JPH0820698A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain a vinyl chloride resin composition, excellent in thermal stability and processability and capable of effectively preventing the plateout phenomenon from occurring. CONSTITUTION:This vinyl chloride resin composition is obtained by blending 100 pts.wt. vinyl chloride resin containing 15-120 pts.wt. polyester-based plasticizer with 0.1-10 pts.wt. polybutadiene copolymer containing a butadiene-based rubber as a rubber component or an acrylic rubber copolymer containing an acrylic rubber as the rubber component. A vinyl chloride resin containing 0.5-10 pts.wt. dibasic lead phosphite or 1-20 pts.wt. ethylene-vinyl acetate-based resin with 55-70wt.% vinyl acetate content may be used in place of the polyester-based plasticizer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition, and particularly when a vinyl chloride resin is molded and processed, a part of the vinyl chloride resin composition such as a stabilizer and a coloring agent is calender roll, take-off roll, The present invention relates to a vinyl chloride resin composition capable of preventing the phenomenon of so-called "plate-out", which is the phenomenon of separation and adhesion to metal surfaces such as embossing rolls, rubber rolls, and cooler rolls.

[0002]

BACKGROUND OF THE INVENTION Vinyl chloride resin compositions utilize transparency and flexibility, strength, weather resistance, cold resistance, heat resistance and calender processability by taking advantage of compatibility with plasticizers. And excellent in extrudability,
Agricultural film sheets, medical film sheets, marking and sticker film sheets, masking and protection film sheets, vehicle oil and solvent resistant sheets, electrical insulating tape film sheets, electric wire films -Widely used in all fields such as sheets, decorative films / sheets for plywood, decorative films / sheets for steel plates, semi-rigid and hard films / sheets, and plates, pipes, molded products.

However, as described above, when a vinyl chloride resin is calendered, a phenomenon of plate-out may occur, and therefore, Japanese Patent Publication No. 3-45745.
Japanese Patent Publication No. 3-45746 and Japanese Patent Publication No. 3-45746 disclose that liquid polybutadiene or a modified product thereof is added for the purpose of preventing plate-out when a vinyl chloride resin is mixed with an epoxy resin or an epoxidized vegetable oil. However, the plate-out prevention effect is not always sufficient.

Further, higher fatty acids, higher fatty acid esters, aromatic alcohol fatty acid esters, silica and the like are generally known to suppress plate-out (hereinafter referred to as "conventional plate-out inhibitors").

However, although the conventional plate-out inhibitor has some effect of suppressing plate-out when added, it is not sufficient and has the following drawbacks.

Higher fatty acid-based compounds delay the gelation property of the vinyl chloride resin composition, reduce the transparency, and cause discoloration during processing. The higher fatty acid ester type and aromatic alcohol fatty acid ester type ones impede the thermal stability of the vinyl chloride resin composition and make it easily discolored during processing.
Silica lowers the thermal stability of the vinyl chloride resin composition, makes it easily discolored during processing, and reduces the transparency when incorporated in a large amount.

Further, when a vinyl chloride resin composition containing a polyester-based plasticizer, a dibasic lead phosphite or an ethylene-vinyl acetate resin is calendered, especially, a calender roll surface, a take-off roll surface, an embossing roll surface, a rubber roll is used. By blowing a part of the vinyl chloride resin composition on the surface and contaminating the surface of each roll,
The thickness accuracy of vinyl chloride products (films / sheets) decreases, and normal tightening cannot be performed, resulting in gloss and roughness of the product surface.
Appearance performance such as transparency decreases. Moreover, the contaminants on the surface of each roll must be removed, resulting in extremely low productivity. However, the conventional plate-out preventing agent not only does not have a sufficient effect of preventing such "blowing", but also causes the above-mentioned problems.

The present invention has been made in view of the above problems of the prior art, and its object is to provide chloride having excellent thermal stability and processability and capable of effectively preventing the plate-out phenomenon. It is to provide a vinyl resin composition.

