JPH11323050A - Vinyl chloride resin composition and coloring agent composition for vinyl chloride resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl chloride resin composition having sufficient stability to chalking and excellent in heat resistance and processability and a coloring agent composition for vinyl chloride resins used therefor. SOLUTION: This vinyl chloride resin composition comprises 100 pts.wt. vinyl chloride resin, 0.1-5 pts.wt. magnesium oxide and/or magnesium hydroxide and 0.001-0.5 pts.wt. copper sulfate. This coloring agent composition for vinyl chloride resins consists essentially of a coloring agent and comprises magnesium oxide and/or magnesium hydroxide in an amount of 0.1-5 pts.wt. based on 100 pts.wt. vinyl chloride resin to be colored and copper acetate in an amount of 0.001-0.5 pt.wt. based on 100 pts.wt. vinyl chloride resin to be colored.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition having sufficient stability against chalking and a colorant composition for a vinyl chloride resin used therein.

[0002]

2. Description of the Related Art Vinyl chloride resin is a general-purpose thermoplastic resin. However, it is unstable to heat and light and is colored at the time of heat molding, the mechanical strength is reduced, or the molded article is poor in weather resistance. There is a major drawback that is easily deteriorated when used outdoors. In particular, when used for rain gutters, pipes, window frames, deck materials, and the like which are used outdoors for a long period of time, the surface of a portion exposed to sunlight causes a whitening phenomenon called "chalking", which significantly impairs the appearance. In order to improve these disadvantages, metal soap, lead compounds, organotin compounds, ultraviolet absorbers, ultraviolet stabilizers, lubricants, fillers, coloring agents, etc. are appropriately selected for vinyl chloride resin to form molded articles. However, a vinyl chloride resin composition that is stable against chalking has not yet been obtained.

[0003]

On the other hand, a technique for preventing chalking by blending copper acetate with a vinyl chloride resin has been proposed (Japanese Patent Publication No. Sho 62-41532). According to this, although a certain anti-chalking effect can be obtained, as described in JP-B-62-41532, a large amount of copper acetate exceeds a predetermined amount (for example, 0 to 100 parts by weight of vinyl chloride resin). (1 part by weight), on the contrary, there is a problem that the effect of preventing chalking is reduced and the heat resistance of the vinyl chloride resin is impaired.

A technique for preventing choking by blending a copper salt of a benzotriazole compound or a copper salt of a benzophenone compound with a vinyl chloride resin has been proposed (JP-A-5-320450). Salts or copper salts of benzophenone compounds are
It is considerably inferior to copper acetate in the action of preventing chalking.

A technique for improving the thermal stability by blending magnesium oxide with a vinyl chloride resin has been proposed (Japanese Patent Publication No. 52-31259), which is also described in Japanese Patent Publication No. 52-31259. As described above, even if the amount of magnesium oxide is increased, the effect of improving the thermal stability reaches a plateau. According to the findings of the present inventors, the addition of magnesium oxide increases the viscosity of the vinyl chloride resin, so that the processability is reduced and the surface condition of the molded product is deteriorated. .

As described above, with the conventionally known anti-chalking agent for vinyl chloride resin, even if the compounding amount is increased, not only the effect corresponding thereto is not obtained, but also the excellent properties of vinyl chloride resin such as heat resistance and processability. At present, a vinyl chloride resin having sufficient stability against chalking has not been obtained. Therefore, an object of the present invention is to provide a vinyl chloride resin composition having sufficient stability against chalking, and also having excellent heat resistance and processability, and a colorant composition for a vinyl chloride resin used therefor. It is in.

[0007]

Means for Solving the Problems In order to solve the above problems, the present invention provides the following configurations. (1) A vinyl chloride resin composition containing 0.1 to 5 parts by weight of magnesium oxide and / or magnesium hydroxide and 0.001 to 0.5 part by weight of copper acetate based on 100 parts by weight of a vinyl chloride resin. (2) Further, hydrotalcite is added to vinyl chloride resin 10
The vinyl chloride resin composition according to the above (1), wherein the composition contains 0.1 to 3 parts by weight with respect to 0 parts by weight. (3) A colorant composition for a vinyl chloride resin containing a colorant as an essential component, wherein magnesium oxide and / or magnesium hydroxide is 0.1 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin. A colorant composition for a vinyl chloride resin, comprising copper acetate in an amount of 0.001 to 0.5 part by weight based on 100 parts by weight of the vinyl chloride resin.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a vinyl chloride resin refers to a homopolymer or a copolymer containing vinyl chloride as a constituent monomer. Magnesium oxide and / or magnesium hydroxide are added to improve the thermal stability of the vinyl chloride resin and prevent chalking. Magnesium oxide is more effective than magnesium hydroxide. The amount of magnesium oxide and / or magnesium hydroxide used is based on 100 parts by weight of vinyl chloride resin.
A suitable range is from 0.1 to 5 parts by weight, preferably from 0.3 to 3 parts by weight. Even when magnesium oxide and / or magnesium hydroxide is used in an amount exceeding the above range, the effect of improving thermal stability and preventing choking can be no longer obtained when used in an amount within the above range. Moreover, since the viscosity of the vinyl chloride resin increases, the processability decreases, and the surface condition of the molded product may be poor. If the amount of magnesium oxide and / or magnesium hydroxide is less than the above range, the effect of improving thermal stability and the effect of preventing choking may not be observed.

