JPS588744A - Vinyl chloride copolymer resin composition - Google Patents

Abstract

PURPOSE:To provide the titled resin compsn. having improved thermal stability and flow characteristics, by blending a Ca-Zn stabilizer or a Ba-Zn stbilizer. CONSTITUTION:0-200phr of a plasticizer such as DOP and 1-5phr of a Ca-Zn stabilizer having a ratio of Ca to Zn of 9:1-6:4 or a Ba-Zn stabilizer having a ratio of Ba to Zn of 8:2-6:4 are blended with 100phr of a vinyl chloride random copolymer composed mainly of vinyl chloride and contg. at least 0.05wt% alkylallyl glycidyl ether of the formula, wherein R is H or 1-4C alkyl.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl chloride resin composition with improved thermal stability and fluidity.

Vinyl chloride resin is widely used as a general-purpose resin because it is inexpensive and has excellent physical and chemical properties. However, this resin has poor fluidity when melted and poor thermal stability, so it easily decomposes in the processing and molding area and is known as a resin with poor processability, and various improvement methods are known. .

For example, there are methods of adding various lubricants and processing aids to vinyl chloride resin, or methods of copolymerizing various comonomers with vinyl chloride, but each of these methods has drawbacks.

Lubricants have poor compatibility with vinyl chloride resin, so if they are added in large amounts, they will not only blow out and stain the surface, but also interfere with secondary processing such as adhesion, lamination, and printing, and deteriorate the appearance due to poor gelation. It also leads to a decline in physical properties. The addition of processing aids aims to improve fluidity by blending polymers that are highly compatible with vinyl chloride resin, and does not cause blistering or deterioration of appearance like lubricants do, but processing aids However, the composition is expensive and the resulting composition has poor hardness and tensile strength. Moreover, if a small amount is added without reducing hardness and strength, the fluidity during molding processing will not be improved sufficiently.

Various attempts have been made to random copolymerize vinyl chloride with comonomers such as acrylic acid, methacrylic acid, vinyl alkyl ether, vinyl acetate, and vinylidene chloride, but the resulting copolymers are inferior to vinyl chloride homopolymers. Although fluidity is improved in all cases, thermal stability is reduced in all cases, and overall evaluation of processability is said to be inferior to homopolymers.

As a result of our research into improving the processability of crucible vinyl resin, the present inventors found that a composition obtained by a specific combination of a comonomer copolymerized with vinyl chloride and a stabilizer added to the resulting copolymer. The present invention was completed by discovering that it has excellent thermal stability and good fluidity.

That is, the present invention relates to the general formula alkyl, lglycidylconitel (R, is H or ld
A vinyl chloride copolymer containing 1 to 4 carbon atoms) [], 05 Wt or more, 100 PHR, plasticizer 0 to 200 PHR, Ca-Zn stabilizer or 4
This is a vinyl chloride copolymer resin composition characterized in that it contains 1 to 5 PHR of a Ba-Zn stabilizer.

The vinyl chloride copolymer used in the present invention has vinyl chloride as its main component, and preferably 0.05 wt or more [0.1 to 1.9 wt] of alkyl glycidyl ether [0.1 to 1.9 wt].
It is a random copolymer containing t%. The alkyl group of alkylaryl glycidyl needle is hydrogen or has 1 carbon number
-4 alkyl groups are used, among which allyl glycidyl ether and meta-allyl glycidyl ether are preferably used.

Acrylic glycidyl ether and methacryl glycidyl ether, which have a similar structure to the above-mentioned alkylallyl glycidyl needle, are not preferred because the obtained copolymer has improved fluidity but has lower thermal stability than that of a homopolymer. . If the content of alkyl glycidyl ether in the copolymer is less than 0.05 wt%, the effect of improving fluidity and thermal stability will be small and the object of the present invention will not be achieved. This is not economical since the polymerization yield will be extremely low.

As the plasticizer to be added to the vinyl chloride copolymer in the present invention, any plasticizer that is usually added to vinyl chloride resins can be used.

The blending amount of the above plasticizer is O~ based on the vinyl chloride copolymer.
It can be arbitrarily selected within the range of 200 PHR. The upper limit of the amount of plasticizer blended is set to 200 PHR because the upper limit of the plasticizer absorption capacity of the copolymer is 200 PHR, and it is practically meaningless to add more plasticizer. .