[0009]

In order to achieve the above object, the present invention is based on 100 parts by weight of a vinyl chloride resin containing 15 to 120 parts by weight of a polyester plasticizer and polybutadiene copolymer containing butadiene rubber as a rubber component. A vinyl chloride resin composition comprising 0.1 to 10 parts by weight of a polymer or an acrylic rubber copolymer containing acrylic rubber as a rubber component is a first invention, and a dibasic lead phosphite is 0.5 to 0.1 to 10 parts by weight of a polybutadiene copolymer containing butadiene rubber as a rubber component or an acrylic rubber copolymer containing acrylic rubber as a rubber component is mixed with 100 parts by weight of vinyl chloride resin containing 10 parts by weight. A vinyl chloride resin composition as a second invention, containing 1 to 20 parts by weight of an ethylene-vinyl acetate resin having a vinyl acetate content of 55 to 70% by weight. To 100 parts by weight, the acrylic rubber copolymer polybutadiene copolymer or an acrylic rubber to butadiene rubber and the rubber component and the rubber component 0.1
A vinyl chloride resin composition prepared by mixing 10 to 10 parts by weight is defined as a third invention.

As the vinyl chloride resin, vinyl chloride homopolymers, vinyl chloride-vinyl acetate copolymers and vinyl chloride-ethylene vinyl acetate copolymers can be used.

In the first invention, as the plasticizer,
Adipic acid type polyester plasticizers, phthalic acid type polyester plasticizers and the like can be used. In addition, as the stabilizer, Pd-based, Sn-based, except for Cd-Ba-based, Ba-
A Zn-based stabilizer, a Ca-Zn-based stabilizer, or the like can be used. Pb-based and Sn-based stabilizers are generally not preferable because they tend to decompose polyester plasticizers and cause defects such as bleeding.

In the second invention, as the plasticizer,
It is possible to use phthalic acid ester-based, adipic acid ester-based, phosphoric acid ester-based, trimellitic acid ester-based resins and the like which are usually used as plasticizers for vinyl chloride resins. Further, as the stabilizer, among the lead-based metal compounds, dibasic lead phosphite is particularly limited for the purpose of improving weather resistance, heat resistance and electric insulation.

In the third invention, as the plasticizer,
It is possible to use phthalic acid ester-based, adipic acid ester-based, phosphoric acid ester-based, polyester-based, or other materials that are commonly used as plasticizers for vinyl chloride resins.
Further, as the stabilizer, Cd-Ba type, Ba-Zn type,
It is possible to use stabilizers which are usually used for vinyl chloride resins, such as Ca-Zn type, Pb type and Sn type.

In addition, pigments, fillers, UV absorbers, processing aids, heat resistance aids, weather resistance improvers and the like can be added as required.

[0015]

In the first invention, when the polyester plasticizer is less than 15 parts by weight, the melt viscosity is high, while when it exceeds 120 parts by weight, the melt viscosity is low and the processing becomes very difficult. In the second invention, if the dibasic lead phosphite is less than 0.5 parts by weight, the thermal stability is poor and it cannot be processed. On the other hand, 1
When it exceeds 0 parts by weight, the slipperiness is strong and the workability is poor.
In the third invention, an ethylene-vinyl acetate resin having a vinyl acetate content of less than 55% by weight hinders transparency and lowers gelation property, while an ethylene-vinyl acetate resin having the same content of more than 70% by weight is used. Resin has little effect of improving impact resistance. Also, the vinyl acetate content is 55 to 70% by weight.
When the amount of the ethylene-vinyl acetate resin is less than 1 part by weight, the effect of improving impact resistance and gelation property is small. On the other hand, when the amount of the resin exceeds 20 parts by weight, the compatibility with the vinyl chloride resin deteriorates, and defects such as flow marks in thickness unevenness occur during calendar processing. If the polybutadiene copolymer containing butadiene rubber as a rubber component or the acrylic rubber copolymer containing acrylic rubber as a rubber component is less than 0.1 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, the effect of preventing plate-out is exerted. It cannot be expected. On the other hand, when it exceeds 10 parts by weight, the calendering workability is deteriorated.

