JPH03103451A - Powdery stabilizer for chlorine-containing resin - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a powder stabilizer for chlorine-containing resins, and in detail,
The present invention relates to a powder stabilizer for chlorine-containing resins that is safe to handle and is characterized by a mixture of a Group IIa metal salt of perchloric acid, a specific inorganic compound, and an organic powder in a specific ratio.

[Prior art and problems to be solved by the invention] Chlorine-containing resins represented by vinyl chloride resins are inexpensive and have characteristics such as excellent weather resistance, moldability, and gas barrier properties. It has been widely used as films, sheets, and various molded products. However, chlorine-containing resins have poor thermal stability, and are known to become colored or have reduced mechanical strength when heated during processing or use.

In order to avoid such disadvantages, one or more types of stabilizers are added to prevent such deterioration.
/Zn-based metal salts of organic acids, metal salts of inorganic acids, organic tin compounds, etc. were used. However, although these stabilizers have a relatively large effect on improving long-term thermal stability as basic thermal stabilizers, they are completely insufficient in terms of improving colorability, and various stabilizing aids, such as , epoxy compounds, polyhydric alcohols, organic phosphorus compounds, organic sulfur compounds, phenol compounds, β-diketone compounds, etc. have been proposed, but this is not yet sufficient.
Further improvements were needed. In recent years, it has been discovered that metal salts of halogen oxyacids, especially metal salts of perchloric acid, are extremely effective in improving the coloring properties of chlorine-containing resins. It has been proposed to use it in combination with metal salts and the like.

For example, JP-A No. 53-11948 proposes the use of an R acid in combination with a metal salt, JP-A No. 5313659 proposes the use of a basic inorganic acid salt, and JP-A No. 58-198-
Publication No. 122951 proposes the combination use with hydrocruci}, and Japanese Patent Application Laid-Open No. 61-34042 proposes the combination use with zeolites. These metal salts of halogen oxygen acids are compounds used in the explosives industry, etc., and careful attention to safety is required when handling them. However, when used as a stabilizer for chlorine-containing resins, the amount used is Moreover, among the metal salts of halogen oxyacids, group Ua metal salts of perchloric acid have a relatively small risk of explosion, etc., and therefore could be used without any particular problem.

However, under the Fire Service Act revised in May 1988, halogen oxyacids such as perchlorates are classified as class 1 oxidizing solids as potentially hazardous materials. This is stipulated by the name, and it is now necessary to determine whether or not it falls under the category of dangerous goods through legally required tests to determine the potential danger of oxidizing power and sensitivity to impact. As a result, metal salts of perchloric acid were found to be dangerous substances as stipulated in the Fire Service Act, and as per the provisions of the same law, there were severe restrictions on their storage and transportation, and they were used as stabilizers for chlorine-containing resins. It became difficult to use.

For this reason, there was a strong desire to find a stabilizer that contained metal perchlorate and was not classified as a hazardous substance under the Fire Service Act. [Means for Solving the Problems] In view of the above-mentioned current situation, the present inventors have conducted extensive studies to find a stabilizer containing metal perchlorate that does not fall under the category of hazardous materials defined by the Fire Service Act. , Group Ua metal salts of perchloric acid themselves fall under the category of hazardous materials stipulated by the Fire Service Act.
The danger of this mixture may be reduced if it is combined with other precepts that do not fall under the category of dangerous substances. However, the effect of other types of bosan is even greater, and when only inorganic powder is used as a premix to be mixed with the group IIa metal salt of perchloric acid, Chapter I
It was discovered that even if the content of Group Ia metal salts was reduced, the risk did not decrease significantly, and that the risk could be significantly reduced by adding an organic powder to the three-pot system. .

Based on the above knowledge, the present inventors have determined that an inorganic substance that not only does not fall under the category of dangerous substances under the Fire Service Act, but also does not have a harmful effect on the stabilizing effect when used as a stabilizer for chlorine-containing resins. As a result of further studies on powders and organic powders, we used hydrotalcites or zeolites, which are themselves useful as stabilizers for chlorine-containing resins, as inorganic powders, and mixed them with organic powders in a specific ratio. ? It has been found that by combining these powders, a powder stabilizer can be obtained which is not classified as a dangerous substance under the Fire Service Act and is useful as a stabilizer for chlorine-containing resins.

