JP2573755B2 - Heat stabilized chlorine-containing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to a thermally stabilized chlorine-containing resin composition.

[0002]

2. Description of the Related Art A chlorine-containing resin composition is an excellent material having various excellent properties. When the resin composition is heated and formed, it is decomposed to cause dehydrochlorination, thereby coloring the product, thereby increasing the commercial value of the product. There is a disadvantage of deterioration. For this reason, thermal stabilization by adding a stabilizer to this has been widely performed.

The stabilizer used herein is a combination of a low-toxic or non-toxic stabilizer and various heat stabilizing aids. For example, an organic metal salt compound, Ba-Z
An organic phosphite compound, a hindered phenolic antioxidant, an epoxy compound, and the like are combined with a metallic soap of n or Ca—Zn.

[0004] The stabilization method of adding these stabilizers is as follows.
Each of them has no problem in terms of toxicity and has a certain effect in prevention of discoloration during thermoforming. However, the fact is that further improvement in the performance was expected. To this end, many proposals have conventionally been made to further improve the performance of the above stabilizers by further adding various stabilizing aids.

The present applicant also proposed a method using a β-diketon compound in JP-B-52-47948 and JP-B-57-9386, and a method using a metal salt compound of β-diketone in JP-B-57-39260. Further, Japanese Unexamined Patent Publication No.
JP-A-80444 discloses a method of using a β-diketone compound and hydrotalcite in combination, JP-B-2-27376 discloses the use of a combination of hydrotalcite and a metal salt of perchloric acid, and JP-B-2-28614 discloses a method using hydrotalcite. It was proposed to add pentaerythritol in combination.

[0006]

The present invention relates to a method for thermoforming a chlorine-containing resin composition by adding a new combination of a non-toxic or low-toxic heat stabilizer and a stabilizing aid to the chlorine-containing resin. The purpose is to prevent the initial coloring when processed and to improve the transparency of the molded article.

[0007]

According to the present invention, there is provided a chlorine-containing resin comprising: (a) a barium-zinc or calcium-zinc metal salt compound of a carboxylic acid and an alkylphenol;
(B) a heat-stabilized chlorine-containing resin comprising a combination of a sulfonyl compound represented by the following general formula and (c) at least one of the following (a) to (c): A composition comprising: (i) at least one β-diketone compound which is alkanoylaroylmethane or dialoylmethane;
(B) at least one selected from complex compounds which are liquid at room temperature and comprise any one of sodium, magnesium, calcium or barium salts of perchloric acid and polyhydric alcohols and derivatives thereof; At least one or more of talcite, A-type synthetic zeolite and calcium hydroxide,

[0008] [Wherein, X represents a chlorine atom or an amino group, Y represents a hydrogen atom, an aralkyl group, a halogenated alkyl group, or an aryl group having a substituent (as a substituent, a carboxy group or a halogenated sulfonyl group)]. Claim 1), wherein the metal salt compound of barium or calcium of a carboxylic acid or an alkylphenol is a combination of an overbased carboxylate carbonate complex or an overbased alkylphenate carbonate complex with zinc carboxylate. 2. The thermally stabilized chlorine-containing resin composition according to claim 2, wherein the alkanoylaroylmethane is stearoylbenzoylmethane and the dialoylmethane is at least one β-diketone compound of dibenzoylmethane. A thermally stabilized chlorine-containing resin composition (Claim 3) and 2. The complex compound according to claim 1, wherein the complex compound which is liquid at a temperature is a complex compound of any one of sodium perchlorate, magnesium perchlorate and barium perchlorate with ethylene glycol monobutyl ether or ethylene glycol monomethyl ether. A thermally stabilized chlorine-containing resin composition (Claim 4). Hereinafter, these inventions will be described.

[0009] The invention of claim 1 provides the chlorine-containing resin with:
(A) Barium of carboxylic acids and alkylphenols
(B) zinc or calcium-zinc metal salt compound;
It is a combination of a sulfonyl compound represented by the following general formula and (c) at least one or more of (a) to (c) shown below.