[0016]

EXAMPLES Examples 1 to 9 of the present invention will be described below in comparison with corresponding Comparative Examples 1 to 9.

[1] Examples 1 to 3, Comparative Examples 1 to 3 (Example 1, Comparative Example 1) A vinyl chloride resin composition compounded as shown in Table 1 below was placed on a 6-inch two-roll mill. Kneading was performed at a roll temperature of 180 ° C. and a sheet thickness of 0.2 mm, and the roll surface was observed 15 minutes after the kneading time, and the stain was evaluated. Also, a sheet having an appropriate size was sampled at a kneading time of 5 minutes and 20 minutes, the color tone was measured by a color difference meter, and the thermal stability was evaluated. The results are shown in Table 1. In addition, the evaluation of dirt is performed in 5 stages, 5 is the worst, and a thick oil film (or powder) is formed on the roll surface, 4 is clearly an oil film (or powder) on the roll surface ) Was observed, 3 was a little oil film (or powder) on the roll surface, 2 was a slight oil film (or powder) on the roll surface, No. 1 indicates that no oil film or the like (or powdery matter) was observed on the roll surface. The color difference meter is Nippon Denshoku Industries Co., Ltd.
Using SZ-Σ80 manufactured by K.K., the color tone was measured using the sheet after 20 minutes of kneading time as the standard, and the color difference was displayed.

(Example 2, Comparative Example 2) The vinyl chloride resin composition blended as shown in Table 2 below was kneaded in the same manner as in Example 1 to stain the roll surface and to stabilize the heat of the product. Was evaluated. The results are shown in Table 2. (Example 3, Comparative Example 3) The vinyl chloride resin composition blended as shown in Table 3 below was kneaded in the same manner as in Example 1 to evaluate the stain on the roll surface and the thermal stability of the product. . The results are shown in Table 3. In addition, the compounding quantity of Tables 1-3 and the following Tables 4-9 shows a weight part.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

As is apparent from Tables 1 to 3, the present Examples 1 to 1
The material of No. 3 has a plate-out prevention effect and has little discoloration during processing (excellent thermal stability). However, as is clear from Table 1, in Comparative Example 1 in which the conventional plate-out inhibitor was blended, some plate-out suppressing effect was observed, but it was not sufficient and discoloration during processing was large. Further, even if the same plate-out preventing agent as in this example is added as in Comparative Example 2 in Table 2, the plate-out preventing effect is small if the added amount is as small as 0.05 parts by weight. Further, as in Comparative Example 3 in Table 3, even if the same plate-out preventing agent as in this example was added, if the addition amount was as large as 15 parts by weight, the plate-out preventing effect was exhibited, but discoloration occurred. It gets a little bigger.

[2] Examples 4 to 6 and Comparative Examples 4 to 6 (Example 4, Comparative Example 4) Vinyl chloride resin compositions formulated as shown in Table 4 below were prepared in the same manner as in Example 1. Kneading was performed and the stain on the roll surface was evaluated. The results are shown in Table 4.

(Example 5, Comparative Example 5) The vinyl chloride resin composition blended as shown in Table 5 below was kneaded in the same manner as in Example 1 to evaluate the stain on the roll surface.
The results are shown in Table 5.

(Example 6, Comparative Example 6) The vinyl chloride resin composition blended as shown in the following Table 6 was kneaded in the same manner as in Example 1 to stain the roll surface and heat stability of the product. Was evaluated. The results are shown in Table 6.

