KR910007594B1 - Vinyl chloride-based resin composition - Google Patents

Abstract

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Description

Vinyl chloride resin composition

The present invention relates to a vinyl chloride resin composition having excellent matte properties. Soft vinyl chloride resins have excellent chemical and physical properties and have good gloss and are used in a wide range of applications such as electric wires, films, sheets, and molded articles. However, depending on the application, it is required to have a matte shape. In the case where the light is overlaid and superimposed, there is a drawback in that it is easy to stick and the appearance is insignificant, and improvement thereof is desired.

As a method of obtaining a matte state in the related art, a method of molding a resin at a relatively low temperature, a method of passing it through a roller or the like having a roughened surface, a method of using a high-polymerization vinyl chloride resin having an average degree of polymerization of about 3,000, an inorganic filler or a resin, The method of adding rubber | gum etc. is known.

However, it is difficult to say that all of these methods are satisfactory. For example, in the method of lowering the molding temperature, the workability is remarkably deteriorated, the temperature range of the matte state is narrow, the staining is likely to occur, and the quality control is difficult.

In the case of using a roller having a rough surface or the like, the gloss peculiar to the soft vinyl chloride resin cannot be sufficiently removed, and a stable matte state cannot be obtained.

The method of using a high degree of polyvinyl chloride resin also causes a significant decrease in processability, and a method of narrowing the temperature to a matte state is also a method.

In addition, the method of adding an inorganic filler or a resin also has a small effect, and when it is added to such a degree as to a matte state, the mechanical strength is remarkable and a whitening phenomenon is caused. It is not known.

The inventors of the present invention have made an exception of a method for obtaining a flexible vinyl chloride resin having excellent matteness and excellent workability, and as a result, a special ethylene-vinyl acetate copolymer-vinyl chloride graft copolymer By adding to the vinyl chloride-based resin, the present inventors have found that the object can be sufficiently achieved.

An object of the present invention is to provide a vinyl chloride-based resin that is excellent in mattness, does not change in a matte state over a wide range of molding temperatures, and is excellent in workability and mechanical strength.

That is, ethylene-vinyl acetate copolymer-vinyl chloride graft copolymer 1 graft-polymerized at a pressure not exceeding the saturated medium pressure of the vinyl chloride monomer in the presence of 100 parts by weight of a vinyl chloride-based resin and an ethylene-vinyl acetate copolymer. To provide a vinyl chloride composition consisting of from 100 to 100 parts by weight and a plasticizer 30 to 200 parts by weight.

Hereinafter, the present invention will be described in detail.

The EVA-VC graftmer used in the present invention is produced by a completely different method from the conventional polymerization method performed in the state of dissolving an ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA) in a vinyl chloride monomer. In other words, the polymerization pressure is carried out in the presence of EVA impregnated with the catalyst at a pressure not exceeding the saturated vapor pressure of the vinyl chloride monomer relative to the polymerization temperature. Eventually, it is performed in a state where the monomer concentration is extremely low, in which substantially no vinyl chloride monomer droplets are present. The EVA-VC graft polymer polymerized in such a state has a high graft ratio and a lot of entanglement of molecular chains, and exhibits a completely different effect from the EVA-VC graft polymer prepared by the conventional method.

This polymerization method includes a method of introducing a vinyl chloride monomer in the state of suspending or emulsifying an EVA impregnated with a catalyst in water, or a method of contacting the vinyl chloride monomer in a gaseous phase while the EVA is fixed or flowing. Apply. As the polymerization pressure, a pressure lower than the saturated vapor pressure of the vinyl chloride monomer relative to the polymerization temperature is selected.

The polymerization temperature is selected in the range of 40 to 80 ° C.

As EVA used, it is manufactured by a high pressure radical polymerization method, a solution, or an emulsion neutralization method, and it is preferable that vinyl acetate content is 5 to 60 weight% and a melt index is 0.1 to 400 g / 10min. Outside this range, problems arise in terms of matte, mechanical strength and the like of the obtained composition.

The ratio of EVA component to EVA-VC graftmer is selected in the range of 10 to 90% by weight, more preferably 20 to 90% by weight. When the ratio of EVA is less than the lower limit, it is difficult to mix uniformly with the vinyl chloride resin, and when the ratio is higher than the upper limit, problems such as a decrease in mechanical strength are caused.

The EVA-VC graftmer thus obtained is mixed with a conventional vinyl chloride resin. As the vinyl chloride-based resin, a chloride obtained by copolymerizing a small amount of vinyl chloride homopolymer or monomers such as vinyl acetate homopolymer, acrylic acid esters, acrylonitrile, vinylidene chloride, ethylene, and propylene by suspension polymerization, emulsion polymerization, bulk polymerization, etc. Vinyl copolymers are used.

Although the mixing ratio of the EVA-VC graftmer and the vinyl chloride resin varies depending on the purpose of use, a mixing ratio of 1 to 100 parts by weight of the EVA-VC graftmer with respect to 100 parts by weight of the vinyl chloride resin is preferable. If it exists in these ranges, the composition excellent in matteness, workability, and mechanical strength can be obtained.

In the composition of this invention, a plasticizer is used. There is no restriction | limiting in particular as said plasticizer, For example, phthalic acid ester, such as dibutyl phthalate and dioctyl phthalate, dibasic acid ester, such as dioctyl adipate, and dioctyl sebacate, other phosphate ester, polyhydric alcohol, and its Derivatives, epoxy fatty acid esters, chlorinated paraffins, polyesters, polyethers and the like.

