JPS6333457A - Vinyl chloride plastisol composition - Google Patents

Abstract

PURPOSE:A plastisol composition capable of providing a molded article having improved non-migration and mildew resistance, obtained by blencing a vinyl chloride resin for paste with a side chain-containing lactone polymer or an oxycarboxylic acid polycondensate. CONSTITUTION:(A) 100pts.wt. vinyl chloride resin having <=30wt%, preferably <=20wt% comonomer content is blended with (B) 25-400pts.wt. side chain- containing lastone polymer(preferably poly-beta-methyl-delta-valerolactone) having >=1,000, preferably 3,000-100,000 weight-average molecular weight or oxycarboxylic acid polycondensate (preferably 3-methyl-5-hydroxyvaleric acid) and, if necessary, other plasticizer, stabilizer, colorant, etc., to give the aimed vinyl chloride type plastisol composition.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a new vinyl chloride plastisol composition, and more specifically, it has excellent so-called non-migration properties without migration of plasticizer from inside the molded product, and The present invention relates to a vinyl chloride plastisol composition that can provide molded articles having mold-proof properties.

``Prior art'' Vinyl chloride, *W resin, can have its physical properties changed over a very wide range by adding plasticizers, and is widely used industrially as a thermoplastic resin suitable for various uses. . Among vinyl chloride resins, vinyl chloride resin for paste becomes plastisol by blending with a plasticizer and can be easily processed, so it has great industrial utility value.Plasticizers for plastisol include dioctyl 7-talate and other plasticizers. Fatty acid esters such as 7-talate ester and nooctyl adibate have excellent plasticizing efficiency and are the most common. However, these plasticizers have a tendency to migrate from the inside of the molded product to the surface, and molded products containing them not only deteriorate in physical properties over time due to a decrease in the amount of plasticizer (this molded product and other If one resin molded product is brought into contact with the other resin molded product for a long time, the plasticizer will migrate to other resin molded products, causing alteration and deterioration of the resin molded product.

For the purpose of non-migration, attempts have been made to use trimellitic acid ester plasticizers and liquid polyester plasticizers obtained by condensation polymerization of 7-divic acid, ethylene glycol, 1,3-butanediol, etc., or their combined use. However, although the transferability is improved to some extent, it is difficult to obtain a polymer with a high molecular weight necessary to achieve sufficient non-migration, and these plasticizers have a zero value price, and the plasticizer efficiency is lower than the above-mentioned value. In order to obtain the same plasticizing efficiency, a large amount of expensive plastic must be used, which is not only economically disadvantageous, but also causes a large amount of plasticization in the resulting molded product. The inclusion of plasticizers causes other adverse effects and cannot be used as a general purpose plasticizer for plastisol compositions.

In order to achieve a high degree of non-migration, flexible polymeric compounds, such as ethylene-
Attempts have been made to blend vinyl acetate copolymer, ethylene-7N oxide-vinyl acetate copolymer, thermoplastic polyurethane, NBR, etc. into vinyl chloride resin, but none of these polymer compounds are solid or solid. It is a semi-solid and cannot be a plastisol.

"Problems to be Solved by the Invention" In view of the above circumstances, the inventors of the present invention have conducted extensive studies on obtaining molded products from plastisol compositions that do not transfer plasticizers, and have found that, among lactone-based polymers, We discovered that a lactone polymer with a lactone polymer has low crystallinity and is liquid even if it has a high molecular weight, and by blending the lactone polymer as a plasticizer in a vinyl chloride The present inventors have discovered that it is possible to obtain a molded product with excellent migration properties and mildew resistance, and have completed the present invention.

That is, an object of the present invention is to provide a vinyl chloride-based plastisol composition from which molded articles with excellent non-migration and anti-mold properties can be obtained.

"Means for Solving the Problems" However, the gist of the present invention is the average weight molecule per 10-11 parts of vinyl chloride resin for paste? -4
A vinyl chloride plastisol composition is prepared by mixing 25 to 400 parts by weight of a lactone polymer or oxycarboxylic acid condensation polymer having 1000 or more iIl chains.

To explain the present invention in detail, the vinyl chloride resin for paste used in the vinyl chloride plastisol composition of the present invention is a fine suspension of vinyl chloride or a mixture of vinyl chloride and a copolymerizable copolymer thereto. Any resin manufactured by a method commonly applied to the production of vinyl chloride resin for pastes, such as a polymerization method or an emulsion polymerization method, can be used.