In addition, in the mixture consisting of the above three components, when an organic compound or a chlorine-containing resin powder that is useful as an additive such as a stabilizer or lubricant for chlorine-containing resin is used as the organic powder, it is possible to stabilize the chlorine-containing resin. Perchloric acid not only does not contain any harmful substances that may impair its properties, but also contains all substances that are useful for stabilizing or improving processability, or from the chlorine-containing resin itself that is stabilized. It is extremely useful as a powder stabilizer for chlorine-containing resins containing metal salts.

That is, the present invention provides (a) Group Ua metal salts of perchloric acid 1-
40% by weight, (b) 5 to 45% by weight of at least one of hydrotalcyi l-i and zeolites, and (c)
Points A and B in the attached drawings among the compositions (compositions in the range surrounded by points A, B', CD, E, and F in the attached drawings) consisting of 25 to 90% by weight of at least one type of organic powder. , C
．． It has M configuration in the range surrounded by D, E, F,
The present invention provides a powder stabilizer for chlorine-containing resins.

Hereinafter, the present invention having the above-mentioned summary will be explained in more detail.

(a) Bokumin perchloric acid IIIa used in the present invention
Group metal salts include barium perchlorate, magnesium perchlorate, calcium perchlorate, and strontium perchlorate, and these may naturally be anhydrous salts or hydrated salts. The hydrotalcites used in the present invention are carbonate double salt compounds of magnesium and aluminum, and these include natural hydrotalcites and hydrotalcites. Hekai hydrotalcite is a compound represented by the following formula, and the ratio of magnesium and aluminum can be changed arbitrarily, and the amount of crystal water contained can also be changed arbitrarily depending on the degree of heat dehydration. I can do it.

Mg+-x41, (OH) z・(coa+) +zz
・mtlzO (In the formula, Partially modified hydrotalcite may be substituted with metal.

The (b) Boken zeolites used in the present invention are aluminosilicates having a three-dimensional zeolite crystal structure, and typical examples include A-type, X-type, Y-type, and P-type zeolites, mordenite, and analcite. , sodalite group aluminosilicates, clinobutyrolite, erionite, chabasite, etc., and some or all of the Group IIa metal ions of these aluminosilicates are ion-exchanged with Group II or Group II metal ions. Examples include metal substitution types. Furthermore, these zeolites may have water of crystallization or may be anhydrous from which water of crystallization has been removed.

The (c) precept organic powder used in the present invention includes:
Although various organic powders can be used, it is particularly preferable to use organic compounds or chlorine-containing resins that are themselves useful as additives such as stabilizers and lubricants for chlorine-containing resins.

As organic compounds that are themselves useful as additives such as stabilizers and lubricants for chlorine-containing resins, additives that are solid at room temperature can be used, such as group (I) aliphatic and/or aromatic monocarboxylic acids. Metal salts; polyhydric alcohols, partial esters of polyhydric alcohols and aliphatic or aromatic monocarboxylic acids and/or aliphatic or aromatic dicarboxylic acids; 2-hydroxyphenylhenzotriazur, 2-hydroxybenzo Light stabilizers such as phenones; β-mono-diketone compounds; eboxy compounds; higher aliphatic carboxylic acids, higher aliphatic alcohols, esters of higher fatty acids such as glycerin or glycols, higher alcohol esters of dibasic acids, lubricants such as waxes, etc. ; and so on.

Group Ⅰ metal salts of aliphatic and/or aromatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, octylic acid,
Decanoic acid, neodecanoic acid, lauric acid, myristic acid,
Examples include metal salts of calcium, magnesium, barium, strontium, zinc, etc. of aliphatic and aromatic monocarboxylic acids such as stearic acid, 12-hydroxystearic acid, benzoic acid, toluic acid, and tert-butylbenzoic acid.

