JP3067173B2 - Manufacturing method of vinyl chloride resin molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides an uneven pattern on the surface of a molded product formed by a processing technique such as dip molding, casting, slush molding, and coating molding using a paste sol. And a method for producing a vinyl chloride molded article having low adhesiveness.

[Conventional technology]

Paste sols are widely used as molding materials for gloves, leather, wallpaper, flooring materials, and the like. As a method of forming a concavo-convex pattern on the surface of a molded product obtained from the paste sol, a method of mechanically embossing, embossing, A method of pouring a paste sol into a mold or embossed paper to form a gel, a method of chemically embossing, and the like are common. However,
These conventional techniques not only increase the number of post-processing steps such as embossing, but also require an embossing roll, embossing type, embossed paper, etc., and have the disadvantage that economic disadvantages cannot be avoided.

[Problems to be solved by the invention]

The present inventors formed a concavo-convex pattern on the surface of a molded article at the same time as molding by simply spraying particles of a vinyl chloride polymer on the film surface formed from the paste sol without going through a process such as embossing. They have found that they can do this and have completed the present invention.

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

[Means for solving the problem]

Thus, the gist of the present invention is to provide a method for producing a molded article of vinyl chloride resin having irregularities on the surface from a paste sol.
A method for producing a molded article of vinyl chloride resin, characterized in that vinyl chloride polymer particles having an average degree of polymerization of 2,000 to 300 μm are sprayed and then melted.

DETAILED DESCRIPTION OF THE INVENTION In detail, the paste sol used in the method of the present invention is obtained by adding a plasticizer, a stabilizer and, if necessary, a filler, a colorant, and an antioxidant to a vinyl chloride resin for paste (hereinafter referred to as paste resin). It is prepared by uniformly mixing an agent, an ultraviolet absorber, and other auxiliaries usually added to a vinyl chloride resin using a mixer or the like. Further, a polyvinyl chloride resin for adjusting the viscosity of the paste sol may be blended.

Paste resin is generally obtained by drying an aqueous latex obtained by emulsion polymerization or fine suspension polymerization of vinyl chloride or a mixture of vinyl chloride and a copolymerizable co-monomer by spray drying or the like, and drying and aggregating the resin. Manufactured by grinding. Examples of comonomers copolymerizable 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, methacrylic esters such as methyl methacrylate and ethyl methacrylate, maleic esters such as dibutyl maleate and diethyl maleate, dibutyl fumarate and diethyl fumarate Fumaric acid esters, vinyl methyl ether, vinyl butyl ether, vinyl ethers such as vinyl octyl ether, acrylonitrile, vinyl cyanides such as methacrylonitrile, ethylene, propylene,
Α-olefins such as styrene, vinylidene chloride, and vinyl halides other than vinyl chloride such as vinyl bromide. These comonomers are 30% by weight or less, preferably 20% by weight or less, of the components of the paste resin. Used in range.

The plasticizer to be added to the paste resin is not particularly limited as long as it is used for the vinyl chloride resin, and is appropriately selected according to the viscosity of the paste sol, the physical properties of the molded product obtained from the paste sol, the application, and the like. Representative examples of the plasticizer include dibutyl phthalate (DBP), butylbenzyl phthalate (BBP), di-2-ethylhexyl phthalate (DOP), di-2-ethylhexyl adipate (DOA),
A polyester plasticizer, tricresyl phosphate, epoxidized soybean oil or the like is used alone or in combination of two or more.

As the vinyl chloride polymer to be sprayed on the film surface formed from the paste sol, one having an average particle diameter in the range of 10 to 300 μm, preferably 20 to 200 μm is used. For the vinyl chloride polymer having an average particle diameter in the range of 20 to 50 μm, the above-mentioned vinyl chloride-blending resin is used, and in other cases, the vinyl chloride polymer usually produced by suspension polymerization is a desired product of the molded article. It is used after appropriately sieving to a particle size according to the surface unevenness. If the vinyl chloride polymer has a very low degree of polymerization, the paste sol is easily melted when the paste sol is heated and the surface irregularities are easily lost. In the method of the present invention, an average degree of polymerization of 2,000 or more is used.