Copper acetate is added for improving the weather resistance of the vinyl chloride resin and preventing chalking, and copper acetate exhibits the most excellent effect as compared with inorganic acid copper and other organic acid copper. The amount of copper acetate used is 0.001 to 0.5 part by weight, preferably 0.01 to 0.3 part by weight, more preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the vinyl chloride resin.
A range of 0.1 parts by weight is suitable. When copper acetate is used in an amount exceeding the above range, the effect of improving weather resistance and the effect of preventing chalking are lower than when using copper acetate in an amount within the above range. In addition, the heat resistance of the vinyl chloride resin may be impaired and the processability may be reduced. On the other hand, when the amount of copper acetate used is less than the above range, the effect of improving weather resistance and the effect of preventing chalking may not be observed.

In the present invention, the use ratio of magnesium oxide and / or magnesium hydroxide to copper acetate is not particularly limited, but [total amount of magnesium oxide and / or magnesium hydroxide]:
The weight ratio of [copper acetate] is preferably in the range of 50: 1 to 5: 1, and more preferably in the range of 30: 1 to 10: 1. If the weight ratio exceeds 50: 1, a problem occurs due to too much use of magnesium oxide and / or magnesium hydroxide or insufficient use of copper acetate, and the weight ratio becomes 5: 5. If the ratio is less than 1, a problem occurs due to an insufficient amount of magnesium oxide and / or magnesium hydroxide or an excessive amount of copper acetate.

In the vinyl chloride resin composition of the present invention, the use of copper acetate slightly lowers the heat resistance of the vinyl chloride resin. Therefore, it is preferable to use a hydrotalcite compound for the purpose of complementing this. The hydrotalcite compound is, for example, a compound represented by the general formula Mg _1-x Al _x (OH) ₂ (A) _{x / 2} · mH ₂ O (where x is a real number in the range of 0 <x ≦ 0.5. A
Is CO ₃ and / or SO ₄ ; m is 0 or a positive real number. ) Is a hydrated double salt compound comprising magnesium and aluminum.

The hydrotalcite compound may be a natural product or a synthetic product. As the synthesis method, JP-B-46-2280, JP-B-50-280
Known methods described in JP-A-30039 and JP-B-51-29129 can be exemplified. Further, in the present invention, the hydrotalcite compound can be used without being limited by its crystal structure, crystal particle diameter and the like.

Further, the surface of the hydrotalcite compound may be made of a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic metal sulfonate such as an alkali metal dodecylbenzenesulfonate, a higher fatty acid amide, or the like. Those coated with higher fatty acid esters or waxes can also be used. Further, a hydrotalcite compound modified with zinc or the like can also be used.

The amount of the hydrotalcite compound used is preferably 0.1 to 3 parts by weight, more preferably 0.3 to 2 parts by weight, and more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the vinyl chloride resin.
-1 part by weight is particularly preferred. Even when the hydrotalcite compound is used in an amount exceeding the above range, no further improvement in heat resistance is observed, and when the amount is below the above range, heat resistance may not be maintained.

The vinyl chloride resin composition of the present invention can contain a coloring agent such as an inorganic pigment and an organic pigment. As inorganic pigments, red iron oxide, yellow iron oxide, iron black, titanium white,
Examples include titanium yellow, chrome yellow, chrome vermillion, chromium oxide green, carbon black, and calcined pigments. Examples of the organic pigment include quinacridone-based, polyazo-based, perylene-based, diketopyrrolopyrrole-based, perinone-based, quinophthalone-based, indanthrene-based, benzimidazolone-based, isoindolinone-based, and phthalocyanine-based pigments. Either one of the inorganic pigment and the organic pigment may be used, or both may be used.

The amount of the coloring agent used is 100 vinyl chloride resin.
The amount is preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 10 parts by weight.
The content is more preferably 2 to 5 parts by weight, particularly preferably 0.5 to 2 parts by weight. If the amount of the coloring agent exceeds the above range, the processability of the vinyl chloride resin may be deteriorated or the mechanical strength of the molded product may be deteriorated.If the amount is less than that, the weather resistance is deteriorated and the molded product deteriorates when used outdoors. May be easier to do.

