JP2753168B2 - Halogen-containing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halogen-containing resin composition stabilized by incorporating a specific stabilizer system, and more particularly, to an overbased carboxylate / carbonate complex of an alkaline earth metal and The present invention relates to a halogen-containing resin composition having improved thermal stability, weather resistance, initial coloring property, thermal coloring property, transparency and the like by adding a specific inorganic compound in combination.

[0002]

2. Description of the Related Art Halogen-containing resins are difficult to stabilize against heat and light and are exposed to ultraviolet rays during hot molding, use at relatively high temperatures, or outdoors. It is known that when used in place, it is liable to undergo decomposition mainly due to dehydrohalogenation.

For this reason, when processing a halogen-containing resin, several kinds of heat stabilizers such as a metal salt of an organic acid, an inorganic basic metal compound, an organic tin compound, an organic phosphite compound, an epoxy compound and a β-diketone compound are used. Attempts have been made to improve the stability of halogen-containing resins by blending them.

[0004] Among these heat stabilizers, metal organic acid salts are used as basic stabilizers for halogen-containing resins. For example, as described in JP-B-52-49019, metal organic acid salts are used. It has also been proposed to use an organic acid metal salt, generally referred to as an overbased complex, in which the metal base in the organic acid salt is used in excess of the stoichiometric amount.

However, in recent years, with the diversification of uses of halogen-containing resins, processing conditions and use environments have become severe, and the stabilizing effects of conventional stabilizers have become insufficient.

For this reason, it is strongly desired to find a stabilizer system which improves not only the thermal stability or colorability at the processing temperature but also the thermal stability at a relatively high temperature of about 100.degree. I was

[0007]

In view of the above situation, the present inventors have made intensive studies to find a stabilizer that can stabilize a halogen-containing resin for a long period of time even under severe use conditions. By adding an overbased carboxylate / carbonate complex of an alkaline earth metal and a specific inorganic compound to a halogen-containing resin, a halogen-containing resin composition having remarkably excellent heat stability, coloring properties, transparency and the like can be obtained. And completed the present invention.

That is, the present invention provides a halogen-containing resin 10
0 parts by weight of at least one kind of (a) an overbased carboxylate / carbonate complex of an alkaline earth metal;
5 to 10 parts by weight and (b) at least one compound represented by the following general formula (I) of the formula (I):
It is intended to provide a stabilized halogen-containing resin composition containing 1 to 5 parts by weight.

[0009]

_{Embedded image} Mg _x1 Zn _x2 Al ₂ · (OH) _{2x1 + 2x2 + 4} · (CO ₃ ) _{1-y / 2} (ClO ₄ ) _y · mH ₂ O (I) (where x1, x2 and y Represents a number that satisfies the condition represented by the following formula, and m represents 0 or an arbitrary integer.
0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 <20, 0 ≦ y
<2)

Hereinafter, the halogen-containing resin composition of the present invention will be described in detail.

As the overbased carboxylate / carbonate complex of an alkaline earth metal which is the component (a) of the halogen-containing resin composition of the present invention, a compound represented by the following formula (II) is preferable.

[0012]

Embedded image R ₂ M × MCO ₃ (II) (R represents a residue of an organic carboxylic acid, M represents an alkaline earth metal, and x represents a positive number greater than 0 in excess of metal. )

In the above general formula (II), examples of the alkaline earth metal represented by M include barium, calcium, magnesium, strontium and the like. Generally 0.
It is preferably from 1 to 60, particularly preferably from 0.5 to 30. Examples of the residue of the organic carboxylic acid represented by R include caproic acid, caprylic acid, pelargonic acid, 2-ethylhexyl acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, and stearic acid. Acids, isostearic acid, 12-hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linoleic acid, oleic acid, arachiic acid, behenic acid, erucic acid, brassic acid and these And similar mixtures of naturally occurring acids such as tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids, benzoic acid, pt-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluyl Acid, xylyl acid,
And the residue of a monovalent carboxylic acid such as naphthenic acid and cyclohexanecarboxylic acid.

The overbased carboxylate / carbonate complex of an alkaline earth metal represented by the general formula (II) can be prepared by a simple mixture of a normal salt of an alkaline earth metal and a carbonate of an alkaline earth metal of a carboxylic acid. Are completely different from each other in that they are complexed by some kind of interaction, and have a feature that they have a high alkaline earth metal content and show a uniform liquid in an organic solvent.