As the metal salt compound (a), barium-zinc and calcium-zinc are preferably used. The organic metal salt compound so-called metal soap used here can be used alone or in combination of two or more.
In addition, the organic acids that bind to the metal include carboxylic acids and phenols.

The carboxylic acid includes a saturated or unsaturated aliphatic carboxylic acid having 2 to 22 carbon atoms, and a carboxylic acid having 7 to 16 carbon atoms.
And a hydroxy or alkoxy acid having 2 to 10 carbon atoms. These are, for example,
Hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, isodecanoic acid, lauric acid, mystic acid, palmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid, behenic acid, oleic acid, ricinoleic acid, linoleic acid , Linolenic acid, oxalic acid, malonic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, benzoic acid, toluic acid, xylic acid, pt-butylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, silica It is cinnamic acid, acrylic acid, methacrylic acid, acetoacetic acid, nicotinic acid, furic acid or a mixed carboxylic acid thereof.

The phenols include, for example, phenol, methylphenol, dimethylphenol, ethylphenol, pt-butylphenol, pt-octylphenol, nonylphenol, dinonylphenol, decylphenol and dodecylphenol.

These organic acid metal salt compounds may be acidic salts or neutral salts, and may be basic salts or overbased salts.

The amount of the metallic soap is 0.1 to 8 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

The stabilizer component (b) according to the first aspect of the present invention.
Is a sulfonyl compound represented by the general formula

[0016] [In the formula, X represents a chlorine atom or an amino group, and Y is a sulfonyl compound represented by a hydrogen atom, an aralkyl group, or an aryl group having a substituent (a carboxy group or a halogenated sulfonyl group as a substituent). .

These include, for example, 4-chlorosulfonylbenzoic acid, α-toluenesulfonyl chloride, 3-chloropropanesulfonyl chloride, trichloromethanesulfonyl chloride, 4-sulfamoylbenzoic acid, formamidine sulfinic acid, benzene- 1,2-disulfonyl chloride. The addition amount of these sulfonyl compounds may be 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the chlorine-containing resin.

The component (c) includes (a) at least one β-diketone compound which is alkanoylaroylmethane or dialoylmethane, and (b) one of sodium, magnesium, calcium or barium salt of perchloric acid. And at least one selected from the group consisting of polyhydric alcohols and their derivatives, which are liquid at room temperature, and (c) at least one of synthetic hydrotalcite, A-type synthetic zeolite, and calcium hydroxide. Is at least one. The β-diketone compound (a) is alkanoylaroylmethane or dialoylmethane, for example, acetylstearoylmethane, benzoylacetone, stearoylbenzoylmethane, palmitoylbenzoylmethane, dibenzoylmethane, benzoyl-
P-anisoylmethane. The mixing ratio of these β-diketone compounds is based on 100 parts by weight of the chlorine-containing resin.
It is 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight.

The sodium perchlorate, magnesium perchlorate, calcium perchlorate or barium perchlorate of (b) can be used in any one of them.
More than one species can be used. These complex compounds are described in JP-B-62-16220 and JP-B-63-46.
No. 2. One or more of these complex compounds composed of various metal salts of perchlorate and polyhydric alcohols can be used.

The polyhydric alcohol and derivatives thereof used herein include, for example, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol, diethylene glycol. Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol, polyethylene glycol, propylene Recall, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, polypropylene glycol, trimethylene glycol, 1,4-butane Diol, glycerin and the like.

In order to form a complex compound between the metal salt of perchlorate and a polyhydric alcohol or a derivative thereof, the reaction ratio is 15:85 to 70:30 by weight, preferably 30:70 to 30:70.
55:45. This complex compound is colorless or yellowish-brown, and is a transparent or translucent liquid at room temperature.