Therefore, examples of comonomers that can be copolymerized with vinyl chloride include vinyl esters such as vinyl acetate, vinyl propionate, vinyl turate, methyl 7-acrylate,
Acrylic esters such as ethyl 7-acrylate and butyl acrylate; methacrylic esters such as methyl methacrylate and methyl methacrylate; maleic esters such as diptyl maleate and diethyl maleate; Maric acid esters, vinyl ethers such as vinyl methyl ether, vinyl butyl ether, vinyl octyl ether,
Examples include vinyl cyanides such as acrylonitrile and methacrylonitrile, a-olefins such as ethylene, propylene, and styrene, and vinyl halides other than vinyl chloride such as vinylidene chloride and vinyl bromide. 30% by weight or less in the constituent components of the system resin,
It is preferably used in a range of 20% by weight or less.

Of course, the comonomers are not limited to those mentioned above.

The lactone polymer, which is one of the components used in the composition of the present invention, is a lactone that easily undergoes ring-opening polymerization as a lactone having 0gA chain, the component of which is a polymer of lactone having an iIl chain. For example, a-methyl-β-propiolactone, α,α-dimethyl-β-propiolactone, β-propiolactone, etc. are not particularly limited.
-Methyl-β-propiolactone, α-ethyl-β-propiolactone, β-methyl-δ-valerolactone, methyl-ε-caprolactone, trimethyl-ε-caprolactone, trimethyl-ε-caprolactone, etc.
Those with 4-shell rings, 6-shell rings, and 7-shell rings are preferred because they easily undergo ring-opening polymerization. In addition, β-methyl-δ-valerolactone was subjected to ring-opening polymerization because it has an asymmetric carbon, has low crystallinity, becomes liquid even in the range of high European average molecular weight, and is easily available industrially. It is most preferable to use poly-β-methyl-δ-valerolactone, and as the oxycarboxylic acid, those having the number of carbon atoms corresponding to the above-mentioned lactone can be used. For example, 3-methyl-5-hydroxy- Valeric acid is preferred and is polycondensed. The weight average molecular weight of these lactone polymers or the corresponding polycondensates of oxycarboxylic acids is preferably 1,000 or more, and desirably 3,000 or more in order to achieve light migration properties. If the weight average molecular weight is less than 1000, the negative effects of the lactone polymer's base groups on the vinyl chloride plastisol composition will become stronger, such as the transparency of the vinyl chloride plastisol composition will deteriorate. In addition, from the viewpoint of non-migration, it is desirable that the molecular weight of the lactone polymer is large, but on the other hand, if the molecular weight becomes large, not only will the ability to plasticize the vinyl chloride resin for paste decrease, but also the lactone polymer will have a large molecular weight. Too
Advantageously, it is less than or equal to ooo.

Therefore, the composition ratio of vinyl chloride resin I for paste (fat and lactone polymer or oxycarboxylic acid condensation polymer) varies depending on the desired degree of plasticization of the vinyl chloride resin for paste and the use of the plastisol composition. Although it varies depending on the requirements, the latter can be determined as appropriate from the range of 25 to 400 parts by weight per 1 part by weight of the former. It is usually produced by uniformly mixing acid condensation polymers at room temperature.

If the lactone polymer content is less than 25 parts by weight, it will be difficult to obtain a plastisol composition from the vinyl chloride resin for paste, while if it exceeds 400 parts by weight, it will be difficult to mold from the vinyl chloride resin for paste. When manufactured, it becomes difficult to maintain its shape.

The composition of the present invention contains vinyl chloride for paste, [so-called and
In addition to the lactone polymer, other plasticizers,
It can contain stabilizers, colorants, blowing agents, crosslinking agents, fillers, etc.

"Effects of the Invention" Since the vinyl chloride plastisol composition of the present invention is used as a plasticizer for vinyl chloride resins, even if molded products obtained from the composition come into contact with other 11 resin molded products, they will not remain plastic. Since the agent exhibits good non-migration properties and does not contain plasticizers with a molecular weight lower than 1000, phenomena such as extraction of plasticizers do not occur, and therefore no change in the hardness of the molded product over time is observed. do not have.

Therefore, the composition of the present invention has high utility value as a material for automobile interior materials, wallpaper, flooring materials, medical films or tubes, packing materials, and the like.

"Examples" Next, the vinyl chloride plastisol composition of the present invention will be described in detail in Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

The viscosity, migration properties, and changes in hardness of the vinyl chloride plastisol compositions obtained in each of the Examples and Comparative Examples were evaluated by the following methods.

