JPH0632956A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which is excellent in heat stability and weatherability, hardly causes zinc burn, scarcely suffers thermal discoloration and is easy to tone in color by compounding a vinyl chloride resin, a specified heat stabilizer, ZnO and TiO2 each in a specified amount. CONSTITUTION:The resin composition consists of: 100 pts.wt. vinyl chloride resin (e.g. TS1000R, a product of Tokuyama Sekisui Co.); 3-8 pts.wt. heat stabilizer consisting of 20-35wt.% ion-substituted hydrotalcite comprising a hydrotalcite (e.g. DHT-4A, a product of Kyowa Chemicals) having 20-80mol% of the carbonate ions substituted by perhalogenate ions (e.g. perchlorate ions), 20-40wt.% metal soap comprising a mixture of a metal soap of zinc (e.g. zinc stearate) and one of a group 2 element (e.g. calcium stearate), and 40-60wt.% polyhydric alcohol (e.g. dipentaerythritol); 0.2-1,5 pts.wt. ZnO; and 2-15 pts.wt. TiO2.

Description

Detailed Description of the Invention

[0001]

This invention relates to a vinyl chloride resin composition.

[0002]

2. Description of the Related Art Weatherability is required when a vinyl chloride resin composition is used for outdoor wall building materials, rain gutters, window frames and the like. Ultraviolet absorbers, zinc oxide, titanium dioxide and the like are known as additives for improving weather resistance.

Ultraviolet absorbers are salicylic acid ester type,
Benzophenone-based, benzotriazole-based, cyanoacrylate-based, etc. are known. However, there is a problem that the ultraviolet absorber sublimes when molded at a high temperature and causes a lot of loss, and the effect of the ultraviolet absorber disappears when the molded product is used outdoors for a long time. Further, most of the ultraviolet absorbers have a yellowish color, and when used in white or pastel molded products, there is a drawback that toning becomes difficult.

Zinc oxide has the characteristic of not transmitting ultraviolet rays, does not sublime during molding, and has a white color tone, and is excellent as a weather resistance improver. In particular, the combined use of titanium dioxide, which is a white pigment, has a remarkable effect on improving the weather resistance. However, when zinc oxide is added to a vinyl chloride resin that does not contain a heat stabilizer, the amount of zinc chloride that results from trapping unstable chlorine increases, and it is called "zinc burn" due to the heat during molding. There is a problem that decomposition of the vinyl chloride resin is likely to occur quickly and a blackened substance is generated during molding.

Therefore, for the above-mentioned use, a composition comprising a vinyl chloride resin, zinc oxide and titanium dioxide, to which a heat stabilizer is further added, is used. As the heat stabilizer, organotin stabilizers, metal soaps, etc. are generally used.

Organotin stabilizers have a small effect of improving lubricity and a small effect of improving dynamic thermal stability, and therefore have a small effect of preventing zinc burning and are hard to be thermally decomposed during molding. Zinc burn occurs with respect to the vinyl chloride resin composition.

Metallic Ken has 1 metallic element
In the case of seeds, the stabilizing effect is small and coloring also occurs, so
It is used in combination with a metal soap of the Group 12 element of the periodic table such as zinc and cadmium and a metal soap of the Group 2 element of the periodic table such as magnesium, calcium and barium. However, if only metal soap is used as the heat stabilizer for the vinyl chloride resin composition containing zinc oxide, the stabilizing effect is small and zinc burning occurs.

In order to improve the heat stabilizing effect of metal soap, non-metal stabilizers such as epoxy compounds and phosphites, and hydrochloric acid scavengers such as calcium silicate and hydrotalcites are used in combination with metal soap. However, the vinyl chloride resin composition for hard products to which zinc oxide is added does not have sufficient heat stabilizing performance, and there is still a drawback that zinc burning is likely to occur.

In order to solve this drawback, JP-A-61-1 is used.
Japanese Patent No. 13630 describes that ion-substituted hydrotalcites in which 20 to 80 mol% of carbonate ions of hydrotalcites are replaced with perhalogenate ions, a polyhydric alcohol and metal soap are used in combination. However, it is described that the polyhydric alcohol is preferably 10 to 100 parts by weight based on 100 parts by weight of the ion-substituted hydrotalcites.