The mixing ratio of the above metal perchlorate or a complex compound with the metal perchlorate is 0.1 to 100 parts by weight of the chlorine-containing resin.
The amount is from 0.01 to 5 parts by weight, preferably from 0.05 to 2 parts by weight.

The component (c) is at least one of synthetic hydrotalcite, A-type synthetic zeolite, and calcium hydroxide. The amount of addition was 1
The amount is 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, based on 00 parts by weight.

According to the first aspect of the present invention, as described above, (a) metallic soap, (b) a sulfonyl compound, and (c) the above (a)
To (c).

The second to fourth aspects of the present invention specify the constituent elements of the first aspect of the present invention.

That is, claim 2 is that a barium or calcium metal salt compound of a carboxylic acid or an alkylphenol is
It is a combination of an overbased carboxylate carbonate complex or an overbased alkyl carbonate carbonate complex and zinc carboxylate.

Claim 3 specifies that the alkanoyl aroyl methane of the β-diketone compound is specified as stearoyl benzoyl methane and the dialoyl methane is specified as dibenzoyl methane.

In a preferred embodiment, the complex compound which is liquid at room temperature is a complex compound of any one of sodium perchlorate, magnesium perchlorate and barium perchlorate with ethylene glycol monobutyl ether or diethylene glycol monomethyl ether. It is.

The present invention, in addition to containing the above-mentioned stabilizer component,
Various stabilizing aids and other additives can be included.
These are organic phosphites, antioxidants, epoxy compounds, polyhydric alcohols and their esters, light stabilizers and the like, and these can be used alone or in combination according to the purpose.

The organic phosphite used here includes, for example, triphenyl phosphite, triisooctyl phosphite, triisodecyl phosphite,
Triisodecylthiophosphite, tribenzylphosphite, trisnonylphenylphosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyltridecylphosphite, distearylpentaerythritol diphosphite, diisodecylpentaerythritoldi Phosphite, diphenylpentaerythritol diphosphite, tris-2,
4-di-t-butylphenyl phosphite, 2,4-di-t-butylphenyl diisodecyl phosphite, trisbutoxyethoxyethyl phosphite, 4,4′-isopropylidene diphenylalkyl (C _{12 to} C ₁₅ )
Diphosphite, 4,4'-isopropylidenedicyclohexyltetratridecyl diphosphite, tetraphenyl (dipropylene glycol) phosphite, pentakis (dipropylene glycol) trisphite, poly (dipropylene glycol) phenyl phosphite and the like.

Acid phosphites in which one or two of the organic residues in the above-mentioned organic phosphites are substituted by hydrogen atoms are also effective, such as diphenyl acid phosphite, monophenyl acid phosphite and diphenyl acid phosphite. Isooctyl acid phosphite, monoisooctyl acid phosphite, phenyl isooctyl acid phosphite, phenyl isodecyl acid phosphite, dinonyl phenyl acid phosphite and the like.

The antioxidants used here include hindered phenols such as alkylated phenols,
Alkylated phenol esters, alkylene or alkylidene bisphenols, polyalkylated phenol esters, alkylene or alkylidene bisphenols, polyalkylated phenols. These are, for example, 2,
6-di-t-butyl-4-methylphenol, 2,2 '
-Methylenebis (4-methyl-6-t-butylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), tetrakis [methylene-3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate] methane. Examples of the sulfur-containing alkyl alkanoate include dilauryl thiodipropionate and distearyl thiodipropionate.

Epoxy compounds include epoxidized unsaturated oils, epoxidized unsaturated fatty acid esters, epoxycyclohexane derivatives and epichlorohydrin derivatives, such as epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxy Alkyl esters such as oxidized safflower oil, epoxidized linseed oil and fatty acid butyl, butyl epoxy stearate and 2-ethylhexyl;
-(2-xenoxy) -1,2 epoxypropane, epoxy polybutadiene, bisphenol-A-diglycidyl ether, 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate and the like.

