JPH0431460A - Transparent flexible vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition prevented from undergoing exudation of plasticizer, etc., and improved in the prevention of odor emission and flexibility by mixing a vinyl chloride resin with an ethylene/vinyl acetate/carbon monoxide copolymer a tin mercaptide stabilizer and a tin maleate stabilizer. CONSTITUTION:40-80wt.% ethylene is copolymerized with 10-60wt.% vinyl acetate and 5-30wt.% CO at 160-230 deg.C under high pressure in the presence of a catalyst to obtain an ethylene/vinyl acetate/carbon monoxide copolymer having a melt flow rate (ASTM D 1238 at 190 deg.C under a load of 2.16kg) of 1-500g/10min. 100 pts.wt. vinyl chloride resin is mixed with 30-160 pts.wt. said copolymer, 0.5-1.5 pts.wt. tin mercaptide stabilizer, 0.5-3.0 pts.wt. tin maleate stabilizer and optionally a lubricant, a plasticizer, an antistatic agent, a colorant, a filler, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a transparent flexible resin composition with good moldability, and particularly to a transparent flexible vinyl chloride resin composition with low odor.

[Conventional technology]

Vinyl chloride resin compositions made by blending vinyl chloride resins such as polyvinyl chloride with liquid plasticizers such as dioctyl phthalate have excellent moldability, transparency, and flexibility, so they are particularly suitable for synthetic resin components and Widely used as packaging material for electronic devices, etc.

However, the liquid plasticizer contained in transparent soft vinyl chloride resin compositions oozes out onto the surface and transfers to the synthetic resin components and products such as electronic devices that come into contact with it, causing the product to deteriorate. It has the disadvantage of reducing quality.

Therefore, in order to improve such drawbacks, a resin composition in which an ethylene-vinyl acetate-carbon monoxide copolymer is blended with a vinyl chloride resin has been proposed (for example, Japanese Patent Application Laid-Open No. 48-26228). .

Since this resin composition does not contain a liquid plasticizer, the liquid plasticizer does not ooze out onto the surface of the resin composition or migrate to the parts that are in contact with it, and has excellent transparency and flexibility. .

[Problem to be solved by the invention]

However, as mentioned above, ethylene-vinyl acetate-carbon monoxide copolymer is blended with vinyl chloride resin, and this is melt-kneaded and extruded using a molding machine such as an extruder, for example, into tubes, films, or sheets. When such a molded product is obtained, it is decomposed and colored by the heat during molding, and a strong odor is generated.

As a result, this odor not only deteriorates the working environment, but also causes the problem that the product loses its value.

Therefore, the present invention solves the above-mentioned conventional problems, and prevents the plasticizer from exuding onto the surface of the composition and migrating to the side of the member that comes in contact with it, and also prevents the molten resin from discoloring or decomposing. The purpose of the present invention is to provide a transparent flexible vinyl chloride resin composition which has excellent flexibility and low odor.

[Means and effects for solving the problems] The transparent flexible vinyl chloride resin composition of the present invention has a vinyl chloride resin composition of 10
0 parts by weight, 30-160 parts by weight of ethylene-vinyl acetate-carbon monoxide copolymer, 0.5-160 parts by weight of mercapto-based Sn stabilizer
1.5 parts by weight and malate Sn stabilizer 0.5-3.0
parts by weight, thereby achieving the above object.

The vinyl chloride resin used in the present invention refers to a homopolymer of vinyl chloride, or a copolymer of vinyl chloride as a main component and one or more other monomers.
The dark vinyl chloride resin can be obtained by suspension polymerization, emulsion polymerization, etc. according to conventional methods.

Other monomers to be copolymerized with vinyl chloride include α-olefins such as ethylene and propylene, vinyl esters such as vinyl acetate, unsaturated carboxylic acid esters such as (meth)acrylic acid ester, and vinyl ethers such as alkyl vinyl ethers. vinyl monomers or vinylidene monomers other than the above, such as styrene, acrylonitrile, or vinylidene chloride.

In the present invention, polyvinyl chloride with an average degree of polymerization of 800 to 1,700 or a vinyl chloride-ethylene copolymer with an ethylene content of 2 to 8% by weight and an average degree of polymerization of 800 to 2,000 is particularly preferred. It may be mixed with the vinyl chloride-ethylene copolymer in any proportion.

Further, the ethylene-vinyl acetate-carbon monoxide copolymer used in the present invention can be used, for example, in the above-mentioned JP-A-48-26222
As described in the publication, ethylene, vinyl acetate, and carbon monoxide are fed in a predetermined ratio into an autoclave equipped with a stirrer together with t-butylperoxyisobutyrate or azodiisobutyronitrile as a catalyst. It can be produced by copolymerizing by mixing and stirring at high speed under high temperature (for example, 160 to 230°C) and high pressure (for example, 24,000 to 27,000 ps+).

