JPS58168646A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To provide a vinyl chloride resin compsn. having excellent transparency and impact resistance, by blending a specified impact modifier and an ethylene/vinyl acetate/carbon monoxide copolymer with a vinyl chloride resin. CONSTITUTION:An impact modifier capable of forming a transparent blend with vinyl chloride resin and an ethylene/vinyl acetate/carbon monoxide copolymer are blended with a vinyl chloride resin. Examples of the impact modifiers are an arom. vinyl compd./methyl methacrylate/butadiene graft copolymer and an arom. vinyl compd./methyl methacrylate/acrylic graft copolymer. Generally, the impact modifier and the ethylene/vinyl acetate/carbon monoxide copolymer are used in an amount of 5pts.wt. or above per 100pts.wt. vinyl chloride resin. A liquid plasticizer in a weight ratio of plasticizer to the ethylene/vinyl acetate/ carbon monoxide copolymer of 1 or below may be used.

Description

[Detailed description of the invention] The present invention relates to a vinyl chloride resin composition.

More specifically, the present invention relates to a vinyl chloride resin composition with excellent transparency and impact resistance.

Transparent semi-rigid vinyl chloride resin compositions are used in the form of single films or composite films for blister packaging and deep-drawn packaging of foods and medicines, taking advantage of their good vacuum formability and shape retention properties. ing. In most cases, such resin compositions contain a methacrylic acid ester-styrene-grafted butadiene 3, an east shock resistance improver such as a 4r form, and a liquid haze agent such as dioctyl phthalate.

When a sheet formed from such a resin composition is used for packaging as described above, it may be bent or unbalanced during the packaging of the contents, during the transportation of the packaged product, or during the subsequent handling process at the store. Pinholes often occur in the thinner portions of the sheet due to stretching during secondary forming, and this causes an extremely poor barrier property of the sheet, which is often encountered. The occurrence of such pinholes is especially likely to occur when handling packages at low temperatures, for example in a freezer.

The liquid oIITiii agent contributes to improving the transparency and vacuum formability of the sheet, but on the other hand, it significantly impairs the impact resistance of the sheet, 41 and the impact resistance at low temperatures.
We also found that this decrease in impact resistance was the cause of pinholes.

Nine, the sheet's equilibrium impact resistance has a primary relationship with the value of izot impact strength specified in JISK-6740 "Rigid vinyl chloride compounds". Using a sheet with a high izod impact strength is advantageous from a practical point of view as there are fewer pinholes, especially when the izod impact strength at 6°C is 50 J/
It has been confirmed that the use of a sheet of +m, preferably 100 J/m or more, can effectively prevent the generation of pinholes.

That is, it has been found that in order to prevent the occurrence of pinholes, it is necessary to use a plasticizer that does not reduce the impact resistance of the sheet, especially the impact resistance at low temperatures.

As a result of investigating the cause, it was found that when 1 ethylene/If vinyl/carbon oxide copolymer is used in place of or in conjunction with a liquid plasticizer, defects such as pinhole formation are not observed, and it is transparent and impact resistant. It was revealed that a resin composition with excellent properties could be obtained. Therefore, the present invention relates to a vinyl chloride resin composition with excellent transparency and impact resistance, and this resin composition includes an impact modifier that can form a transparent blend with the vinyl chloride resin. and an ethylene/vinyl acetate/carbon oxide copolymer, and, if necessary, a liquid plasticizer such as an aromatic or aliphatic polycarboxylic acid ester.

Vinyl chloride resins include not only vinyl chloride homopolymers, but also other comonomers, such as α-olefins such as ethylene and propylene, vinyl esters such as vinyl acetate and acrylic esters, alkyl vinyl ethers, etc. vinyl ethers, other vinyl halides such as vinyl bromide and vinyl fluoride, and other vinyl compounds such as styrene, acrylonitrile, and vinylidene chloride.
Alternatively, a copolymer tube with a vinylidene compound or the like can be mentioned.

Examples of impact resistance modifiers that can form transparent compounds with these vinyl chloride resins include aromatic vinyl compound-methyl methacrylate craft acrylic polymers (see Aromatic No. 463) and aromatic vinyl compound-methyl methacrylate craft acrylic polymers (Japanese Patent Application Laid-open No. (see Publication No. 51-82339), etc., and these are already commercially available and in use as Kane Ace B series (Kusatsuki Chemical products), Metaplay W series (Mitsubishi Shi/-Men products), etc.