However, even if an ion-substituted hydrotalcite compound is used as a heat stabilizer together with a polyhydric alcohol and a metal soap in a vinyl chloride resin composition for hard products to which zinc oxide is added, the ion-substituted hydrotalcite will be used. 10 to 1 of polyhydric alcohol to 100 parts by weight of talcites
In the range of using 00 parts by weight, zinc burning is likely to occur,
If the amount of ion-substituted hydrotalcites is increased to such an extent that zinc burning does not occur, there is a problem that the molded body becomes reddish during molding due to the heat coloring property. Further, if the amount of zinc oxide is reduced to such an extent that zinc burning does not occur, not only the weather resistance is lowered, but also the molded body becomes reddish at the time of molding due to the thermal coloring property of the ion-substituted hydrotalcites.

[0011]

DISCLOSURE OF THE INVENTION In view of these points, the present invention is a vinyl chloride system which has high thermal stability, is unlikely to cause zinc burning, is excellent in weather resistance, is low in heat colorability, and is easy in toning. An object is to provide a resin composition.

[0012]

As the vinyl chloride resin used in the present invention, a homopolymer of vinyl chloride, and another monomer or two or more monomers containing vinyl chloride as a main component and copolymerizable therewith And copolymers of these polymers, and chlorinated products of these polymers or mixtures of these polymers.

The monomers copolymerizable with the above vinyl chloride include α-type compounds such as ethylene, propylene and 1-butene.
Olefin, vinyl acetate, vinyl propionate, vinyl stearate and other vinyl esters, styrene, α
-Styrenes such as methyl styrene, vinyl ethers such as isobutyl vinyl ether, cetyl vinyl ether and phenyl vinyl ether, alkyl (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate, vinylidene chloride, halogen such as vinyl fluoride Vinyl chlorides, cyclohexylmaleimide,
Examples include N-substituted maleimides such as phenylmaleimide.

The average degree of polymerization of the vinyl chloride resin is not particularly limited, but if it is less than 300, a molded product having sufficient strength cannot be obtained, and if it exceeds 1400, the molding performance is deteriorated. A vinyl chloride resin of 1400 is preferable, and a polymerization degree of 700 to 1400 is preferable for a vinyl chloride resin composition for hard products such as building materials.

The heat stabilizer used in the present invention is
It is composed of ion-substituted hydrotalcites, a metal soap containing zinc metal soap and a metal soap of Group 2 element of the periodic table, and a polyhydric alcohol.

The above ion-substituted hydrotalcites are
20-80 mol% of carbonate ions of hydrotalcites
Is substituted with perhalogenate ion, and any method can be adopted for the production method thereof. For example, JP-A-61-1
Japanese Patent No. 113630 proposes a method for producing ion-substituted hydrotalcites by contacting hydrotalcites with perhalogen acid or a water-soluble perhalogenate salt in the presence of water.

The above-mentioned hydrotalcites are complex metal salts represented by the general formula (1), and are obtained from natural minerals such as hydrotalcite. The components of the hydrotalcites may contain, in place of magnesium ions, one or more divalent metal ions such as manganese, iron, cobalt, nickel and copper. Further, instead of part of aluminum, one or more kinds of trivalent metal ions such as iron and cobalt may be contained. Also,
One or more of anions such as fluorine, chlorine, bromine, nitric acid, sulfuric acid, ferrocyanic acid, acetic acid, and oxalic acid may be contained in place of the carbonate ions.

[Chemical 1] (In the formula, X, Y and Z are 8 ≧ X / Y ≧ 0.25 and Z
/(X+Y)>0.05, and a is 0.25 ≦ a /
It is a positive number that satisfies (X + Y) ≦ 1.0. )

Examples of the above-mentioned hydrotalcites are DHT-4 manufactured by Kyowa Chemical Co., Ltd., represented by the formula (2).
A etc. can be given.

[Chemical 2]

When the ion substitution ratio of the hydrotalcites to the ion substituted hydrotalcites is low, the effect of improving the thermal stability is small, and when the ion substitution ratio is high, the ion substituted hydrotalcites themselves decompose the vinyl chloride resin to color it. Therefore, it is limited to 20 to 80 mol%, preferably 30 to 80 mol%.
It is 70 mol%. As the perhalogen acid, perchloric acid and periodic acid can be used. Further, as the water-soluble perhalogen acid salt, an alkali metal salt or an alkaline earth metal salt of perchloric acid or periodic acid can be used.