Viscosity> A lactone polymer or a plasticizer, a stabilizer, etc. as shown in Table 1 are blended with a vinyl chloride resin for paste, and a plastisol composition is obtained using a hover mixer or the like in a conventional manner. , Shear rate 1, 35 using Weisenberg viscometer
The viscosity in ec-- was measured.

Transferability〉 The plastisol composition obtained in the viscosity evaluation was placed on a glass plate at approx.
．． After coating to a thickness of 6 mm, heat and melt at 200°C for 5 minutes to form a sheet. ), 160° by stacking multiple pieces of the
C, press for 5 minutes under the conditions of 100kg/c+*2,
A sheet with a thickness of 3 mm was shaped into an rR shape. A test piece with a width of 2 mm and a length of 50 mm was cut out from this press sheet, and its transferability was evaluated under two conditions: dry and wet.

The evaluation criteria were as follows: No change in the surface condition was visually observed as an O mark, and the evaluation was graded into four grades: 01Δ, X, from good to good.

Dry conditions: Layer the test piece on each of the polystyrene sheet, ABS sheet, and metallic painted sheet, sandwich this between glass plates, and dry for 30 minutes.
After being left in the open at 60° C. for 7 days under a back mold of 0 gr, the test pieces were separated by 94° and the surface condition of each sheet was examined.

Wet conditions: After leaving the test piece alone in an oven adjusted to a temperature of 80°C and a humidity of 90% for 12 days, the test piece was taken out, and the test piece was further tested in the same manner as under dry conditions. The surface condition of each ABS sheet and metallic painted sheet was investigated.

Hardness change〉 Transition U, using the sheet created for the test, JIS
Hardness was measured according to K6301. Furthermore, 25 sheets
The hardness was measured after standing at ℃ for 3 months.

<Mold Resistance> The sheet prepared for the migration test was cut to a size of 100 cm and pasted on the inside of a thermostatic water tank containing water at 30°C, and mold growth was visually observed and evaluated after one month.

The evaluation criteria were as follows.

0 Niji-), no symptoms were observed.

O: Mildew was observed on 1/3 or less of the sheet.

Δ: Mildew growth is observed on 1/3 to 2/3 of the sheet.

×: Mildew was observed on two or more layers of the sheet.

Example 1 Vinyl chloride resin for paste (trade name Vinyiki P-440 (
100ia parts of Mitsubishi Kasei Vinyl Co., Ltd. (5t)) are blended with poly-β-methyl-δ-valerofuctone somts having an average weight molecular content of 12,000 and a hydroxyl value of 9, and 1 part of Ba/Zn-based stabilizer triple J. Plastisol was obtained and subjected to evaluation of viscosity, hardness, and migration properties.

Example 2 Evaluation was performed in the same manner as in Example 1, except that poly-β-methyl-δ-parellolaccine having a molecular weight of 2000 and a hydroxyl group of 1157 was used in Example 1.

Example 3 Evaluation was performed in the same manner as in Example 1, except that the amount of poly-β-methyl-δ-valerolactone was changed to 100 parts by weight.

Example 4 Evaluation was carried out in the same manner as in Example 1, except that in Example 1, the vinyl chloride resin for paste was used as Vinyiki R-1069 (trade name, manufactured by Mitsubishi Kasei Vinyl Co., Ltd.).

Example 5 Evaluation was carried out in the same manner as in Example 2, except that the vinyl chloride resin for paste used was the trade name VI=*R-1069.

Example 6 In Example 1, 5x parts of mineral spirit were further blended and evaluated.

Comparative Example 1 Except for using a trinolift acid ester plasticizer (trade name D-1170 (manufactured by Mitsubishi Kasei Vinyl Corporation)) in place of poly-β-methyl-δ-valerolactone in Example 1, Evaluation was performed in the same manner as in Example 1.

Comparative Example 2 Poly-β-methyl-δ-parerolac) in Example 1
General-purpose polyester plasticizer (product name D-40)
9 (manufactured by Mitsubishi Kasei Vinyl Co., Ltd.)) was used, but evaluation was performed in the same manner as in Example 1.

Claims (3)

[Claims] (1) Per 100 parts by weight of vinyl chloride resin for paste,
A vinyl chloride plastisol composition comprising 25 to 400 parts by weight of a lactone polymer or oxycarboxylic acid condensation product having a side chain having a weight average molecular weight of 1000 or more. (2) The vinyl chloride plastisol composition according to claim 1, wherein the lactone polymer is poly-β-methyl-δ-valerolactone. (3) The vinyl chloride plastisol composition according to claim 1, wherein the oxycarboxylic acid condensation product is a polyester of 3-methyl-5-hydroxyvaleric acid.