JPH0480006A - Manufacture of vinyl chloride resin molded product - Google Patents

Abstract

PURPOSE:To obtain a molded product having an uneven surface reduced in stickiness by scattering vinyl chloride basis polymer particles having a specific mean particle size over the surface of a film formed from a past sol of a vinyl chloride basis resin to melt the same. CONSTITUTION:A paste sol is prepared by uniformly mixing a plasticizer, a stabilizer and an auxiliary agent added if necessary with a vinyl chloride basis resin. The vinyl chloride basis polymer to be used scattered over the surface of the film formed from the paste sol has a mean particle size of 10 - 300 mum, pref., 20 - 200 mum and the degree of the polymerization thereof is 70 or more, pref., 2000 or more because of paste sol of a vinyl chloride basis polymer too low in its degree of polymerization is melted at the time of heating to easily lose surface unevenness. For example, the aforementioned vinyl chloride basis polymer particles are scattered over the surface of the film formed to release paper by continuously applying the plastisol to the release paper in uniform thickness and melted under heating at 150 - 300 deg.C for 1 - 10 min. This molded product generates no close adhesion even in a stacked state and, especially, a glove is low in stickiness when the uneven surface thereof is made inside and easily detached.

Description

[Detailed Description of the Invention] [Industrial Field 11] The present invention provides dip molding, pressure molding,
This invention relates to a method for producing a vinyl chloride molded product with low stickiness by imparting an uneven pattern to the surface of the molded product using processing techniques such as slanche molding and coating molding.

[Prior art] Paste sol is widely used as a molding material for gloves, leather, wallpaper, flooring, etc., but mechanical embossing is the only way to create uneven patterns on the surface of molded products obtained from it. Common methods include processing, gelling a paste sol by pouring it into an embossing mold or embossed paper, and chemically embossing. However, these conventional techniques not only increase post-processing steps such as embossing, but also require embossing rolls, embossing molds, embossing paper, etc., and have the disadvantage that they are economically disadvantageous.

[Problem to be solved by the invention]

The present inventors have realized that without going through processes such as embossing,
They discovered that by simply scattering vinyl chloride polymer particles on the surface of a film formed from a paste sol, it is possible to form an uneven pattern on the surface of a molded product at the same time as molding. Ta.

That is, an object of the present invention is to provide a method for manufacturing a vinyl chloride resin molded article having an uneven surface with low stickiness.

Means for Solving Problem C] Therefore, the gist of the present invention is to provide a method for manufacturing a vinyl chloride resin molded article having an uneven surface from a paste sol. Diameter lO
A method for producing a vinyl chloride resin molded article, which comprises dispersing vinyl chloride polymer particles of ~300 IIm and then melting the particles.

To explain the present invention in detail, the paste sol used in the method of the present invention consists of a vinyl chloride resin for paste (hereinafter referred to as paste resin), a plasticizer, a stabilizer, and if necessary, a filler, a coloring agent, and an oxidizing agent. It is prepared by uniformly mixing inhibitors, ultraviolet absorbing agents, and other additives normally added to vinyl chloride resin using a mixer or the like. Also, the viscosity of paste sol! Vinyl chloride blend resin for 11m may be blended.

Paste resin is generally produced by drying an aqueous latex obtained by emulsion polymerization or fine suspension polymerization of vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable with it, by a method such as spray drying, and then producing a dried agglomerated resin. Manufactured by grinding. Examples of comonomers that can be copolymerized with vinyl chloride include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate; acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; and methyl methacrylate and ethyl methacrylate. Methacrylic acid esters, maleic esters such as dibutyl maleate and diethyl maleate, fumaric acid esters such as dibutyl fumarate and diethyl fumarate, vinyl ethers such as vinyl methyl ether, vinyl butyl ether, vinyl octyl ether, These comonomers include vinyl cyanides such as acrylonitrile and methacrylonitrile, α-olefins such as ethylene, propylene, and styrene, and vinyl halides other than vinyl chloride such as vinylidene chloride and vinyl bromide. It is used in an amount of 30% by weight or less, preferably 20% by weight or less in the constituent components.

The plasticizer added to the paste resin is not particularly limited as long as it is used for vinyl chloride resin, but it depends on the viscosity of the paste sol, the physical properties of the molded product obtained from the paste sol,
It is selected as appropriate depending on the purpose and the like. Typical examples of plasticizers include dibutyl phthalate (DBP), butylhensyl phthalate (BBP), and di-2-ethylhexyl phthalate (D.

P), di-2-ethylhexyl adipate (D.

A), polyester plasticizer, tricresyl phosphate, epoxidized soybean oil, etc. are used alone or in combination of two or more.

The vinyl chloride polymer to be sprayed onto the surface of the film formed from the paste sol has an average particle size in the range of 10 to 300 μm, preferably in the range of 20 to 200 μm. The above-mentioned vinyl chloride blending resin is used as the vinyl chloride polymer with an average particle size in the range of 20 to 50 μm, and for other vinyl chloride polymers, which are usually produced by suspension polymerization, are used to form the desired shape of the molded product. It is used after being sieved to an appropriate particle size depending on the surface unevenness. If the vinyl chloride polymer has a polymerization degree that is too low, it will easily melt when the paste sol is heated and the surface unevenness will disappear (therefore, if the polymerization degree is too low, the surface unevenness will disappear).
It is suitable to use the above number, preferably 2000 or more.