Examples of polyhydric alcohols and partial esters of polyhydric alcohols and aliphatic or aromatic monocarboxylic acids and/or aliphatic or aromatic dicarboxylic acids include trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dicarboxylic acids. Polyhydric alcohols such as pentaerythritol, sorbitol, mannitol, and the above polyhydric alcohols and monocarboxylic acids such as palmantic acid and stearic acid and/or succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and terephthalic acid. Examples include partial esters with dicarboxylic acids such as acids.

As light stabilizers such as 2-hydroxyphenylbenzotriazole type and 2-hydroxybenzophenone type, 2-
(2-hydroxy-5-methylphenyl)henzotriazole, 2-(2-hydroxy-5-tertiary octylphenyl)penzotriazole, 2-(2-hydroxy-
3-tert-butyl 5-methylphenyl)-5-chlorobenzotriazole, 2-[2-hydroxy-3,5-di(
α,α-Dimethylbenzyl)phenyl]penzotriazole, 2,2゛-methylenebis[4-tert-octyl-6
-(2-henzotriazolyl)]phenol, 2.4-
Examples include dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-5-methoxybenzophenone). As the β-diketone compound, dibenzoylmethane,
Examples include stearoylbenzoylmethane and dehydroacetic acid.

Examples of the epoxy compound include epibis type or novolac type epoxy resin, tris(2,3-epoxybrobyl) isocyanurate, diglycidyl terephthalate, hydroquinone diglycidyl ether, glycidyl methacrylate copolymer, and the like.

Examples of lubricants include higher fatty acids such as stearic acid, higher alcohols such as stearyl alcohol, esters such as glycerin monostearate, neopentyl glycol distearate, distearyl phthalate, and distearyl adipate, montan wax, and paraffin wax. , waxes such as polyethylene wax, stearic acid ξ-do, methylene bis stearic acid amide, ethylene bis stearic acid amide, etc. Furthermore, it is preferable to use the same type of chlorine-containing resin as the chlorine-containing resin to be stabilized, such as polyvinyl chloride, polyvinyl chloride,
Copolymers of vinyl chloride and other copolymerizable heptanomers (hinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-maleic anhydride copolymer) Coalescence, vinyl chloride-N-phenylmaleimide copolymer, vinyl chloride-N-phenylmaleimide copolymer, hinyl chloride-ethyl acrylate copolymer, vinyl chloride-urethane copolymer! Union,
(vinyl chloride-ethylene-vinyl alcohol copolymer, etc.)
, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, etc.

In the powder stabilizer of the present invention, (a) perchloric acid II
The mixing ratio of at least one of group a metal salt, (b) hydrotalcites and zeolite}1, and at least one of (c) organic powder is limited in terms of safety and effectiveness as a stabilizer. (a) 1 to 40% by weight of precepts, (b) rIi. min 5-45% by weight, ((J component 2
5 to 90% by weight (point A in the attached drawing,
Of the range surrounded by B', C, D, E, and F, the composition must be within the range surrounded by points A, B, C, D, E, and F in the attached drawing. (The composition in the range surrounded by points B, B', and C in the attached drawings is outside the scope of the present invention), and in particular, of the composition in the above range, (a) some 5 to 35% by weight; (middle) a certain amount of 10 to 40% by weight and (c)
A composition containing 30 to 85% by weight of components is preferred from the viewpoint of safety and stabilizing effect.

If component (a) is less than 1% by weight, the amount of stabilizer added will be too large to achieve the desired effect,
Moreover, if it exceeds 40% by weight, there is a problem in terms of safety. Furthermore, if the amount of (b) a certain amount or (c) the amount of precepts is outside the above range, a problem will arise in terms of safety.