II without inhibiting the effect of such an impact resistance improver.
] Ethylene/vinyl acetate that can be used as 'm' agent -
Carbon oxide copolymer is about 40-80% ethylene by weight.
, preferably about 60-70%, vinyl acetate about 15-6
0%, preferably about 20 to 35%, and -carbon oxide is copolymerized at a ratio of about 5 to 30%, preferably about 5 to 15%, and if necessary, further It is a product obtained by copolymerizing other comonomers, and the details of its manufacturing method are described in, for example, U.S. Patent No. 3. It is described in the specification of '78Q140.

Resin compositions made by blending these impact resistance modifiers and ethylene/vinyl acetate/carbon oxide copolymers with vinyl chloride resins have excellent transparency, impact resistance, and vacuum formability. In order to further improve the molding processability in extrusion mode, a small amount of a liquid plasticizer that has been commonly used can also be added. Generally vinyl chloride resin 1001
The impact modifier is used in an amount of about 6 parts by weight or more, preferably about 10 parts by weight or more, and the ethylene/vinyl acetate/carbon oxide copolymer is added in a proportion of about 51 parts by weight or more, based on 1 part by weight. It is preferably used in a proportion of about 10 parts by weight or more, but when a one-liquid plasticizer is blended, it is used in a weight ratio of 1 or less to the ethylene-vinyl acetate-carbon oxide coelectrolyte. %, preferably less than or equal to about 100 ml. This is because if it is used in a proportion greater than that, the impact resistance strength will be reduced by a large amount.

There are no particular restrictions on the liquid plasticizer, as long as it is a liquid plasticizer that is commonly used as a plasticizer for vinyl chloride resins, such as dioctyl heptalate (DOP), lyoctyl trimellitate, dioctyl adipate, etc. esters or g of aromatic or aliphatic polycarboxylic acids,
Since recall and aromatic polymers are composed of aliphatic dicarboxylic acids, molecular weight polyester plasticizers and the like are used.

The vinyl chloride resin composition according to the present invention can be easily processed into a K film or sheet by a calendar molding method, which is a conventional method for molding a vinyl chloride resin film or sheet, or by an extrusion molding method. It is possible. The formed film or sheet has excellent transparency and scratch resistance, and can be made into a desired shape by adjusting the addition ratio of the ethylene/vinyl acetate/carbon oxide copolymer and the liquid adhesive. Since it has vacuum formability and shape retention properties, it can be appropriately used as a vacuum packaging material for foods or a blister packaging material for mulberry products.

Next, the present invention will be explained with reference to examples.

Example 1 Prepare a mixture with the following composition.

Polyvinyl chloride (average polymerization [800) 10
0 parts by weight This mixture was rolled at 170t using two rolls.
After kneading for 0 minutes, the mixture was pressed for 4 minutes at 1.80 tons to form a press sheet with good transparency.

Comparative Example 1 In Example 1, 15 parts by weight of fiKDOP was used instead of 26 parts by weight of the ethylene/vinyl acetate/carbon oxide copolymer, and a press sheet was formed. The amount of 7tDOP used is
The relative proportions of 3 parts by weight of carbon oxide copolymer and 2 parts by weight of DOP were determined based on the empirical rule that they give sheets of the same flexibility, and were compared with the following examples. The same is true in the example.

When the physical properties of the press sheets obtained in Actual Example 1t4 and Comparative Example 1 are determined, the following 1st! The results shown in iK were obtained.

Table 1 11 U Shikoku 1-u Setman 1lc-j%m Wholesale=Mpupil↓Tensile strength MPa) JIS K-67432a6
2A5 elongation (%) #200 956℃
208 3624℃
lOγδ 54 soft thermal expansion (t) JIS
-6745263F Examples 2 to 5, Comparative Examples 2 to 4 Using the blended raw materials used in Example 1 and Comparative Example 1,
A press sheet was similarly molded from a mixture having the composition shown in Table 2 below.