The above-mentioned overbased carboxylate / carbonate complex of an alkaline earth metal exhibits an excellent stabilizing effect which cannot be attained by a simple mixture because of forming such a complex.

The above-mentioned overbased carboxylate / carbonate complex of an alkaline earth metal can be prepared, for example, by reacting the above organic carboxylic acid with a stoichiometric excess of an alkaline earth metal carbonate; A method in which a stoichiometric excess of an alkaline earth metal oxide or hydroxide is reacted and then treated with carbon dioxide, or an alkaline earth metal carbonate of an organic carboxylic acid is reacted with an alkaline earth metal carbonate. It can be manufactured by a conventionally well-known method such as a method of causing the above. The overbased carboxylate / carbonate complex of alkaline earth metal thus produced is characterized by the type of metal, the type of acid, the content of metal, the metal ratio, and the like. Here, the term “metal ratio” is a term indicating the total chemical equivalent of the metal in the salt with respect to the equivalent of the amount of the metal that forms the neutral salt, and x + 1 in the above general formula (II)
Is equivalent to

The following (Synthesis Example 1) to (Synthesis Example 3) show simple synthesis examples of the above overbased carboxylate / carbonate complexes of alkaline earth metals.

(Synthesis Example 1) Synthesis of overbased barium oleate / carbonate complex Barium hydroxide anhydride 41 was added to 300 g of methylcellosolve.
g of oleic acid 11 g
And nonylphenol 10g and alkylbenzene solvent 3
6 g of the mixture was added and stirred for about 30 minutes. Next, a carbon dioxide gas is blown into the reaction, and the produced water is distilled off for 150 minutes.
After gradually raising the temperature to 0 ° C. and reacting, dehydration and demethylcellosolve were performed under reduced pressure to obtain a brown viscous overbased barium oleate carbonate complex (Ba = 32%,
Metal ratio = 12) was obtained.

(Synthesis Example 2) Synthesis of overbased barium octoate / carbonate complex Barium hydroxide anhydride 34 was added to 480 g of methylcellosolve.
g slowly added to dissolve, then 6 g of octylic acid,
Nonylphenol 20g and alkylbenzene solvent 3
4 g of the mixture was added and stirred for about 30 minutes. Next, a carbon dioxide gas is blown into the reaction, and the produced water is distilled off for 150 minutes.
C. and then dehydrated and demethylcellosolved under reduced pressure to obtain a brown viscous overbased barium octoate carbonate complex (Ba = 28).
%, Metal ratio = 10).

(Synthesis Example 3) Synthesis of Overbased Calcium Olate / Carbonate Complex In a suspension of 30 g of calcium hydroxide in 300 g of methanol, carbon dioxide gas was blown at 15 ° C. to cause a reaction, followed by 11 g of oleic acid. A mixture of 10 g of nonylphenol and 63 g of an alkylbenzene-based solvent was added, and the temperature was gradually raised to 150 ° C. while distilling off methanol and produced water, followed by dehydration under reduced pressure to obtain a light brown viscous basic calcium. Olate carbonate complex (Ca
= 13%, metal ratio = 20).

The above-mentioned alkaline earth metal overbased carboxylate / carbonate complex can be easily produced by the method as described above, and various commercially available complexes can also be used as they are. . Representative examples of these commercially available complexes include, for example, LZ-2116 (overbased barium oleate / carbonate complex: specific gravity 1.47, manufactured by Lubrizol Corporation, USA).
Ba = 34%), LZ-2117 (overbased calcium oleate / carbonate complex: specific gravity 1.07, Ca =
LZ-5341 (overbased calcium oleate / carbonate complex: specific gravity 1.16, Ca = 1)
4.3%).

The amount of the overbased carboxylate / carbonate complex of the alkaline earth metal is 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the halogen-containing resin. It is.

The compound represented by the above general formula (I) which is the component (b) of the halogen-containing resin composition of the present invention includes:
For example, the compounds shown in Table 1 below can be mentioned.

[0024]

[Table 1]

The compound (b) is added in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, per 100 parts by weight of the halogen-containing resin.

The overbased carboxylate / carbonate complex of the alkaline earth metal and the compound represented by the general formula (I) in the present invention can be separately added to the resin. Through
It can be added by blending with another liquid or liquefiable stabilizer composition. In some cases, such a one-pack (blend) stabilizer can improve the stabilizing effect. . The following [Preparation of stabilizer composition] shows a simple preparation example of the stabilizer composition.