Further, such an ethylene-vinyl acetate-carbon monoxide copolymer is commercially available8, for example, Elvaloy 741 manufactured by DuPont.

In the above ethylene-vinyl acetate-carbon monoxide copolymer, the content of the ethylene component is 40 to 80% by weight, preferably 50 to 70% by weight, and the content of the vinyl acetate component is 10 to 60% by weight, preferably is 10 to 40% by weight, -
The content of carbon oxide component is 5 to 30% by weight or 5% by weight.
A weight range of ~20 weight percent is desirable. In addition, it is also possible to copolymerize other monomers such as (meth)acrylic acid esters, if necessary.

The above ethylene-vinyl acetate-carbon monoxide copolymer preferably has a melt flow rate of 1 to 500 g/10 minutes, preferably 10 to 50 g/10 minutes.The melt flow rate is determined according to ASTM D 123B or JIS.
Based on K 7210, temperature 190℃, load 2
．． This is a value measured under the condition of 16 kg.

Such an ethylene-vinyl acetate-carbon monoxide copolymer is blended in an amount of 30 to 160 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 30 parts by weight, the composition will have poor transparency and flexibility. vice versa,
If the blending amount exceeds 160 parts by weight, the composition tends to become sticky.

Generally, the above-mentioned vinyl chloride resin and ethylene-vinyl acetate-carbon monoxide copolymer are blended by mixing them, but those obtained as follows can also be used.

(1) So-called graft polymers obtained by radical polymerization of vinyl chloride alone or vinyl chloride and other monomers that can be copolymerized with vinyl chloride in the presence of an ethylene-vinyl acetate-carbon monoxide copolymer. The graft polymer also contains a mixture of ethylene-vinyl acetate-carbon monoxide copolymer and vinyl chloride homopolymer or vinyl chloride copolymer).

(2) Ethylene-vinyl acetate-
A mixture of oxygenated carbon copolymers.

(3) A mixture of the above graft polymer and a vinyl chloride resin.

In addition, as the stabilizer used in the present invention, for example, mercapto-based S commercially available from Nitto Kasei Kogyo Co., Ltd.
n stabilizer (product name: TVS#1320), and malate-based Sn stabilizer (product name: TVS#8102 or TVS
#6LP) is mentioned. Such a stabilizer is a mercapto-based Sn stabilizer O85 to 1.0% per 100 parts by weight of vinyl chloride resin. 5 parts by weight and 0 malate Sn stabilizers
5 to 3.0 parts by weight is blended.

The reason why the stabilizer is blended in the above ratio is as follows.

That is, the mercapto-based Sn stabilizer has 1. This is because if more than 5 parts by weight is blended, the odor of the decomposed product will become noticeable, and if less than 0.5 parts by weight is blended, the molded article will be colored.

On the other hand, the reason why the malate Sn stabilizer is added to the mercapto Sn stabilizer is that the malate Sn stabilizer has lower odor than the mercapto Sn stabilizer. However, malate-based Sn stabilizers lack thermal stability. Therefore, in the present invention, low odor is achieved by minimizing the amount of mercapto Sn stabilizer blended, and the problem of coloring is compensated for by blending low odor malate Sn.

However, the proportion of the malate Sn stabilizer needs to be in the range of 0.5 to 3.0 parts by weight as described above. 3
．． This is because if more than 0 parts by weight is added, ie will ooze out onto the surface of the composition.

The composition of the transparent flexible vinyl chloride resin composition according to the present invention is as described above, but when molding a molded article from the blended composition, lubricants, plasticizers, antistatic agents, colorants, fillers, etc. Compounding agents generally used for vinyl chloride resins may be blended in small amounts as necessary within a range that does not impair the purpose of the present invention.

The blended composition blended as described above is supplied to a molding machine such as an extruder, either as a blended powder or in the form of a pellet after being melt-kneaded, and molded into a mold, such as a tube or film. Or molded into a molded object such as a sheet]
- to be done.

〔Effect of the invention〕

In the present invention, since a specific amount of ethylene-vinyl acetate-carbon monoxide copolymer is blended into the vinyl chloride resin,
It is possible to obtain a resin composition that has excellent transparency and flexibility and does not ooze out a desensitizer. Furthermore, in the present invention,
Since the above-mentioned specific stabilizer is blended, it is possible to sweep a composition that not only has excellent transparency and flexibility, but also has low odor and does not easily cause coloring.

Conventional soft vinyl chloride resin compositions contain large amounts of plasticizers such as dioctyl phthalate, so there is a problem with the liquid plasticizers oozing out onto the surface of the composition or migrating to the parts it comes in contact with. However, as mentioned above, the flexible vinyl chloride resin composition of the present invention does not contain such a liquid plasticizer, so if the plasticizer leaches onto the surface of the composition, it may not be able to affect the parts it comes in contact with. No migration issues arise.

The transparent flexible vinyl chloride resin composition of the present invention has low odor,
Applications where transparency and flexibility are required, such as synthetic resin products, food products, and electronic I! It can be suitably used as packaging materials in various fields such as containers.