Examples 8 to 9, Comparative Example b Methyl methacrylate-styrene grafted acrylic polymer (Mitsubishi Rayon product Metablen w-s) was used instead of the methyl methacrylate-styrene grafted butadiene polymer
A similar press sheet was molded from a mixture having the composition shown in Table 4 below using the blended raw materials used in Example 1 and Comparative Example 1, except that oo) was used.

Table 4 Polyvinyl chloride loo 100
100-carbon oxide copolymer 25 15
-DOP
-615 Acrylic polymer 15
15 15 dioctyltin mercapto
2 2 2 dibutyltin dilaurate α
6 α6 α5 Montanic acid wax
α2 α2 α2 obtained good press sea) O1
The results are shown in Table 6 below.

Table 6 Measurement Items Example 8 Example 9 Comparative Example δ Tensile Strength (MPa) 3 Upper 5 3
L3 2a6 elongation (%) 204 215
105 Izot Kayabusa J/711) 5℃ 1 to U F0 3424℃ 83
0 640 60 Soft temperature ('C)
29 33 38 Agent Patent Attorney Toshio Yoshida Proceeding Amendment (Spontaneous) October 1982
May 27th, Commissioner of the Japan Patent Office Yasugi, Ka-1 1. Indication of the case 1982 Patent Application No. 54073 2. Name of the invention Vinyl chloride resin composition 3. Person making the amendment Relationship to the case Name of patent applicant 4 Polychemical Co., Ltd. 4, Agent address: 5 Mayuya Building, 1-2-7 Shiba Daimon, Minato-ku, Tokyo
01 No. 5, Scope of Claims column and Detailed Description of the Invention column 6 of the specification to be amended, Contents of the amendment (1) ``Permission request 0 scope 2 Attachment 0 as shown in page 27, (2)
"Vinyl esters such as vinyl acetate, etc." in lines 2 and 3 of page 5 are replaced with "vinyl esters such as vinyl acetate, α,β-unsaturated carboxylic acid esters of acrylate esters, etc." ” is corrected.

〔Attachment〕

Claim 1: Transparency and impact resistance obtained by blending a vinyl chloride resin with an impact modifier that can form a transparent compound with the resin and an ethylene/vinyl acetate/carbon dioxide copolymer. A vinyl chloride resin composition with excellent properties.

Claim 1, wherein the impact modifier is blended in an amount of about 5 parts by weight or more per 100 parts by weight of the vinyl chloride resin.
The vinyl chloride resin composition described in .

2. The vinyl chloride resin composition according to claim 1, wherein the ethylene/vinyl acetate/carbon oxide copolymer is blended in an amount of about 5 parts by weight or more per 100 parts by weight of the vinyl chloride resin.

4. Claim 1 further containing a liquid plasticizer
The vinyl chloride resin composition described in .

5. The vinyl chloride resin composition according to claim 4, wherein the liquid plasticizer is an ester of an aromatic or aliphatic polyvalent carbon fiber.

6. Vinyl chloride 'Ji according to claim 4 or @5, wherein the oily flexible ψ side is used in a weight ratio of 1 or less to the ethylene/vinyl acetate/carbon oxide copolymer. ! , IN fat composition.

Claims (1)

[Claims] Transparency obtained by blending a vinyl chloride resin with an anti-storm reforming agent that can form a transparent compound with the resin and an ethylene/vinyl acetate/carbon oxide copolymer. and a vinyl chloride resin composition with excellent impact resistance. Claim 1, wherein the λ shock-resistant storm reformer is blended in a proportion of about 6 parts by weight or more per 100 parts of vinyl chloride resin.
The vinyl chloride resin composition described in . 9. The vinyl chloride resin composition according to claim 1, wherein the ethylene/vinyl acetate/carbon oxide copolymer is added in a proportion of about 6 parts by weight or more per 100 parts by weight of the vinyl chloride resin. 4.1! 9. The vinyl chloride resin composition according to claim 1, wherein a liquid softening agent is blended into the vinyl chloride resin composition. 2. The vinyl chloride resin composition according to claim 1, wherein the liquid opaque agent is an ester of an aromatic or aliphatic polycarboxylic acid. Claim 4 or #!, wherein the G liquid plasticizer is used in a weight ratio of 1 or less to the ethylene/vinyl acetate/carbon oxide copolymer. The vinyl chloride resin composition according to item 5.