[Preparation of stabilizer composition] LZ-2116, compound No. 1, zinc benzoate, benzoic acid, an aromatic hydrocarbon-based solvent and a glycol ether-based solvent were charged at a composition ratio shown in Table 2 below. Stirring was performed at 5 ° C. for 5 hours to prepare a stabilizer composition.

[0028]

[Table 2] * 1: Overbased barium oleate / carbonate complex manufactured by Lubrizol Co., USA: specific gravity 1.47, Ba = 34%

The halogen-containing resin stabilized by the halogen-containing resin composition of the present invention includes a suspension polymerization method,
Vinyl chloride homopolymer or vinyl chloride produced by a known method such as a bulk polymerization method or an emulsion polymerization method and vinyl chloride and ethylene, propylene, vinyl acetate, (meth) acrylic acid ester, maleic anhydride, phenylmaleimide, cyclohexylmaleimide, etc. Copolymer, polyvinylidene chloride, polyvinyl bromide, chlorinated vinyl chloride, chlorinated polyethylene, graft polymer of ethylene / vinyl acetate copolymer and vinyl chloride, urethane resin having unsaturated group and vinyl chloride And a mixture of these with other thermoplastic resins.

Further, the halogen-containing resin composition of the present invention contains a metal such as carboxylic acid, organic phosphoric acid or phenol (Li, Na, K, Ca, Ba, Mg, Sr, Zn,
Cd, Sn, Cs, Al, organic Sn) salts can be added. Examples of the carboxylic acid include caproic acid,
Caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid, chlorostearic acid, 12-ketostearic acid , Phenylstearic acid, ricinoleic acid, linoleic acid, linoleic acid,
Oleic acid, arachinic acid, behenic acid, erucic acid, brassic acid and similar acids and mixtures of the above naturally occurring acids such as tallow fatty acid, coconut oil fatty acid, tung oil fatty acid, soybean oil fatty acid and cottonseed oil fatty acid, benzoic acid, pt -Butyl benzoic acid, ethyl benzoic acid, isopropyl benzoic acid,
Toluic acid, xylyl acid, salicylic acid, 5-t-octyl salicylic acid, naphthenic acid, cyclohexane carboxylic acid, etc., as organic phosphoric acids, mono- or di-octyl phosphoric acid, mono- or di-dodecyl phosphoric acid, mono- or di-octadecyl phosphoric acid, Mono- or di- (nonylphenyl) phosphoric acid, nonylphenyl phosphonate, stearyl phosphonate and the like can be mentioned, and phenols include phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol and the like.

The amount of the metal salt to be added is as follows.
It is preferably 0.05 to 10 parts by weight based on 00 parts by weight.

Among the above-mentioned metal salts, it is preferable to add a zinc carboxylate in combination to improve the colorability.

The halogen-containing resin composition of the present invention may further contain various additives usually used as additives for halogen-containing resins, for example, organic phosphite compounds, epoxy compounds, β-diketo compounds, plasticizers, and the like. Agents and the like can also be blended.

Examples of the organic phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (mono- and di-mixed nonylphenyl) phosphite, diphenyldecyl phosphite, diphenyl (tridecyl) phosphite, and the like. Phenyl dioctyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, tridecyl phosphite, dibutyl acid phosphite,
Dilauryl acid phosphite, diphenyl acid phosphite, di (nonylphenyl) acid phosphite, distearyl pentaerythritol diphosphite, di (tridecyl) pentaerythritol diphosphite, phenyl-4,4'-isopropylidene diphenol
Pentaerythritol diphosphite, tetra (C ₁₂ ~
C ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, and hydrogenated 4,4'-isopropylidenediphenol polyphosphite the like.

Examples of the epoxy compound include epoxidized animal and vegetable oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized tallow oil, epoxidized castor oil, and epoxidized safflower oil. Epoxidized methyl stearate, -butyl, -2
-Ethylhexyl, -stearyl ester, epoxidized polybutadiene, tris (epoxypropyl) isocyanurate, epoxidized tall oil fatty acid ester, epoxidized linseed oil fatty acid ester, bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicyclohexene diepoxide, 3 And epoxy compounds such as 1,4-epoxycyclohexylmethylepoxycyclohexanecarboxylate.