Organic phosphoric ester compounds such as nonylphenoxypolyethoxyphosphate, tridecylhydroxypolyethoxyphosphate, octylphenoxypolyethoxyphosphate, and the like are used as processing aids. Further, the metal adduct thereof, for example, magnesium, calcium or barium salt of monodi-mixed isooctyl phosphate, sodium, magnesium, calcium, barium or zinc salt of mono-di-mixed stearyl phosphate is useful as a heat stabilizing aid.

Others used as light stabilizers are represented by benzotriazoles and hindered amines, for example, 2- (3,5-di-t-butyl-).
2-hydroxyphenyl) benzotriazole, 2-hydroxyphenyl-5-chlorobenzotriazole, dimethyl succinate-1- (2-hydroxyethyl) -4
-Hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-
Diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene-[(2,2,6
-Tetramethyl-4-piperidyl) imino], 2-
(3,5-di-t-butyl-hydroxybenzyl) -2
Bis (1,2,2 ', 6,6-pentamethyl-4-piperidyl) -n-butylmalonate.

Other stabilizing aids include polyhydric alcohols such as pentaerythritol, dipentaerythritol, mannitol and sorbitol. The polyhydric alcohol, aliphatic monohydric or dihydric carboxylic acid,
Heterocyclic carboxylic acid, an ester compound with an amino acid or rosin, for example, pentaerythritol stearate, dipentaerythritol adipate, dipentaerythritol pyrrolidone carboxylate, dipentaerythritol glutamate, wood rosin pentaerythritol, and the like nitrogen-containing Β-aminocrotonic acid, which is a compound, and ester compounds such as 1,3 and 1,4-butanediol and thiodiethylene glycol.

The above-mentioned stabilizing aid and processing aid can be appropriately used for the purpose of further improving thermal stability, weather resistance and workability.

Examples of the chlorine-containing resin in the present invention include polyvinyl chloride, copolymers with vinyl chloride, for example, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-urethane copolymer, polyvinyl chloride. And chlorinated polyvinyl chloride.

The chlorine-containing resin composition of the present invention can obtain a wide range of molded products from hard to soft by increasing or decreasing the amount of a plasticizer, for example, a phthalate ester, depending on the use of the molded product. If necessary, a filler, a pigment, an antistatic agent, an anti-fogging agent, a flame retardant, a screening agent, a cross-linking agent, a foaming agent and other processing agents can be appropriately used in combination.

[0040]

[Embodiment 1] Test pieces were prepared from the chlorine-containing resin composition using the stabilizer components (a) and (b) used in claim 1 of the present invention, and the thermal stability of the test pieces was examined. In the test, the following composition was kneaded for 5 minutes with a kneading roll heated to 180 ° C. A 3 mm uniform sheet was prepared, and the following experiment was performed using the sheet as an original sheet.

Formulation Polyvinyl chloride (degree of polymerization 1050) 100 parts by weight Dioctyl phthalate 28 〃 Epoxidized soybean oil 2 Barium stearate 0.5 亜 鉛 Zinc stearate 0.2 過 Overbased barium oleate carbonate complex 0.8 0.8 2 -Zinc ethylhexanoate 0.8 {Diphenylisooctyl phosphite 0.6} Stabilizer component (b) Test 1 described in Table 1. A test piece was prepared from the original sheet and placed in a gear oven aging tester heated to a certain temperature for a certain time,
The time required for the initial coloring due to thermal deterioration and the black color separation was determined.

Test 2. From the original sheet, a test piece similar to the test 1 was prepared, and 12 test pieces were stacked on a metal mold.
Pressure molding was performed at kg / cm ² for 10 minutes to obtain a pressed plate having a thickness of 3 mm. The coloring and transparency produced by this press thermoforming were examined. The results are shown in Table 1. Table 1
Also shows a comparative example. As shown in the table, it can be seen that all of the present invention obtained good results.

