form a thin-walled molded product, the surface condition was extremely poor, and the physical properties such as impact resistance and weather resistance were too poor to be of practical use. (Margin below)
Table 1] Yin-liu-ni-neichi Seiko-ji (spontaneous) April 26, 1980 1. Case description 1982 Patent Office No. 37162 2. Name of invention Vinyl chloride resin composition 3. Amendment Relationship with the patent applicant case: Patent applicant postal code: 530 Address: Patent Department, 2-4-4 Nishitenma, Kune-ku, Osaka
(06) 365-2181 Patent Department Tokyo resident T1 (
03) 434-95524, Subject of amendment 1'l) Definition of the claims and detailed description of the invention.

& Contents of amendment (1) The scope of claims in the specification will be amended nine times as attached.

(2) Specification page 5, line 6 to line 7, page 7, line 1θ~
In line 11 and line 9 of page 11, the words [methyl methacrylate] will be amended to read "polymethyl methacrylate."

(3) Page 7, line 11 of the specification and page 17, table 1 (line 9)
In line 1), correct [MMAJ] to [PMMAJ.

(4) In the 8th line from the bottom of page 10 and the 3rd line of page 11 of the specification, the words [80 to 100 parts by weight] shall be amended to read ``100 parts by weight.''

a List of attached documents + one or more documents stating the scope of claims after IJ amendment Claim 1: 100 parts by weight of vinyl chloride resin, 5 parts by weight of short glass fibers
30 to 30 parts by weight, 5 to 50 parts by weight of mica, 10 to 50 parts by weight of calcium carbonate, chlorinated polyethylene,
5 to 20 parts by weight of at least one modifier selected from ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene copolymer; Adding 1 to 5 parts by weight of at least one processing aid selected from acrylate acrylonitrile-styrene copolymer and polymethyl methacrylate and 0.05 to 0.5 parts by weight of an ultraviolet absorber. A vinyl chloride resin composition.

Claims (1)

[Claims] 1. 100 parts by weight of vinyl chloride resin, 5 parts by weight of short glass fibers
5 to 50 parts by weight of mica, 10 to 50 parts by weight of calcium carbonate, chlorinated polyethylene,
5 to 20 parts by weight of at least one modifier selected from ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene copolymer; 1 to 5 parts by weight of at least one processing aid selected from acrylate-acrylonitrile-styrene copolymer and methyl methacrylate; and 0 parts by weight of an ultraviolet absorber.
．． 05 to 0.5 parts by weight of a vinyl chloride resin composition.