KR100196340B1 - Vinyl chloride resin composition - Google Patents

Abstract

A vinyl chloride resin composition comprising 0.002 -.0.02 moles of zinc carboxylate per 100 G of vinyl chloride resin and 0.3-5 moles of compound having two or more alcoholic hydroxyl groups in one molecule per mole of zinc carboxylate. This composition produces a product having a good chlorine-membrane surface due to the irregularities of the fine wrinkles formed on the surface.

Description

Vinyl Chloride Resin Composition and Chlorine (Chlorine)-Sasang Products

The present invention relates to vinyl chloride resin compositions for vinyl chloride resin products, and to chlorine-finish products or surface chlorine treated products produced therefrom.

In applications such as wall coverings, flooring, vehicle interiors, power lines and everyday goods, the demand for chlorine-finish vinyl chloride resin products is increasing when one wants surface gloss and reduction, glare-free reflections, dry feel, and a smooth appearance. Chlorine-finding methods include several methods: (1) physically rough surface formation, (2) compounding with specific components that produce rough surfaces, or (3) coating the surface with a cloudy lacquer.

Method (1) includes embossing, sand blasting, and scattering into fine particles during the molding process with a microstructured pin die.

A disadvantage of mechanical embossing is that it is unsatisfactory chlorine- mapping due to the viscoelasticity of the material resulting in the blurring of the embossed circles that occur after the embossing operation. Another disadvantage of mechanical embossing is that the embossing die is contaminated during the embossing operation. Sand blasting is only applicable to products with hard surfaces and requires a complex mechanism for trapping and recovering fine particles. Scattering fine particles also requires special equipment for constant scattering and recovery of fine particles.

Method (2) is a vinyl chloride resin with different particle diameters, blending, blending with vinyl chloride resin with different degrees of polymerization, incorporation into certain polymers other than vinyl chloride resin, partial crosslinking, and calcium carbonate Incorporation of the same amount of inorganic filler. The first three methods have the disadvantage of being highly dependent on the molding conditions, i.e. a satisfactory chlorine effect is not obtained at high temperature molding temperatures. The incorporation of large amounts of filler adversely affects the physical properties of the product, i.e. reduces the tensile strength.

Method (3) is effective for chlorine- mapping but economically inferior in requiring special coating materials and additional steps for coating and drying.

The present invention has been completed to address the above-mentioned problems with conventional chlorine-finding processes for vinyl chloride resin products.

It is an object of the present invention to provide a good chlorine-finding surface because of its ability to form uniformly small irregularities when squeezed by an apparatus for casting, dipping, or coating of plastisol or organosol. It is to provide a vinyl chloride resin composition for producing a molded article having.

The present invention relates to a vinyl chloride resin in which 0.002-0.02 mol of zinc carboxylate and 0.3-5 mol of compound having two or more alcoholic hydroxyl groups in one molecule per mol of zinc carboxylate are mixed with 100 g of vinyl chloride resin. In the composition.

The vinyl chloride resin composition of the special composition mentioned above produces a molded article having fine chlorine-finishing facets of fine wrinkles.

The vinyl chloride resin composition of the present invention is based on a vinyl chloride resin that is a homopolymer of vinyl chloride, or a vinyl chloride copolymer or a mixture thereof with a comonomer copolymerizable with vinyl chloride. Exemplary comonomers include vinyl acetate, acrylate esters, and methacrylate esters.

Vinyl chloride resins used in the present invention are usually produced by emulsion polymerization, particulate suspension casting, suspension polymerization, or bulk polymerization. This is not particularly limited to the particle diameter. Their average diameter ranges from 0.1 to 200 μm. Preference is given to those having an average diameter of 0.1-80 μm, which are used in plastisol or organosol form.

The zinc carboxylates used in the present invention should preferably be zinc salts of monocarboxylic acids with 3-18 carbon atoms. One or more zinc carboxylates may be used. Examples include zinc octanoate, zinc hexanoate, zinc butanoate, zinc propionate, zinc narrowanoate, zinc pentanoate, zinc nonanoate, zinc decanoate, zinc 2-ethyl hexanoate, Zinc laurate, zinc palmitate, and zinc stearate. Zinc salts of mono carboxylic acids having 6 to 10 carbon atoms are preferred because they are liquid at room temperature and readily soluble in common hydrocarbons or carbitol solvents, which facilitates uniform diffusion into the vinyl chloride resin, thereby Reduce the amount required for effectiveness.

According to the invention, the zinc carboxylate should be incorporated at 0.002 -.0.02 moles, preferably 0.0025-0.002 moles per 100 g of vinyl chloride resin. In amounts of up to 0.002 moles, zinc carboxylate does not add a satisfactory chlorine- mapping effect and is only a waste.

Zinc carboxylates are heat stabilizers for vinyl chloride resins and are often used in combination with alkaline earth metal salts of carboxylic acids such as calcium carboxylates and barium carboxylates. However, the latter is detrimental to the chlorine- mapping effect intended in the present invention. Therefore, it should be used in an amount of 0.7 mol or less, preferably 0.5 mol or less per zinc carboxylate.