When the amount of the ion-substituted hydrotalcites is small, the effect of improving the thermal stability is small, so that the thermal decomposition of the vinyl chloride resin is accelerated, and when the amount is large, it causes the thermal coloring property. ~ 35% by weight.

The metallic soap used in the present invention comprises zinc metallic soap and periodic table Group 2 element metallic soap.

The above zinc metal soap is an organic fatty acid zinc salt, and examples thereof include zinc stearate, zinc laurate, zinc naphthenate, zinc 2-ethylhexanoate, zinc ricinoleate, and the like. And may be used in combination of two or more.

The metal salt of Group 2 element of the periodic table is an organic fatty acid metal salt such as barium, calcium, magnesium, etc., and calcium stearate, calcium laurate, calcium naphthenate, calcium 2-ethylhexanoate, calcium ricinoleate. , Barium stearate, barium laurate, barium naphthenate, 2
-Barium ethylhexanoate, barium ricinoleate,
Examples thereof include magnesium stearate and the like, and these may be used alone or in combination of two or more kinds.

In the above-mentioned metallic soap, in order to suppress the accumulation of zinc chloride that occurs, the metallic soap of zinc is 50 to 75% by weight, and the metallic soap of Group 2 element of the periodic table is 50 to 75% by weight. It is preferably 25% by weight.

[0025] In metal soap, at least or at least a small amount of vinyl soap accelerates the thermal decomposition of the vinyl chloride resin, so 20% in the heat stabilizer is used.
-40% by weight.

Examples of the polyhydric alcohol include monopentaerythritol, dipentaerythritol, polypentaerythritol, mannitol, sorbitol and the like.

When the amount of polyhydric alcohol is small, "zinc burn" occurs.
When the amount of the heat stabilizer is 40% by weight, the polyhydric alcohol itself does not have a heat stabilizing effect, so that the vinyl chloride resin is rapidly decomposed.

The heat stabilizer used in this invention is
It consists of ion-substituted hydrotalcites, a metal soap containing zinc metal soap and a metal soap containing a Group 2 element of the periodic table, and a polyhydric alcohol. Each component is individually mixed with a vinyl chloride resin. Alternatively, in order to improve dispersibility, only the heat stabilizer may be mixed while being heated to obtain a powdery material, and the obtained powdery material may be mixed with a vinyl chloride resin.

When the amount of the heat stabilizer added is large, the heat coloring property is large, and when the amount is small, the heat stabilizing effect is small and the thermal decomposition of the vinyl chloride resin is accelerated.
It is 3 to 8 parts by weight with respect to parts by weight.

If the amount of zinc oxide added is large, "zinc burn" will occur.
When the amount is less than the above, the weather resistance is deteriorated and the thermal coloring property is increased, so that the amount is 0.2 to 1.5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

If the amount of titanium dioxide added is too large, plate-out will occur at the time of molding, and it will cause choking, while if it is too small, it will have a yellowish color and poor weather resistance, so 100 parts by weight of vinyl chloride resin will be used. For 2 to 15
Parts by weight.

The vinyl chloride resin composition of the present invention comprises
For example, acrylic impact modifier, chlorinated polyethylene, impact modifier such as ethylene-vinyl acetate, antioxidant such as hindered phenol, phosphite stabilizer, heat stabilizer such as epoxidized soybean oil, polyethylene wax. ,
Lubricants such as fatty acid esters, pigments such as carbon black, azo pigments and ferrocyan pigments may be added.

As a method for molding a molded body from the vinyl chloride resin composition of the present invention, a conventionally known method can be adopted. For example, an extrusion molding method, an injection molding method, a calender molding method and the like can be mentioned.

[0034]

EXAMPLES Next, examples of the present invention will be described. Examples 1-9, Comparative Examples 1-9 Hydrotalcites (Kyowa Chemical Co., Ltd., trade name DHT-
4A) 294 parts by weight was dispersed in 3000 parts by weight of water to form a slurry, and then 74.4 parts by weight of 70% perchloric acid aqueous solution was gradually added. After the reaction was completed, 0.74 parts by weight of water was added. It was neutralized with calcium oxide and evaporated to dryness to obtain ion-substituted hydrotalcites in which about 40% of carbonate ions of hydrotalcites were replaced with perchlorate ions. Table 1
The predetermined amount of hydrotalcites, ion-substituted hydrotalcites, zinc stearate, calcium stearate, and dipentaerythritol shown in (4) were supplied to a Henschel mixer (manufactured by Kawata Manufacturing Co., Ltd.) and mixed at 150 ° C. The mixture was pulverized by a jet mill pulverizer to obtain a powdery heat stabilizer (hereinafter referred to as S0 to S6).