The particle size of the powder stabilizer consisting of the above-mentioned three components of the present invention is not particularly limited, but is generally preferably about 1 μm to about 100 μm from the viewpoint of dispersibility in chlorine-containing resins. In addition, the method for preparing the powder stabilizer of the present invention can be applied to a conventional method for preparing powder stabilizers, such as a method in which each component is ground and then mixed in a predetermined amount, or a method in which a predetermined amount of each precept is mixed. Examples include a method of post-pulverizing, a method of mixing and crushing a predetermined amount of any two precepts, and then mixing the remaining precepts.
From a safety point of view, (a) Precept IIa of perchloric acid
The group metal salt and (b) bokubun are mixed and crushed, and then (c) kibun is mixed and crushed, or (a) bokubun and Φ) bokubun are mixed and crushed, and this and separately crushed. (c) A method of mixing the precipitates with powder of precepts is preferred.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited by the following examples.

Example-1 (a) Barium perchlorate as a part, (b) Hydrotalcite as a part (DHT-4A: manufactured by Kyowa Chemical)
(Using polyvinyl chloride resin as the Cl component and changing its ratio, a falling ball impact sensitivity test and a combustion test as specified in the Fire Service Act were conducted.

The falling ball impact sensitivity test is based on "Safety of Reactive Chemical Substances and Carpentry Products" (Daai Publishing, published November 28, 1988) 13
The combustion test was carried out according to the method described on pages 6 to 139.
This was carried out according to the method described on pages 48-150. The outline is as follows.

■． Falling ball impact sensitivity test (1) Comparison with potassium chlorate
Drop it O times, and if all explosions, end the test (Case A)
), if all are non-explosive, perform the following test (2). If both detonation and detonation occur after 10 drops, the steel ball is dropped an additional 30 times (40 times in total) (Case B). (2) Comparison with potassium nitrate From the 50% explosion point when potassium nitrate is used, the steel ball is
The test is terminated if all explosions occur (Case C) and all non-explodes (Case D). If both explosion and non-explosion occur in 10 falls, 30 more falls (total 4
0 times) Drop the steel ball (Case E).

(3) Judgment case A: Rank I Case B: Number of explosions is 20 or more Number of explosions of rank I is 20
Less than 20 times Rank ■ Case C: Rank ■ Case D 2nd rank ■ Case E: Number of explosions is 20 or more Rank ■ Number of explosions is 20
Uncircumcised rank ■ ■． Combustion test (1) Measurement of combustion time Using potassium bromate (A) and potassium perchlorate (B) as standard substances, mix the standard substance and wood flour in a ratio of 1=1, and measure the combustion time of each. , combustion time A and combustion time B.

The test material and wood flour were mixed at a ratio of 1:1 and 8:2, their combustion times were measured, and the shorter time was taken as the combustion time S.

(2) Judgment combustion time S≦burning time A: Rank I burning time A<burning time S≦burning time B: rank ■burning time B<
Burning time S: Rank ■■. Comprehensive Judgment The results of the above-mentioned falling ball impact sensitivity test and combustion test were combined to determine whether or not the product falls under the category of dangerous goods based on the following criteria.

*1 As a highly oxidizing substance, it falls under Fire Service Law Dangerous Substances Class-M Class 1 Oxidizing Solid.

*2: As a moderately oxidizing substance, it falls under the Fire Service Law Hazardous Materials Class 1 Class 2 Oxidizing Solid.

*3 As a substance with low carbon dioxide properties, it falls under the category 3 oxidizing solid under the Fire Service Law Hazardous Substances.

N4: It does not fall under the category of dangerous goods under the Fire Service Act.

(a), (b) and (c) Mixing ratio of Sanboku (intensity ratio)
The test results are shown in Table 1 below.

Example 2 (a) Barium perchlorate 5% by weight as a preservative, (b) 10% hydrotalcite (DHT-4A) as a precipitate
Weight %, (c) rIj. The same test as in Example 1 was conducted using a three-part powder stabilizer using a compound used as a stabilizer for chlorine-containing resins, such as an organic acid metal salt compound.

Also, for comparison, (a) barium perchlorate IO weight%
, (1) j Hewei Hydrotalcite (DHT-4A) 5
When using 0% by weight and 40% by weight of organic acid metal salt (Comparative Example 2-1), (a) 20% by weight of barium perchlorate, (b) synthetic hydrotalcite (DHT-4A)
When using 50% by weight and 30% by weight of organic acid metal salt (
Regarding Comparative Example 2-2), a test similar to the above was conducted.