Inorganic pigments are less expensive than organic pigments, but pigments such as petals have a tendency to deteriorate the vinyl chloride resin. However, the vinyl chloride resin composition of the present invention contains a larger amount of inorganic pigments such as petals than conventional ones (for example, 0.1 to 100 parts by weight of vinyl chloride resin).
5 parts by weight, preferably 0.5 to 2 parts by weight), and is less likely to deteriorate. Therefore, according to the present invention, a vinyl chloride resin composition having a darker color (for example, a brown color with a petal pattern (brown color used for rain gutters, etc.)) that is less likely to cause chalking than before can be obtained. be able to.

The vinyl chloride resin composition of the present invention may contain, if necessary, a metal soap, a lead-based stabilizer, an organic tin stabilizer, an ultraviolet absorber, an ultraviolet stabilizer, a lubricant, a filler, a colorant, a plasticizer. And the like. The method for producing the vinyl chloride resin composition of the present invention is not particularly limited, and magnesium oxide and / or magnesium hydroxide, copper acetate, and additives to be added as needed are added directly to the vinyl chloride resin and mixed. A colorant composition in which magnesium oxide and / or magnesium hydroxide, copper acetate, and additives, if necessary, are blended with a colorant. May be mixed with a vinyl chloride resin.

The present invention also provides this coloring composition. That is, the colorant composition of the present invention contains, in addition to the colorant, magnesium oxide and / or magnesium hydroxide and copper acetate. A resin composition can be manufactured. The compounding amount of each component in the colorant composition of the present invention is blended so that the compounding amount of each component with respect to 100 parts by weight of the vinyl chloride resin is in the range described above in the finally prepared vinyl chloride resin composition. There is a need. That is, in the vinyl chloride resin composition, copper acetate is used in an amount of 0.001 to 0.5 such that magnesium oxide and / or magnesium hydroxide is 0.1 to 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. It is necessary to mix the hydrotalcite compound in an amount of 0.1 to 3 parts by weight. The specific amount of each component is determined in consideration of the amount of the colorant composition used for the vinyl chloride resin.

Since the vinyl chloride resin composition of the present invention is excellent in the effect of preventing chalking, it is very effective when used as a molded product used outdoors, such as rain gutters, pipes, window frames, deck materials, and the like. Although effective, the use is not particularly limited and can be suitably used for any of the known uses.

[0021]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Examples 1 to 5 and Comparative Examples 1 to 10 100 parts by weight of a vinyl chloride resin (degree of polymerization: 1100) were blended with the respective additives in the proportions shown in Table 1. This mixture was mixed for 3 minutes with a high-speed mixer and kneaded with two rolls at 170 ° C. for 5 minutes.
A sheet having a thickness of 5 mm was prepared, a sheet having a thickness of 1 mm was formed by hot pressing, and exposed outdoors. Using a sheet not exposed outdoors as a standard, the color change after 12 months, 18 months, and 24 months of exposure was measured using a spectrophotometer (Macbeth Color Eye CE manufactured by Macbeth).
-3000) and expressed as a ΔL value. The smaller the ΔL value, the greater the anti-chalking effect.

As the hydrotalcite compound, Kyowa
Alkamizer 2 (Mg _0.75Al_0.25(O
H)_Two(CO_Three)_0.125・ H_TwoA compound represented by O
The average particle size is 1.0 μm or less). [Example 6] Color concentrator excellent in chalking
17.5 parts by weight Carbon black 1.25 parts by weight Hydrotalcite compound 12.5 parts by weight Copper acetate 0.5 parts by weight Magnesium oxide 37.5 parts by weight Low molecular weight polyethylene wax 28. 25 parts by weight Plasticizer (dioctyl phthalate) 2.5 parts by weight A total of 100 parts by weight was added to a gate mixer (manufactured by Inoue Seisakusho)
And raise the temperature to 90 to 95 ° C while heating with steam
After stirring to a three-roll mill with a heating temperature of 100 ° C
And kneaded and dispersed. Next, cool the kneaded dispersion to room temperature.
After that, a feather mill (manufactured by Hosokawa Micron) 3m / m screen
After crushed by lean, color of particle size 20-30 mesh
A concentrate was obtained.

Next, vinyl chloride resin (degree of polymerization 1100)
To 100 parts by weight, the respective additives were blended at the blending ratios shown in Table 1, and sheets were prepared in the same manner as in Examples 1 to 5 and Comparative Examples 10 to 10, and similar tests were performed. 1 is shown.