Other compounds detrimental to the chlorine- mapping effect, such as alkaline earth metal salts of carboxylic acids, include tin compounds (eg dibutyl tin dilaurate and dibutyl tin malate) and lead compounds (eg lead sulfate, lead phosphite, and lead). Stearates), which are common heat stabilizers for vinyl chloride resins. These tidal compounds or lead compounds, when used in combination with tin carboxylates, should be used in amounts of up to 0.3 moles per mole of zinc carboxylates. Other compounds that are detrimental to the chlorine- mapping effect include alkali metal carboxylates and should be used in amounts of up to 0.3 moles per mole of zinc carboxylate.

The compound (polyhydric alcohol) which has two or more alcoholic hydroxyl groups in one molecule is mixed in the vinyl chloride resin composition of this invention. Examples of polyhydric alcohols are glycerin, pentaerythritol, dipentaerythritol, sorbitol, 1, 4-sorbitan, 1.5-sorbitan, and mannitol.

They also include sorbitan partial esters (eg sorbitan monolaurate, sorbitan monopalmitate, sorbitan monooleate, and sorbitan mono, including partial esters formed from polyhydric alcohols and fatty acids having 12-18 carbon atoms). Stearates, sorbitan distearate), glycerin partial esters (eg glycerin monolaurate and glycerin monooleate), condensed glycerin partial esters (such as diglycerine monolaurate, tetraglycerine oleate, hexaglycerine laurate, And decaglycerin laurate), partial esters of pentaerythritol and fatty acids (such as pentaerythritol monolaurate and dipentaerythritol monostearate), trimethylolpropane monoesters (such as trimailolpropane monostearate) ), And hydroxycarboxylic acid and glycerol The partial esters (glycerol monohydroxy stearate) may be mentioned as an example.

According to the invention, the polyhydric alcohols should be used at 0.3-5 moles, preferably 0.5 -.4.5 moles per mole of zinc carboxylate mentioned above (the molar amount is based on the polyhydric alcohols having three hydroxyl groups per molecule). . At less than 0.3 moles, the polyhydric alcohols do not produce the desired chlorine-finishing effect. In amounts greater than 5 moles, the polyhydric alcohol flows out of the molded article, causing rough surface irregularities that harm the uniform chlorine-finding effect. Result. In addition, excess polyhydric alcohols have high production costs. In the case of polyhydric alcohols having any number of hydroxyl groups except three, the standard amount (0.3-5 moles) mentioned above should be corrected by multiplying by the factor calculated by dividing 3 by the number of hydroxyl groups per molecule.

In the case of partial esters of polyhydric alcohols and fatty acids, or mixtures of partial esters, the number of hydroxyl groups in one molecule is not limited and an appropriate amount should be determined by trial and error based on the above-mentioned amounts.

Various additives commonly used for vinyl chloride resins, such as, for example, plasticizers, fillers, dyes, stabilizers, and blending resins, can be incorporated into the vinyl chloride resin compositions of the present invention. However, as mentioned above, some stabilizers can be detrimental to the chlorine- mapping effect.

For example, the vinyl chloride resin composition of the present invention is in the form of a plastisol or organosol composed of vinyl chloride resin and various components. It is processed into films, sheets, leather, and other molded articles by casting, dipping, or coating. The molded article is finished by heat treatment for gelation. The heat treatment can be carried out by an oven or a drying tunnel. This step is important for the full development of the chlorine- mapping effect.

Chlorine-finishing effect depends on the heating time of the heating temperature. For small ovens, heating should be performed for at least about 40 seconds at 200 ° C., at least 80 seconds at 180 ° C., at least 120 seconds at 160 ° C., or at least 160 seconds at 140 ° C.

Suitable heating conditions should be selected according to the specific composition.

The vinyl chloride resin composition of the present invention is not particularly limited in its form and molding method. It can be taken in the form of powder and pellets in addition to plastisols and organosols. The transverse or pellet form can be made from an extruded grade vinyl chloride resin having an average particle diameter of 100-150 μm. Such compositions may undergo calendaring, extrusion molding, or injection molding. The resulting molded article will have a chlorine-finding surface upon post-heating. For example, a thin sheet may be heated while maintaining the surface at about 200 ° C. for at least about 40 seconds for a chlorine-finishing effect.

Compositions incorporating an expanding agent may also be subjected to chlorine finishing in the same manner. Powder compositions for bed coating electrostatic coating or cast-sintering may also be subjected to chlorine finishing.

As long as the resulting composition achieves the desired object of the present invention, there is no particular limitation on the method for producing the vinyl chloride resin composition of the present invention. For example, either polyhydric alcohol or zinc carboxylate can be added first during the production of vinyl chloride resin.