Examples of the β-diketo compound include dehydroacetic acid, dibenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, and metal salts thereof are also useful.

Examples of the plasticizer include phthalate plasticizers such as diheptyl phthalate, dioctyl phthalate and diisononyl phthalate; adipate plasticizers such as dioctyl adipate, diisononyl adipate and di (butyldiglycol) adipate; phosphate plasticizers; Examples include polyester plasticizers, chlorinated paraffin plasticizers, and trimellitate plasticizers.

In addition, if necessary, additives usually used for halogen-containing resins, such as crosslinking agents, fillers, foaming agents, antistatic agents, antifogging agents, plateout preventing agents, surface treatment agents, lubricants, Flame retardants, fluorescent agents, fungicides, fungicides, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, zeolites, powdered silica (silica), perchloric acid Sodium, magnesium perchlorate, barium perchlorate and the like can be blended.

Further, the halogen-containing resin composition of the present invention comprises:
It can be used irrespective of the processing method of the halogen-containing resin, and can be suitably used, for example, for calendering, roll processing, extrusion molding, pressure molding, paste processing, powder molding, and the like. .

[0040]

EXAMPLES Next, the halogen-containing resin composition of the present invention will be described in detail with reference to examples, but the present invention is not limited by the following examples.

Example 1 A mixture of the following (combination) was kneaded on a roll at 180 ° C. for 7 minutes and then pressed at 170 ° C. for 5 minutes to form a mixture having a thickness of 0.5 mm.
Created a sheet. Cut the test piece from this sheet,
The coloring property (initial coloring property) was evaluated on a scale of 10 and the transparency was evaluated as 5
It was evaluated on a scale. Further, the test piece was heated in a gear oven at 190 ° C., and the time until blackening (thermal stability) was measured.

With respect to the evaluation criteria of the coloring property, 1 represents a state without any coloring (yellow, reddish, etc.), and as the numerical value increases,
Coloring becomes severe. The evaluation criterion for transparency indicates that 1 is completely clear, and the transparency decreases as the numerical value increases.

The results are shown in Table 3 below.

(Combination) parts by weight Polyvinyl chloride resin (manufactured by Nippon Zeon: Geon 103 EP-8) 95 diisononyl adipate 35 epoxidized soybean oil 10 zinc oleate 0.2 calcium ricinoleate 0.3 calcium calcium benzoate 0. 05 Trisnonylphenyl phosphite 0.5 LZ-2117 ^{* 2} 0.1 Sample compound (see Table 3) 0.1 * 2: Overbased Ca oleate / carbonate complex manufactured by Lubrizol Corporation

[Table 3]

Example 2 A test piece was prepared in the same manner as in Example 1 with the following (combination) composition, and the heat stability and the transparency were tested in the same manner as in Example 1. The whiteness of the test piece was measured as the initial coloring property.

The results are shown in Table 4 below.

(Combination) parts by weight Polyvinyl chloride resin (manufactured by Zeon Corporation: Geon 103 EP-8) 95 Acrylic impact modifier (Kanebuchi Chemical: Kaneace B-31) 5 dioctyl phthalate 8 epoxy stearic acid Octyl 4 Zinc stearate 0.2 Barium stearate 0.5 Zinc benzoate 0.2 Tetra (C _12-15 alkyl) bisphenol A diphosphite 1.5 Titanium oxide 5 Compound No. 1 0.5 Sample compounds (see Table 4) (See Table 4)

[Table 4] # Determined addition amount (parts by weight) from metal content * 3 Lubrizol, USA, overbased barium phenolate / carbonate complex (Ba = 28%, specific gravity: 1.3)
0) * 4 Overbased barium oleate / carbonate complex (Ba = 34%, specific gravity: 1.47) manufactured by Lubrizol, USA * 5 Overbased calcium oleate / carbonate complex (Ca = 14.2) manufactured by Lubrizol, USA %, Specific gravity: 1.
07) * 6 Lubrizol, USA, overbased calcium oleate / carbonate complex (Ca = 14.3%, specific gravity: 1.
16) * 7 Overbased barium octoate carbonate complex synthesized in (Synthesis Example 1) * 8 Overbased barium octoate carbonate complex synthesized in (Synthesis Example 2) * 9 Basic calcium oleate carbonate complex