[0024]

[Table 1]

Examples 1 and 2 and Comparative Examples 1 to 6 use carbon black as a coloring agent. In Comparative Example 1, since neither magnesium oxide nor copper acetate was contained, the ΔL value was extremely large, indicating that the choking of the vinyl chloride resin was remarkable. In Comparative Example 2, copper acetate and a hydrotalcite compound for compensating for heat resistance impaired by copper acetate were added to the composition of Comparative Example 1,
ΔL value is smaller than that of Comparative Example 1,
It is shown that copper acetate has an anti-chalking effect. However, when the amount of copper acetate is further increased as in Comparative Example 3, the heat resistance is significantly impaired by the copper acetate, so that the addition of the hydrotalcite compound cannot be compensated for, and burning occurs, making molding impossible. . That is, it can be seen that the choking prevention effect of copper acetate has a limit.

In Comparative Examples 4 to 6, magnesium oxide was added to the composition of Comparative Example 1. Comparative Examples 4, 5, and 6 are in ascending order of the amount of magnesium oxide added.
Comparative Examples 4, 5, and 6 are in the order of smaller L values, and it can be seen that the effect of preventing chalking does not increase even when the amount of magnesium oxide added is increased. Further, in Comparative Example 6, not only the ΔL value was large, but also the surface condition was poor due to a decrease in workability due to an increase in the viscosity of the vinyl chloride resin. In other words, it is understood that the choking prevention effect of magnesium oxide is limited.

On the other hand, in Examples 1 and 2, magnesium oxide and copper acetate were used in an appropriate amount ratio in combination, so that even after 24 months of outdoor exposure, the ΔL value was very excellent, being less than 1. This shows the prevention effect. In addition, there is no decrease in heat resistance or workability as seen in Comparative Examples 3 and 6. Examples 3 to 5, Comparative Examples 7 to 10
Is a pattern using a red petal as a coloring agent.

In Comparative Example 7, since neither magnesium oxide nor copper acetate was contained, the ΔL value was very large.
It can be seen that the chalking of the vinyl chloride resin is remarkable.
In Comparative Examples 8 and 9, copper acetate and a hydrotalcite compound for compensating for the heat resistance impaired by copper acetate were added to the composition of Comparative Example 7, and the ΔL value was smaller than that of Comparative Example 1. It shows that copper acetate has an anti-chalking effect. Comparative Example 10
In this example, magnesium oxide was added to the composition of Comparative Example 1, and it was shown that magnesium oxide had an anti-chalking effect. Although not mentioned as a comparative example, when red iron oxide is used as a coloring agent, a decrease in heat resistance is observed when a large amount of copper acetate is used, and a decrease in workability is observed when a large amount of magnesium oxide is used.

On the other hand, in Examples 3 to 5, since magnesium oxide and copper acetate were used in an appropriate amount ratio in combination, the ΔL value was as very good as about 1 even after 24 months of outdoor exposure. This shows the prevention effect. In addition, no decrease in heat resistance or workability is observed. In Example 6, a color concentrate (colorant composition) was manufactured and then mixed with a vinyl chloride resin. The colorant composition contains magnesium oxide, copper acetate, and a hydrotalcite compound, each of which is 1.5 parts by weight of magnesium oxide, 0.02 parts by weight of copper acetate, and 100 parts by weight of vinyl chloride resin. The talcite compound is used in an amount of 0.5 parts by weight.
Even in the vinyl chloride resin composition of Example 6, since magnesium oxide and copper acetate were used in an appropriate ratio, the ΔL value was less than 1 even after 24 months of outdoor exposure, showing a very excellent anti-chalking effect. ing. In addition, no decrease in heat resistance or workability is observed.

[0030]

According to the present invention, it is possible to obtain a vinyl chloride resin composition having sufficient stability against chalking and having excellent heat resistance and workability. Further, by using the colorant composition for a vinyl chloride resin of the present invention, an excellent vinyl chloride resin composition as described above can be obtained.

Claims (3)

[Claims] 1. A vinyl chloride resin composition containing 0.1 to 5 parts by weight of magnesium oxide and / or magnesium hydroxide and 0.001 to 0.5 part by weight of copper acetate based on 100 parts by weight of a vinyl chloride resin. . 2. The vinyl chloride resin composition according to claim 1, further comprising 0.1 to 3 parts by weight of hydrotalcite based on 100 parts by weight of the vinyl chloride resin. 3. A colorant composition for a vinyl chloride resin containing a colorant as an essential component, comprising: magnesium oxide and / or magnesium hydroxide in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin. Copper acetate was added in an amount of 0.00
A colorant composition for a vinyl chloride resin, which is contained in an amount of 1 to 0.5 part by weight.