[0043] Embodiment 2. FIG. Test pieces were made from the chlorine-containing resin composition using the stabilizer components (a) to (c) used in claim 2 of the present invention, and the thermal stability of the test pieces was examined. Compounding polyvinyl chloride (degree of polymerization 1050) 100 parts by weight diisononyl adipate 48 "epoxidized soybean oil 2 barium stearate 0.5 zinc stearate 0.2" overbased barium dodecyl phenate carbonate complex 0.8〃 2- Zinc ethylhexanoate 0.8 {Diphenyldecyl phosphite 0.6} Stabilizer components (b) to (c) As shown in Table 2, a sheet similar to that of Example 1 was made from the above composition.
Using this, tests similar to tests 1 and 2 of Example 1 were performed.

Further, the original sheet was placed in a gear oven aging tester in the same manner as in Test 1, and the heat deterioration due to high temperature and long time and its coloring were examined. The results are shown in Table 2. The table also shows comparative examples. As can be seen from the table, all of the examples of the present invention have obtained good results.

Incidentally, Na-BG (Note-1) in Table 2 is
Complex salt of sodium perchlorate-ethylene glycol monobutyl ether (45:55 weight ratio), Mg-BG
(Note-2) is a complex salt of magnesium perchlorate-ethylene glycol monobutyl ether (35:65 weight ratio),
Ba-MDG (Note-3) is a complex salt of barium perchlorate-diethylene glycol monomethyl ether (30:70 weight ratio), and Alkamizer # 2 (Note-4) is a synthetic hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd. Brand name, GSL
-1000 (Note-5) is an A-type zeolite and is a trade name of Toyo Soda Kogyo Co., Ltd.

[0046]

[0047]

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08K 5/07 KGV C08K 5/07 KGV 5/41 5/41 (56) References JP-A Sho57 JP-A-143341 (JP, A) JP-A-56-16543 (JP, A) JP-A-57-80444 (JP, A) JP-T-60-502108 (JP, A) JP-B-2-27376 (JP, B2) Japanese Patent Publication No. Sho 63-462 (JP, B2) Japanese Patent Publication Sho 62-16220 (JP, B2)

Claims (4)

(57) [Claims] 1. A chlorine-containing resin comprising (a) a barium-zinc or calcium-zinc metal salt compound of a carboxylic acid and an alkylphenol, (b) a sulfonyl compound represented by the following general formula, and (c) the following (a): A heat-stabilized chlorine-containing resin composition comprising a combination of at least one of (c) to (c). (B) at least one kind of β-diketone compound which is alkanoylaroylmethane or dialoylmethane; (b) room temperature comprising any one of sodium, magnesium, calcium or barium salt of perchloric acid and a polyhydric alcohol and a derivative thereof. (C) at least one or more of synthetic hydrotalcite, A-type synthetic zeolite and calcium hydroxide. General formula [In the formula, X represents a chlorine atom or an amino group, and Y represents a hydrogen atom, an aralkyl group, a halogenated alkyl group, or an aryl group having a substituent (as a substituent, a carboxy group or a halogenated sulfonyl group)]. 2. The barium or calcium metal salt compound of a carboxylic acid or an alkylphenol is a combination of an overbased carboxylate carbonate complex or an overbased alkylphenate carbonate complex with zinc carboxylate. A thermally stabilized chlorine-containing resin composition according to any one of the preceding claims. 3. The thermally stabilized chlorine-containing resin composition according to claim 1, wherein the alkanoylaroylmethane is stearoylbenzoylmethane, and the dialoylmethane is at least one β-diketone compound that is dibenzoylmethane. 4. The complex compound which is liquid at room temperature is a complex compound of any one of sodium perchlorate, magnesium perchlorate and barium perchlorate with ethylene glycol monobutyl ether or ethylene glycol monomethyl ether. The thermally stabilized chlorine-containing resin composition according to claim 1.