In order to produce a molded article by the method of the present invention, specifically, to produce a film by a coating method, for example, a plastisol is continuously applied to a release paper to a uniform thickness, and the average particle size is applied to the coating surface. A vinyl chloride polymer particle having a diameter of 10 to 300 μm is sprinkled and adhered by an appropriate method, and then
At a temperature of 150-300 ° C, preferably 180-280 ° C,
Heat and melt together with the coating under the conditions of 10 minutes, preferably 2 to 5 minutes. If the heating temperature is high and the heating time is long, the molded product will burn, whereas if the heating temperature is low and the heating time is short, the physical properties of the molded product will be inferior. It is desirable to appropriately select from the range.
Further, for example, to manufacture a vinyl chloride resin glove by a dipping method, a heated or unheated glove mold is immersed in a paste sol to form a uniform sol film on the glove mold, and then the vinyl chloride is formed. It is produced by a method in which a system polymer is sprayed and then heated to the above-mentioned temperature, the melt is cooled, and the molded article is released. For gloves, dip thickness is 0.1 ~
Desirably 0.3 mm. The method of the present invention, in addition to the above-mentioned molding method, casting, all processing techniques of paste sol such as slush molding are used, the uneven pattern of the molded product surface, the viscosity of the paste sol, the average particle size of the spray polymer, The degree of the concavo-convex pattern can be easily determined by a few preliminary experiments, although it depends on various conditions such as the degree of polymerization of the polymer and heating conditions, that is, the difference in the meltability between the paste sol and the polymer.

〔The invention's effect〕

According to the method of the present invention, it is possible to extremely easily produce a molded article having the same uneven surface as embossing simply by spraying and melting the vinyl chloride polymer on the film surface of the paste sol, The molded article does not adhere even when it is placed in a laminated state, and gloves in particular have low tackiness when the uneven surface is on the inside, do not cause discomfort, and are easily detachable.

〔Example〕

Next, the present invention will be described in detail in Examples, the method of the present invention,
The present invention is not limited to the following examples unless the gist is exceeded.

Examples 1 and 2, Comparative Examples 1 to 4 The following composition (weight ratio) was stirred with a Hobart mixer to prepare a paste sol.

 Paste resin (average degree of polymerization 1500, binica P415 Mitsubishi
100 DOP 100 Tin-based stabilizer (product name: T-17MJ, manufactured by Katsuta Kako) 3 Apply the obtained paste sol on a glass plate.
Using an IF, a film was formed to a thickness of 200 μm, and as shown in Table 1,
A vinyl chloride-based polymer was uniformly dispersed and adhered to the surface.
Then in a gear oven at a temperature of 200 ° C or 250 ° C for 3 hours.
After heating and melting for 5 minutes, this was separated from the glass plate after cooling,
A molded article having an uneven pattern on the surface was obtained. The state of the uneven pattern
Judgment was made visually and by touching fingers, and the following four evaluations were made.

 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.

 ×: Uneven pattern was not obtained.

As can be seen from Table 1, molded articles having various uneven patterns can be produced depending on the average degree of polymerization, the average particle size, and the heating conditions of the spraying polymer. In Example 4, the average degree of polymerization is low, so that a better uneven pattern is produced by a method such as lowering the melting temperature. However, when the melting temperature is lowered, the physical properties such as the tensile strength of the molded article itself are lowered, which is very preferable. It doesn't seem to be a solution.
Further, the molded article of Example 4 does not stick by simply overlapping, but easily peels off.

Example 3 Paste resin (binica P415) 100 DOP 80 DOA 20 Epoxidized soybean oil 2 Stabilizer (AC-111, manufactured by Adeka Argus Co.) 2 Gelling agent (Aerosil) 1 Homogenize the above composition (weight ratio) with a Hobart mixer
The plastisol was prepared by stirring. Soak the glove mold in the sol
After pickling and dripping the sol, binica Floating 90BX
Each of them was placed in a tank, and each was attached to the sol film surface. Next
In a heating furnace, heat and melt at 280 ° C for 3 minutes and then cool
And the PVC resin gloves have an uneven pattern from the glove type
The mold was released so that the surface of the mold became the inner surface (dip molding).

Comparative Example 5 Binica Binica instead of 90BX After using P415
Outside, molded vinyl chloride resin gloves in the same manner as in Example 3.
did.

 Binica Good uneven pattern can be obtained with 90BX attached
Is less sticky when wearing gloves
It was easy. Meanwhile, Binica The one with P415 attached is concave
No convex pattern, close contact with hand, and uncomfortable when detached
Gave.

Claims (1)

(57) [Claims] 1. A method for producing a molded article of vinyl chloride resin having irregularities on a surface thereof from a paste sol, wherein a film having an average particle size of 10 to 300 μm and an average degree of polymerization of 2,000 or more is formed on the surface of the film formed from the paste sol. A method for producing a vinyl chloride-based resin molded product, comprising: spraying and melting vinyl chloride-based polymer particles.