To manufacture a molded article by the method of the present invention, specifically to manufacture a film by a coating method, for example, plastisol is continuously applied to a uniform thickness on a release paper, and the coated surface is coated with an average particle of plastisol. Vinyl chloride polymer particles with a diameter of 10 to 300 μm are scattered and adhered by an appropriate method, and then heated at a temperature of 150 to 300°C, preferably 180 to 280°C.
It is heated and melted together with the coating film at a temperature of °C for 1 to 10 minutes, preferably 2 to 5 minutes. If the heating temperature is high and the heating time is long, the molded product will burn, while if the heating temperature is low and the heating time is short, the physical properties of the molded product will be poor.
It is desirable to select an appropriate condition from the above-mentioned range in consideration of the physical properties of the molded article. In addition, by the dip method, for example,
To manufacture gloves made of vinyl chloride resin, a heated or unheated glove mold is immersed in a paste sol to form a uniform sol film on the glove mold, and then a polyvinyl chloride 4 composite is sprinkled on the mold, and then It is manufactured by a method in which the molten product is heated to the above-mentioned temperature, then cooled, and the molded product is released from the mold. In the case of gloves, it is desirable that the dip thickness be between 0.1 and 0.3. In addition to the above-mentioned molding method, the method of the present invention uses all paste sol processing techniques such as casting and slush molding. Although it varies depending on various conditions such as the degree of polymerization of the polymer and heating conditions, that is, the difference in meltability between the paste sol and the polymer, the degree of the uneven pattern can be easily determined by some preliminary experiments.

[Effects of the Invention] According to the method of the present invention, a molded product having an uneven surface similar to embossing can be produced extremely easily by simply dispersing a vinyl chloride polymer on the film surface of a paste sol and heating and melting it. In addition, the molded products do not stick together even if they are placed in a stacked state, and gloves in particular have low stickiness when rubbed against the uneven surface, do not cause discomfort, and are easy to put on and take off. be.

〔Example〕

Next, the present invention will be explained in detail with reference to Examples, but the method of the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Examples 1 to 6, Comparative Example 1 The following composition (weight ratio) was stirred with a Hobart mixer to prepare a paste sol.

Paste resin (average degree of polymerization 1500. 100 vinyl strength @P415 manufactured by Mitsubishi Kasei Vinyl Corporation) DOP
100 Tin stabilizer (product name T-
17MJ, manufactured by Katsuta Kako) 3 The obtained paste sol was coated on a glass plate with a coating knife to a thickness of 200 μm.
A thick film was formed, and the vinyl chloride polymer shown in Table 1 was uniformly spread and adhered to the surface. Next, it was heated and melted in a gear oven at a temperature of 200°C or 250°C for 3 minutes, and after cooling, it was peeled off from the glass plate to obtain a molded product having an uneven pattern on the surface. The condition of the uneven pattern was judged visually and by touch, and evaluated into the following four categories.

◎; A large and sufficient uneven pattern is observed.

○: A small uneven pattern is observed.

Δ: An uneven pattern is obtained, but the surface is too smooth.

×: An uneven pattern cannot be obtained.

＼ ＼ ＼ ＼ ＼ ＼ Table■ *Mitsubishi Kasei Vinyl Co., Ltd. As can be seen from Table 1, molded products with various uneven patterns can be produced depending on the average degree of polymerization, average particle size, and heating conditions of the spraying polymer. In Example 6, since the average polymerization 1 is low, a better uneven pattern can be produced by methods such as lowering the melting temperature, but when the melting temperature is lowered, the physical properties such as tensile strength of the molded product itself deteriorate, so it is not preferable. I don't think it's a strategy. In addition, the molded product of Example 6 does not stick when simply stacked on top of each other and is easily peeled off.

Example 7 Paste resin (Viniki P415) 100
DOP 80DO
A 20 Epoxidized soybean oil 2 Stabilizer (product name AC
-111, manufactured by Afir Argus Co., Ltd.) 2. Gelling agent (Aerosil) 1. Plastisol was prepared by uniformly stirring the above composition (weight ratio) using a Hobart mixer. After dipping the glove type into the sol and cutting off the drippings of the sol, apply Vinyryoku@90BX or Vinyyoku@P
415 were placed in a tank in which they were suspended, and each was allowed to adhere to the surface of the sol film. Next, it was heated and melted in a heating furnace at a temperature of 280° C. for 3 minutes, and then cooled, and the vinyl chloride resin glove was released from the glove mold so that the surface having the uneven pattern was on the inner surface S (dinbu molding).

Gloves to which Vinyryoku 090BX was attached had a good uneven pattern, had low stickiness when worn with gloves, and were easy to put on and take off. On the other hand, the one to which Vinyryoku@P415 was attached did not have an uneven pattern, stuck tightly to the hand, and also caused discomfort when being put on and taken off.

Patent applicant: Mitsubishi Kasei Vinyl Corporation (1 other person) teenager Reason Man

Claims (3)

[Claims] (1) In the method of manufacturing a vinyl chloride resin molded article with an uneven surface from a paste sol, after scattering vinyl chloride polymer particles with an average particle size of 10 to 300 μm on the surface of a film formed from a paste sol. Method for manufacturing a vinyl chloride resin molded product characterized by melting (2) The method for producing a vinyl chloride resin molded article according to claim 1, wherein the vinyl chloride polymer has an average degree of polymerization of 700 or more. (3) A vinyl chloride resin glove characterized in that vinyl chloride polymer particles having an average particle size of 10 to 300 μm are sprinkled on the surface of a glove-like membrane formed by dipping a glove shape in a paste sol and then melted. Production method