The stabilizer used in the present invention is Ca-Zn based or Ba
- It is a Zn-based composite stabilizer, and if the stabilizer is Ca-Zn-based, it has a Ca to ZnO ratio of 9:1 to 6:4, Ba-
For Zn-based materials, those having a Ba:Zn ratio of 8:2 to 6:4 are preferably used. The blending amount of the above-mentioned stabilizer is 1 to 5 PHR based on the polymer IQQ PHR. If the ratio of Zn in the stabilizer is less than b of Ca or b of Ba, the performance of the stabilizer will be extremely reduced;
The 6th precept is a phenomenon commonly known as Zn burn when the - of Ba is exceeded (
This is a phenomenon in which deterioration progresses rapidly without a certain period of time), which is not desirable. If the amount of stabilizer added is less than I PHR, the stabilizing effect will be insufficient, and if the amount added exceeds 5 PHR, pluming of the stabilizer will occur, both of which are undesirable.

Incidentally, fillers, processing aids, pigments, and the like can be appropriately added to the composition of the present invention within a range that does not impair the purpose of the present invention.

The present invention will be explained in more detail below using Examples and Comparative Examples. The t-copolymerization method and test method used in Examples and Comparative Examples are shown below.

(1) M synthesis method: In a 1.0 m'' stainless steel polymerization vessel purged with nitrogen, vinyl chloride monomer 250114, partially saponified polyvinyl alcohol (saponification rate 80%) 25 (1
, a predetermined amount of alkylarylglycidyl needle, and 500% pure water. After preliminarily stirring at room temperature for 10 minutes, the temperature was raised while stirring, and when the temperature reached 57C, 2.4- 250 g of a 30 titre solution of dimethylvaleronitrile is added, and the polymerization reaction is continued for about 5 hours. After the reaction is completed, unreacted monomers are removed, and the remaining slurry is dehydrated and dried to obtain a polymer. 1. (2) Thermal stability test: Test placed in a car oven adjusted to 180 tl:' Measure the time it takes for the piece to change color.

(at aim: Koka type flow tester (nozzle:
1y3XiO brain, load 1i: 100 wa, temperature 150C
Nufii80t? ) to measure the extrusion rate (6d/s e O).

Examples 1-2, Comparative Examples 1-3 A: Vinyl chloride homopolymer (degree of polymerization 1030), B: 99.5 wt% vinyl chloride and 0 allyl glycidyl ether
．． A copolymer consisting of 5 wt% (degree of polymerization 990),
C: Copolymer consisting of 995 wt% vinyl chloride and 0.5 wt% methallyl glycidyl ether (polymerized rIi98
0), D: Copolymer of 99.0 wt% heel chloride and methacrylic glycidyl ether 1, Qwt% (degree of polymerization 1010), E: Vinyl chloride 95. Owt and vinyl acetate 5. (copolymer consisting of 1wt%** (degree of polymerization 93
0) was prepared according to the polymerization method described above. For each 100 parts of these polymers (A to E), 30 parts of I) OP, Ca-
2 parts of Zn-based stabilizer (1-product ferro product, Cl-10) was blended and kneaded for 10 minutes with a 150 tr 8-inch roll.
Compositions (A' to E') were obtained. Table 1 shows the results of the thermal stability test and fluidity test (150C) conducted on the above composition.

7- Examples 3 to 6, Comparative Example 4 F: 99.0 wt% vinyl chloride and allyl glycidyl ether 1. A copolymer consisting of Qwt (degree of polymerization 950),
G: Copolymer consisting of 99.7 wt% vinyl chloride and allyl glycidyl ether (L3Wt9J (degree of polymerization 1000)
), H: Copolymer consisting of 99.9wt vinyl chloride and 0.1wt1 allyl glycidyl ether (degree of polymerization 103
0) was prepared according to the polymerization method described above. Polymers A and B used in Example 1 and Comparative Example 1 and each of the above polymers () to H
), 30 parts of DOP, Ba-Zn stabilizer (Adeka Argus product, mark AC-169) 2
Blend 5 parts of each and roll 1 part with 180C 8 inch roll.
After kneading for 0 minutes, compositions (A", B", F" to H") were obtained. Table 2 shows the results of the thermal stability test and fluidity test (150 tr) conducted on the above composition.

81 Examples 7 to 8, Comparative Examples 5 to 9 Various stabilizers shown in Table 3 were blended with Polymer G used in Example 5 and Polymer A used in Comparative Example 1, and 180C
A thermal stability test and a fluidity test (180'C) were conducted on the composition obtained by kneading it for 10 minutes using an 8-inch roll. The obtained results are also shown in Table 3.

Section 3 Table-1 Table 5-2 that's all

Claims (1)

[Claims] 0.05 wt'I of the alkyl allyl glycidyl ether (R is H or an alkyl group having 1 to 4 carbon atoms)
A vinyl chloride copolymer characterized by blending 0 to 200 PHR of a plasticizer and 1 to 5 PHR of a Ca-Zn stabilizer or a Ba-Zn stabilizer to 100 PER of a vinyl chloride copolymer containing r or more. Polymerized resin composition.