[Explanation of Examples]

Hereinafter, non-limiting examples of the present invention will be described.

Disaster ■ Soil vinyl chloride-ethylene copolymer (average degree of polymerization 1300,
Ethylene component content (4%) 100 parts by weight, ethylene-vinyl acetate-carbon monoxide copolymer (Elvaloy 741
; manufactured by DuPont) 100 parts by weight, mercapto-based Sn stabilizer (TVS #1320; manufactured by Nitto Kasei Kogyo) 1 part by weight,
Malate Sn stabilizer (TVS#8102; manufactured by Nitto Kasei Kogyo Co., Ltd.) 0.5 parts by weight, Malate Sn stabilizer (TV
S#6LP; Nitto Kasei Kogyo Co., Ltd.) 1.0 parts by weight, epoxidized soybean oil (0-130P, Adeka Argus Co., Ltd.) 10
parts by weight and 1.0 parts by weight of a lubricant (Hiwax 4202E; manufactured by Mitsui Petrochemicals) were kneaded for 5 minutes with a roll heated to 180°C to create a sheet, which was then cut to obtain pellets. .

This bullet is set at 65m with a T-die with a radius of 650m.
Feed into single screw extruder with width cylinder 1:120°C1
Cylinder 2: 140℃, Cylinder 3: 150℃, T
A sheet with a thickness of 1.0 mm was molded under the conditions of die: 160° C. and extrusion rate: 40 kg/Hr, and odor, transparency, exudation, and yellowing degree ΔYl were evaluated. The evaluation method and results are shown below.

(1) Odor; The odor of the sheet was evaluated by determining the frequency and degree of odor intensity as shown below.

Table 1 As a result of evaluation on 10 adults including men and women, the average value of Example 1 was 1.

(2) Transparency: The total light transmittance of a 1.0 m thick sheet was measured in accordance with JIS K 7105. As a result, in Example 1, the total light transmittance was 91.0%.

(Leakability: A sheet with a thickness of 1.0 mm was left in a hot air bath at 40°C for one month, and the degree of dirt on the sheet surface was observed. As a result, the dirt on the surface of the sheet was I was not able to admit.

(4) Yellowing degree ΔYI: The yellowing degree ΔYl of a 1.0 ms thick sheet was measured in accordance with JIS K 7103. As a result, yellowing degree Δ
Yl was 4.5.

Disaster 1 Spot 1 The amount of mercapto-based Sn stabilizer is 0.5 parts by weight, 7L.
The amount of /-t-based Sn stabilizer TVS #8102 was 1.0.
The same procedure as in Example 1 was carried out except that the parts by weight were changed. As a result, the odor of the sheet was 1/2, and the transparency was 90.5.
%, no exudation was observed, and the yellowing index ΔYl was 5.1.

Comparison ■ The amount of soil mercapto-based Sn stabilizer is 2.0 parts by weight,
A sheet was produced in the same manner as in Example 1 except that the malate-based Sn stabilizer was not blended. As a result, the odor of the sheet was 3, the transparency was 90.8%, no oozing was observed, and the yellowing index ΔY was 4.4.

1.Malate-based Sn stabilizer TVS#8102 content 2.5
A sheet was produced in the same manner as in Example 1 except that the mercapto-based Sn stabilizer was not blended. As a result, the odor of the sheet was 1/2, the transparency was 88.5%,
Bleeding was observed, and the yellowing index ΔYl was 25.

The main compounding amount of the mercapto-based Sn stabilizer was 0.3 parts by weight, 0.5 parts by weight of the malate-based Sn stabilizer (TVS#8102i manufactured by Nitto Kasei Kogyo Co., Ltd.), and the malate-based Sn stabilizer (TVS#
A sheet was produced in the same manner as in Example 1, except that the amount of 6LPi (manufactured by Nitto Kasei Kogyo Co., Ltd.) was 1.0 parts by weight. As a result, the odor of the sheet was 1/2, the transparency was 90.6%, no oozing was observed, and the degree of yellowing ΔY■ was 18.7.

Stabilized twisted soil mercapto-based Sn stabilizer blending amount 1. 0 parts by weight, 2 parts by weight of malate-based Sn stabilizer' (TVS #8102),
A sheet was produced in the same manner as in Example 1, except that the malate-based Sn stabilizer (TVS#6LP) was used in an amount of 2.0 parts by weight. As a result, the odor of the sheet was 1, and the transparency was 87.8.
%, exudation was observed, and the yellowing index ΔYl was 4.2.

Table 2

Claims (1)

[Claims] (1) 100 parts by weight of vinyl chloride resin and 30 to 16 parts of ethylene-vinyl acetate-carbon monoxide copolymer
0.5 to 1.5 parts by weight of a mercapto Sn stabilizer, and 0.5 to 3.0 parts by weight of a malate Sn stabilizer.