The amount to be used may be selected according to the purpose of use, but it is usually about 30 to 200 parts by weight based on 100 parts by weight of the vinyl chloride resin, and is added at an appropriate time for softening according to each use. It is not impossible to add more than 200 parts by weight, but it is difficult to dry up and causes difficulties in molding.

Moreover, a filler, various modifiers, various additives, etc. are added to the composition of this invention as needed.

Examples of the filler include calcium carbonate, barium sulfate, talc, clay, mica, silica, aluminum hydroxide, magnesium hydroxide, silicates, carbon black, and the like. The addition amount is 100 parts by weight or less based on 100 parts by weight of the vinyl chloride resin.

As the modifier, resins such as ABS, MBS, chlorinated polyethylene, acrylic resins, polyurethanes, and rubbers such as NBR are used as necessary.

In addition, various preparations such as dyes, heat stabilizers, flame retardants, ultraviolet absorbers, lubricants, antistatic agents and antifogging agents may be added.

Next, in the method for producing a composition of the present invention, the composition is mixed with a super mixer, a Hansel mixer, or the like to absorb a plasticizer, and then heated and kneaded with a kneader such as a roll mill, a banbury mixer, a kneading extruder, or the like. And forming into a shape according to each use.

The composition of the present invention can sufficiently exhibit such mattness even if any molding method is applied.

For example, calendar molding, inflation molding, extrusion molding, injection molding, compression molding and the like can be employed. The molding temperature varies depending on the composition, the molding method, etc., but has a very good matte property over a wide range of about 120 to 230 ° C., and also has excellent workability and high speed processing compared to conventional straight vinyl chloride resins. .

It demonstrates concretely by an Example below.

[Production of EVA-VC Grafter]

To a 50-liter autoclave, 20 kg of pure water, 5 g of polyvinyl alcohol and EVA indicated in the first table are added in a pellet form, and 500 ml of a toluene solution, which is a peroxide catalyst, is added. After degassing and nitrogen substitution are repeated, the vinyl chloride monomer is introduced into the gas phase while stirring at low speed, and then graft-polymerized at a predetermined polymerization temperature. The polymerization pressure is maintained during the polymerization at 0.9 times the saturated steam pressure of the vinyl chloride monomer over the polymerization temperature. After the completion of the polymerization, the unreacted monomer is released, and the resulting pelleted graftmer is taken out, dehydrated and dried. The vinyl chloride content in the EVA-VC graftmer is obtained by quantification of Cl.

TABLE 1

[Examples 1 to 8]

To 100 parts by weight of vinyl chloride resin having an average degree of polymerization of 1,300, a predetermined amount of EVA-VC graftmer shown in the first table, 4 parts by weight of tin stabilizer, 100 parts by weight of DOP (dioctylphthalate) as a plasticizer, and 1 weight of pigment Add and mix in a supermixer. The powder obtained is kneaded at 175 ° C. for 5 minutes by a heating roll mill and taken out into a sheet form. The sheet is cut into pellets with a sheet cutter. The pallet is compressed into a sheet form at a predetermined temperature by a 40 mm extruder to observe mattness and workability. The result was put together in the 2nd table | surface, and was shown. Matte tackiness and workability are determined according to the following criteria.

[Matte]

◎: No stain and extremely good matte effect

○: It has a matte effect.

△: smear occurs

×: not showing matt

[Processability]

The state of the extruded sheet is collectively determined.

◎: Extremely good with oiliness and appearance

○: Good with oiliness and appearance

(Triangle | delta): There is a problem with either a meteor or an appearance.

×: inferior with oiliness and appearance

Comparative Example 1

The same operation as in Example 1 was carried out with a composition having 100 parts by weight of a vinyl chloride resin having an average degree of polymerization of 1,300, 4 parts by weight of a tin stabilizer, 100 parts by weight of DOP as a plasticizer and 1 part by weight of a pigment. The results are shown in the second table.

TABLE 2

As apparent from the above results, it was found that the addition of the EVA-VC graftmer maintains the matte even at high temperature and is excellent in workability.

[Examples 9 to 11]

The composition was 100 parts by weight of vinyl chloride resin having an average degree of polymerization of 1,300, 10 parts by weight of EVA-VC graftmer, 4 parts by weight of tin stabilizer, 100 parts by weight of DOP, 30 parts by weight of calcium carbonate and 1 part by weight of pigment, and the same operation as in Example 1. Is done.

The results are shown in Table 3.

The same operation as in Example 1 was carried out with a composition having 100 parts by weight of a vinyl chloride resin having an average degree of polymerization of 1,300, 4 parts by weight of a tin stabilizer, 100 parts by weight of DOP, 30 parts by weight of calcium carbonate and 1 part by weight of a pigment. The results are shown in Table 3.

TABLE 3

[Examples 12 to 14]

Operation similar to Example 2 is performed except having changed the quantity of plasticizers. The results are shown in Table 4.

TABLE 4

Claims (1)

Enylene-vinyl acetate copolymer-vinyl chloride graft copolymer 1 to 100 graft-polymerized at a pressure not exceeding the saturated vapor pressure of the vinyl chloride monomer in the presence of 100 parts by weight of a vinyl chloride resin and an ethylene-vinyl acetate copolymer Vinyl chloride-based resin composition consisting of parts by weight and 30 to 200 parts by weight of a plasticizer.