Example 3 (a) 10% by weight of barium perchlorate as component, (b)
Hydrotalcites or zeolites 3 as an ingredient
0% by weight, (c) barium stearate 2 as a precept
The same test as in Example 1 was conducted using a three-command powder stabilizer containing 0% by weight, 10% by weight of zinc laurate, and 30% by weight of polyvinyl chloride resin.

The results are shown in Table 3 below.

In Table 3, Alcamizers ■ and ■ are Kyowa Chemical's Gokai Hydrotalcite, and Alcamizer ■ is a zinc-substituted (magnesium: zinc-3: l) composition of the above-mentioned Examples and Comparative Examples in the drawings. Shown as points. Dots A to A indicate the blending ratio of each component in Comparative Examples 1-1 to 1B, dots K to C indicate a certain blending ratio of each component in Examples 1-1 to 1-6, and dot S indicates the blending ratio of each component in Comparative Examples 1-1 to 1-1B. Example 2-1~
2-5 shows the blending ratio of each certain part, taiyu and chi show the mixing ratio of each certain part in Comparative Examples 2-1 and 2-2, respectively, and dot shows the mixing ratio of each certain part in Examples 3-1 to 3-8. The mixing ratio of each portion is shown below.

As is clear from the above results, group A metal salts of perchloric acid fall under the category of dangerous substances under the Fire Service Act, and even when mixed with only the two commandments of inorganic compounds, perchlorine Acid No.
Even if the content of Group A metal salts is reduced, it still falls under the category of hazardous materials under the Fire Service Act, and even when organic powder is further mixed with this, the content of Group IIa metal salts of perchloric acid is reduced. Even if I let you/i! It is clear that these stabilizers pose a safety problem and can only be used under strict restrictions stipulated in the Fire Service Act. On the other hand, the stabilizer of the present invention, which is a mixture of specific three components in a specific ratio, has a significantly reduced risk, and even though it contains Group Ua metal salts of perchloric acid, It is clear that this is an extremely safe powder stabilizer that does not fall under the category of hazardous materials under the Fire Service Act.

This indicates that these three precept-based powder stabilizers have a specific blending ratio in terms of safety. In addition, the powder stabilizer of the present invention is composed of precepts that do not adversely affect the stabilizing effect when used as a stabilizer for chlorine-containing resins, so it contains a Group IIIa metal salt of perchloric acid. It is extremely useful as a powder stabilizer for chlorinated resins.

〔Effect of the invention〕

The powder stabilizer for chlorine-containing resins of the present invention comprises perchloric acid No. Ua
Although it contains group metal salts, it is extremely safe and does not fall under the category of hazardous materials under the Fire Service Act, and it has excellent stabilizing effects.

[Brief explanation of drawings]

The drawing is a triangular graph showing the blending ratio of the three precepts of the present invention, and in the figure, the range surrounded by points A, B, C, D, E, and F indicates the composition of the powder stabilizer of the present invention. show.

Claims (5)

[Claims] (1) (a) Group IIa metal salt of perchloric acid 1 to 40% by weight
, (b) 5 to 45% by weight of at least one of hydrotalcites and zeolites, and (c) 25 to 90% by weight of at least one of organic powder,
A powder stabilizer for chlorine-containing resins having a composition within the range of points A, B, C, D, E, and F in the attached drawings. (2) The powder stabilizer for chlorine-containing resins according to claim (1), wherein the Group IIa metal salt of perchloric acid is barium perchlorate. (3) Claim (1) wherein the organic powder is a chlorine-containing resin powder.
) Powder stabilizer for chlorine-containing resins. (4) The powder stabilizer for chlorine-containing resins according to claim (1), wherein the organic powder is an organic compound used as an additive for chlorine-containing resins. (5) The powder stabilizer for chlorine-containing resins according to claim (1), wherein the organic powder is a Group II metal salt of an organic monocarboxylic acid.