Example 3 The following (combination) compound was kneaded on a roll at 160 ° C. for 5 minutes and then pressed at 160 ° C. for 5 minutes to form a sheet having a thickness of 0.5 mm. A test piece was prepared from this sheet, the test piece was heated in a gear oven at 190 ° C., and the time until blackening (thermal stability) was measured. In addition, the coloring (thermal coloring) of the test piece after heating at 190 ° C. for 60 minutes was observed,
It was evaluated on a 10-point scale. At that time, 1 indicates no coloring and 10 indicates remarkable coloring. In addition, 1
The mixture was heated in a gear oven at 10 ° C., and the number of days until blackening (heat aging) was measured.

The results are shown in Table 5 below.

(Combination) parts by weight polyvinyl chloride resin (manufactured by Nippon Zeon: Geon 103 EP) 100 di (C _9-11 alkyl) phthalate 40 epoxidized soybean oil 2 zinc stearate 0.1 barium stearate 0.2 Dibenzoylmethane 0.1 Phenyldi (tridecyl) phosphite 0.6 Barium perchlorate 0.1 Stabilizer composition (See Table 5) (See Table 5)

[Table 5]

Example 4 The following components were kneaded on a roll at 180 ° C. for 7 minutes and then pressed at 170 ° C. for 5 minutes to form a 0.5 mm thick sheet. A test piece was prepared from this sheet, heated in a gear oven at 190 ° C., and the time until blackening was measured. In addition, in a fade meter at a black panel temperature of 83 ° C., the coloring (weather resistance) of the test pieces after light irradiation for 10 days and 20 days was evaluated on a 10-point scale. 1 indicates no coloring, and 10 indicates remarkable coloring. In addition, 110
After heating in a gear oven at 2 ° C. for 2 weeks, coloring (heat aging) of the test pieces was evaluated on a 10-point scale. 1 indicates no coloring, and 10 indicates remarkable coloring.

The results are shown in Table 6 below.

(Combination) parts by weight polyvinyl chloride resin (TK-1300 manufactured by Shin-Etsu Chemical Co., Ltd.) 100 di (C _9-11 alkyl) phthalate 80 chlorinated paraffin 10 calcium carbonate 15 epoxidized soybean oil 4 zinc stearate 0 .4 Barium stearate 0.5 Phenyldi (tridecyl) phosphite 0.5 Stabilizer composition (see Table 6) 1.0

[0054]

[Table 6]

From the results shown in Tables 3 to 6, when an overbased phenolate / carbonate complex, which is an overbased complex other than the component (a) of the present invention, was used, a conventional metal carboxylate was used. It can be seen that when used or when a metal carboxylate and a metal carbonate are used in combination, there is almost no improvement effect as compared with the case where a normal metal carboxylate is used.

On the other hand, the composition of the present invention using the overbased carboxylate / carbonate complex of the metal and the compound represented by the above general formula (I) only significantly improves the heat stability and the coloring property. In addition, it is extremely excellent in transparency, and it is clear that the effect of the present invention is remarkably excellent.

[0057]

The halogen-containing resin composition of the present invention has remarkably excellent heat stability, colorability, transparency and the like.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kenji Nakazawa 5-2-13-Shirahata, Urawa-shi, Saitama Prefecture Asahi Denka Kako Kogyo Co., Ltd. (72) Inventor Shinji Shinbube 5-2-2 Shirahata, Urawa-shi, Saitama No. 13 Asahi Denka Kogyo Co., Ltd. (56) References JP-A-2-284946 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 27/00-27/24 C08K 3/00-13/08

Claims (1)

(57) [Claims] (1) 100 parts by weight of a halogen-containing resin, (a)
0.05 to 10 parts by weight of at least one kind of an overbased carboxylate / carbonate complex of an alkaline earth metal and (b) 0.001 to 5 parts by weight of at least one kind of a compound represented by the following general formula (I) A stabilized halogen-containing resin composition comprising the above components. _{Embedded image} Mg _x1 Zn _x2 Al _2. (OH) _{2x1 + 2x2 + 4.} (CO ₃ ) _{1 -y / 2} (ClO ₄ ) _y .mH ₂ O (I) (where x 1, x 2 and y Represents a number that satisfies the condition represented by the following formula, and m represents 0 or an arbitrary integer.
0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 <20, 0 ≦ y
<2)