The vinyl chloride resin composition of the present invention produces a molded article having an excellent chlorine finishing effect upon heat treatment after a molding operation. The molded article thus obtained has a chlorine-finish surface of low gloss, good feel, and a simple appearance.

The vinyl chloride resin composition of the present invention is applicable to wall covering, flooring, leather, canvas, vehicle interiors, coated steel sheets, coated cotton cloths, coated yarns, instrument handle coats, protective gloves, toys and everyday items. .

The invention is described in detail with reference to the following examples.

Examples 1-9 and Comparative Examples 1-3

Plastisol was prepared from the following components by combining using a twin-screw-stering-mixer for 15 minutes.

Vinyl chloride resin

* Sumilit ^R PXNHA (produced by Sumitomo Chemical Co., Ltd.) with an average particle diameter of 1.1 μm

65 g of di-2-ethylhexyl phthalate

Calcium Carbonate ^* 40g

* Whiton ^R SB red (Product of Shirashi Kogyo Co., Ltd)

Titanium White ^* 5g

* R-820 (Product of Titan Kogyo Co., Ltd)

Zinc Octoate ^{* As} Table 1

* KV-75A-1, 59% solution (product of Kyodo Yakuhin Co., Ltd)

Sorbitan monolaurate as shown in Table 1

The resulting plastisol was cast on flame retardant paper to form a 200 μm thick coating using an experimental knife coater. The coated flame retardant paper was passed through a tunnel dryer for mild heat treatment so that the coating film was semi-gelled.

After cooling, the rectangular test pieces were cut out of the coated flame retardant paper. The test pieces were completely gelled by heating in an oven at 210 ° C. for the different times shown in Table 1. Eventually, it was tested and evaluated for 60 ° C. reflection. (%) The smaller the 60 ° reflectance value, the better the chlorine-treatment effect. 60 ° C. reflectance for practical use should be 30% or less, preferably 10% or less.

Example 10-16 and Comparative Example 4-5

The same procedure of Example 7 was repeated except that the polyhydric alcohols shown in Table 2 were substituted for sorbitan monolaurate. The results are also shown in Table 2.

Example 17-20 and Comparative Example 6-8

The same procedure of Example 6 was repeated except that zinc carboxylate was substituted for zinc octoate as shown in Table 3. The results are also shown in Table 3.

Incidentally, the example of Comparative Example 6 showed a low reflectance value, but this is not a practical use because of the rough surface irregularity.

Examples 21-26 and Comparative Examples 9-12

The procedure was repeated as in Example 5 except that the composition incorporated any of tin stabilizer (KS-22, manufactured by Kyodo Yakuhin Co., Ltd), calcium octoate, and potassium octoate shown in Table 4. .

The results are also shown in Table 4.

Claims (11)

The vinyl chloride resin composition which mixed 0.002-0.02 mol of zinc carboxylates and 0.3-5 mol of compounds which have 2 or more alcoholic hydroxyl groups in 1 molecule per mol of said zinc carboxylates with respect to 100 g of vinyl chloride resins. The vinyl chloride resin composition according to claim 1, wherein the zinc carboxylate is a zinc salt of mono carboxylic acid having 3 to 18 carbon atoms. The vinyl chloride resin composition according to claim 2, wherein the zinc carboxylate is a zinc salt of mono carboxylic acid having 6 to 10 carbon atoms. The vinyl chloride resin composition according to claim 3, wherein the zinc carboxylate is selected from zinc hexanoate, zinc heptatoene, zinc octoate, zinc nonanoate, and zinc decanoate. The vinyl chloride resin composition of claim 1, wherein the amount of zinc carboxylate is 0.0025 to 0.02 moles per 100 g of vinyl chloride resin. The vinyl chloride resin composition according to claim 1, wherein the compound having two or more alcoholic hydroxyl groups per molecule is a polyhydric alcohol or a partial ester formed from the polyhydric alcohol and a fatty acid. 7. The vinyl chloride resin composition according to claim 6, wherein the polyhydric alcohol is selected from sorbitol, pentaerythritol, and glycerin. 7. The partial ester of claim 6, wherein the partial ester formed of the polyhydric alcohol and the fatty acid is selected from the group consisting of sorbitan partial esters, glycerin partial esters, condensed glycerin partial esters, pentaerythritol partial esters, condensed pentaerythritol partial esters, trimethylolpropane monoesters, And a partial ester formed of glycerin and hydroxy carboxylic acid. 7. The partial esters formed of polyhydric alcohols and fatty acids according to claim 6 are sorbitan monolaurate, sorbitan monofilmite, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, glycerin monolaurate and Vinyl chloride resin composition selected from diglycerin monolaurate. The vinyl chloride resin composition according to claim 1, wherein the amount of the compound having two or more alcoholic hydroxyl groups per molecule is 0.5 to 4.5 moles per mole of zinc carboxylate. A chlorine (chlorine) -thalamic product obtained by molding a vinyl chloride resin composition as defined in claim 1 and heat-treating the resulting molding.