[0026]

[Table 4]

[0027]

[Table 5]

[0028]

[Table 6]

As is apparent from Tables 4 to 6, the present Example 4 to
No. 6 has an effect of preventing plate-out, and as shown in Table 6, there is little discoloration during processing (excellent thermal stability). However, as can be seen in Table 4,
Comparative Example 4 containing a conventional plate-out preventing agent does not show a plate-out preventing effect. Further, even if the same plate-out preventing agent as in the present example is added as in Comparative Example 5 in Table 5, the effect of preventing plate-out is not observed unless the added amount is as small as 0.05 parts by weight. Further, as in Comparative Example 6 in Table 6, even if the same plate-out preventing agent as in the present example was added and the addition amount was as large as 15 parts by weight, the plate-out preventing effect was exhibited, but discoloration occurred. growing.

[3] Examples 7-9, Comparative Examples 7-9 (Example 7, Comparative Example 7) Vinyl chloride resin compositions formulated as shown in Table 7 below were prepared in the same manner as in Example 1. Kneading was performed to evaluate the stain on the roll surface and the thermal stability of the product. The results are shown in Table 7. (Example 8, Comparative Example 8) A vinyl chloride resin composition blended as shown in Table 8 below was kneaded in the same manner as in Example 1 to evaluate the stain on the roll surface and the thermal stability of the product. . The results are shown in Table 8. (Example 9, Comparative Example 9) A vinyl chloride resin composition blended as shown in Table 9 below was kneaded in the same manner as in Example 1 to evaluate the stain on the roll surface and the thermal stability of the product. . The results are shown in Table 9.

[0031]

[Table 7]

[0032]

[Table 8]

[0033]

[Table 9]

As is apparent from Tables 7-9, the present Example 7-
The material of No. 9 has the effect of preventing plate-out, and has little discoloration during processing (excellent thermal stability). However, as is clear from Table 7, in Comparative Example 7 containing the conventional plate-out inhibitor, some plate-out suppressing effect is observed, but it is not sufficient and discoloration during processing is large. Moreover, even if the same plate-out preventing agent as in the present example is added as in Comparative Example 8 in Table 8, the plate-out preventing effect is small if the addition amount is as small as 0.05 parts by weight. Furthermore, as in Comparative Example 9 in Table 9, even if the same plate-out preventing agent as in the present example was added and the addition amount was as large as 15 parts by weight, the plate-out preventing effect was exhibited, but discoloration occurred. growing.

[0035]

According to the vinyl chloride resin composition of the present invention, the plate-out prevention effect is great, the film / sheet thickness accuracy is not deteriorated, and the appearance performance such as gloss and roughness of the product surface is good. is there. Further, since the work of removing the contaminants on the surface of each roll is unnecessary, the productivity does not decrease. It also has good thermal stability and does not discolor during processing. In addition, the effect that can prevent "eye phenomenon" in extrusion molding can be expected.

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Claims (3)

[Claims] 1. A polybutadiene copolymer containing butadiene rubber as a rubber component or an acrylic rubber copolymer containing acrylic rubber as a rubber component in 100 parts by weight of a vinyl chloride resin containing 15 to 120 parts by weight of a polyester plasticizer. 0.1 to 10 parts by weight of a vinyl chloride resin composition. 2. A polybutadiene copolymer containing butadiene rubber as a rubber component or an acrylic rubber containing a rubber component as a rubber component in 100 parts by weight of a vinyl chloride resin containing 0.5 to 10 parts by weight of dibasic lead phosphite. A vinyl chloride resin composition comprising 0.1 to 10 parts by weight of a rubber copolymer. 3. A polybutadiene copolymer having a butadiene rubber as a rubber component in 100 parts by weight of a vinyl chloride resin containing 1 to 20 parts by weight of an ethylene-vinyl acetate resin having a vinyl acetate content of 55 to 70% by weight, or An acrylic rubber copolymer containing acrylic rubber as a rubber component is used in an amount of 0.1 to 10
A vinyl chloride resin composition containing 1 part by weight.