[0035]

[Table 1]

A predetermined amount of vinyl chloride resin shown in Tables 2 and 3 (manufactured by Tokuyama Sekisui company, trade name TS1000R; degree of polymerization 10)
50), the above heat stabilizer, zinc oxide, and titanium dioxide are used as an acrylic impact modifier (Kanebuchi Chemical Co., Ltd., trade name K-
5 parts by weight of FM) and 1 part by weight of polyethylene wax (manufactured by Mitsui Petrochemical Co., Ltd., product name High Wax 220MP) are supplied to a Henschel mixer (manufactured by Kawata Manufacturing Co., Ltd.) and mixed by natural heat until the temperature reaches 120 ° C., and powdered. A resinous mixture was obtained.

The resin mixture thus obtained was evaluated as follows, and the measurement results are shown in Tables 2 and 3. 1) Thermal stability (1) Powder thermal stability About 10 parts by weight of the obtained resin mixture was placed in an aluminum vat, placed in a gear oven set at 190 ° C., and taken out at 10 minute intervals, and the resin mixture powder was black. The time to turn into was measured. (2) Sheet heat stability The obtained resin mixture was kneaded with an 8-inch mixing roll set at 200 ° C. for 3 minutes to obtain a 1 mm thick sheet, and the obtained sheet was cut into 50 × 50 mm to prepare a sample. Obtained. The obtained sample was put in a gear oven set at 200 ° C. and taken out at intervals of 10 minutes, and the time for the sheet to turn black was measured. (3) Dynamic Thermal Stability 65 parts by weight of the obtained resin mixture was supplied to a roller type rotor (HAKKE, Plastomill) to supply 195
Kneading was carried out at a temperature of 30 rpm and the start time of torque increase was measured.

2) Thermal coloring property The obtained blended composition was kneaded with an 8-inch mixing roll set at 200 ° C. for 3 minutes to obtain a 1 mm-thick sheet. The obtained sheet was 200 ° C. and a pressure of 100 kgf / c.
A sheet having a thickness of 3 mm was obtained by press molding at m ² for 5 minutes.
The yellowing degree (YI) of this sheet was measured using a color computer manufactured by Suga Test Instruments Co., Ltd.

3) Weather resistance The press sheet used for the above-mentioned measurement of thermal colorability was irradiated with a high pressure mercury lamp (H400-F, manufactured by Toshiba) at 63 ° C. for 1000 hours, and the yellowing degree (ΔYI) after irradiation was standardized before irradiation. ) Was measured.

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

The vinyl chloride resin composition of the present invention comprises
Ion-substituted hydrotalcites 20 to 3 in which 100 parts by weight of vinyl chloride resin and 20 to 80 mol% of carbonate ions of hydrotalcites are replaced with perhalogenate ions
3 to 8 parts by weight of a heat stabilizer comprising 20 to 40% by weight of a metal soap consisting of 5% by weight, a metal soap of zinc, and a metal soap of a Group 2 element of the periodic table, and 40 to 60% by weight of a polyhydric alcohol. , Zinc oxide 0.2 to 1.5 parts by weight, and titanium dioxide 2 to 15 parts by weight, so that the thermal stability is excellent and the thermal coloring property is low. Therefore, zinc burning or coloring does not occur at the time of molding, and it is easy to give a color tone. Further, the obtained molded product has excellent weather resistance and can be suitably used for products for outdoor use such as outer walls of building materials, rain gutters, window frames and the like.

Claims (1)

[Claims] 1. A metal of zinc with 100 parts by weight of a vinyl chloride resin, 20 to 35% by weight of ion-substituted hydrotalcites in which 20 to 80 mol% of carbonate ions of hydrotalcites are replaced with perhalogenate ions. Metal Ken 20-4 composed of Ken Ken and metal Ken of Group 2 elements of the periodic table
3 to 8 parts by weight of a heat stabilizer consisting of 0% by weight and 40 to 60% by weight of a polyhydric alcohol, 0.2 to 1.5 parts by weight of zinc oxide,
And a vinyl chloride resin composition comprising 2 to 15 parts by weight of titanium dioxide.