JPS6146016B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilizer for chlorine-containing resins made of a novel boron compound, and provides a stabilizer that can constitute a chlorine-containing resin composition having excellent thermal stability. As is well known, when chlorine-containing resins are heated and molded, they undergo thermal decomposition mainly due to dehydrochlorination, which has major drawbacks such as coloring of molded products and reduction in mechanical strength. There is. For this reason, in order to suppress thermal decomposition of the resin, a heat stabilizer is added to the chlorine-containing resin for molding. There are a wide variety of compounds conventionally used as heat stabilizers, with typical examples being organotin compounds,
Examples include metal soaps, inorganic metal compounds, organic phosphite esters, epoxy compounds, and antioxidants. In practical use, these compounds are used singly or in combination as needed, but they are still not sufficient, and there is a strong demand for an excellent heat stabilizer. Prior art in which boron compounds have been used as stabilizers for chlorine-containing resins include Japanese Patent Publication No. 35-8244 (method for stabilizing halogen-containing vinyl resins);
−11494 (Resin stabilization method), Special Publication No. 11494 (Sho 42)
No. 11495 (method for stabilizing resins), Japanese Patent Publication No. 19176/1976 (stabilizing compositions for resins), and Japanese Patent Publication No. 111346/1983 (method for stabilizing halogen-containing polymers). However, even these were not completely satisfactory. In view of these circumstances, the present inventors continued intensive research and found that the groups represented by the following formulas () to () -OR ¹ SR ² () -OR ¹ SR ¹ O- () -OR ¹ SR ³ SR ¹ O- () (In the formula, R ¹ is an alkylene group, or a group in which the hydrogen atom bonded to the carbon atom of this group is substituted with a hydroxyl group, mercapto group, or alkyl group. R ²
is a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, an arylalkyl group, an alkylaryl group, or an arylalkenyl group. R ³ is an alkylidene group or a group in which the hydrogen atom bonded to the carbon atom of this group is substituted with an alkyl group. )
The present invention was completed based on the discovery that a stabilizer for chlorine-containing resins made of a specific boron compound having at least one compound has an excellent thermal stabilizing effect. A typical example of the boron compound as a stabilizer for chlorine-containing resins of the present invention is shown by the general formula: etc. can be mentioned. [In general formulas (1) to (15), R ¹ , R ² , and R ³ are as described above. The group represented by R ⁴ is a hydroxyl group, an alkyloxy group, an alkenyloxy group, or a hydrogen atom bonded to a carbon atom of these groups is substituted with a hydroxyl group, an alkyl group, a mercapto group, an alkyloxy group, or a hydroxyalkyloxy group. It is the basis. The group represented by R ⁵ is an alkylene group, a group in which the hydrogen atom bonded to the carbon atom of this group is substituted with a hydroxyl group, an alkyl group, a hydroxyalkyl group, an alkyloxy group, and a −R ¹ SR ¹ − group. . X, Y, and Z are an oxygen atom, an alkylenedioxy group, or a group in which the hydrogen atom bonded to the carbon atom of this group is substituted with a hydroxyl group, an alkyl group, a hydroxyalkyl group, an alkyloxy group, and -OR ¹ SR ¹ It is an O- group. x is a number from 0 to 2. y is a number from 1 to 5. ] To explain the general formula, examples of the group represented by R ¹ include an alkylene group having 2 or 3 carbon atoms, or a group in which the hydrogen atom bonded to the carbon atom of this group is substituted with a hydroxyl group, mercapto group, or alkyl group. be able to. Specific examples of R ¹ include ethylene, trimethylene, propylene, hydroxyethylene, hydroxytrimethylene, mercaptoethylene, mercaptotrimethylene, octylethylene, dodecylethylene and the like. Examples of the group represented by ^R2 include a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a phenyl group, an arylalkyl group having 7 to 9 carbon atoms, and an alkylaryl group having 7 to 15 carbon atoms. and an arylalkenyl group having 8 or 9 carbon atoms. Specific examples of ^R2 include hydrogen atom, methyl, ethyl, propyl, octyl, dodecyl, stearyl, allyl, hexenyl, octenyl, oleyl, phenyl, benzyl, phenethyl, β-phenylpropyl, tolyl, xylyl,
Examples include ethyl phenyl, butylphenyl, octylphenyl, nonylphenyl, styryl, cinnamyl, and the like. Examples of the group represented by R ³ include an alkylidene group having 1 to 9 carbon atoms, or a group in which a hydrogen atom bonded to a carbon atom of this group is substituted with an alkyl group. Specific examples of ^R3 include methylene, ethylidene, propylidene, butylidene, pentylidene, 1-methylethylidene, 1-ethylpropylidene, and 1-methyloctylidene. Examples of the group represented by R ⁴ include a hydroxyl group, an alkyloxy group having 1 to 18 carbon atoms, an alkenyloxy group having 3 to 18 carbon atoms,
Alternatively, examples include groups in which the hydrogen atom bonded to the carbon atom of these groups is substituted with a hydroxyl group, an alkyl group, a mercapto group, an alkyloxy group, or a hydroxyalkyloxy group. Specific examples of ^R4 include hydroxy, methoxy, ethoxy, propoxy, butoxy, octyloxy, decyloxy, lauryloxy, stearyloxy, allyloxy, hexenyloxy, octenyloxy,
Oleyloxy, hydroxyethyloxy, hydroxypropyloxy, hydroxypropenyloxy, hydroxystearyloxy, 1-ethylbutyloxy, 2-ethylhexyloxy, 2-
Mercaptoethyloxy, 3-mercaptopropyloxy, methoxyethyloxy, methoxylauryloxy, butoxyoleyloxy, hydroxyethyloxyethyloxy, hydroxypropyloxyethyloxy, hydroxymethyloxypropyleneoxy,

【formula】

【formula】

【formula】

[Formula] etc. can be mentioned. The group represented by R ⁵ is an alkylene group having 1 to 6 carbon atoms, or a group in which the hydrogen atom bonded to the carbon atom of this group is substituted with a hydroxyl group, an alkyl group, a hydroxyalkyl group, an alkyloxy group, and -
An example is R ¹ SR ¹ - group. Specific examples of ^R5 include methylene, ethylene, trimethylene, propylene, butylene, hexylene, ethylethylene, methyltrimethylene, dimethylethylene, methoxypropylene, methoxybutylene,

[Formula] -CH ₂ CH ₂ SCH ₂ CH ₂ -, etc. can be mentioned. The group represented by Examples include substituted groups and -OR ¹ SR ¹ O- groups. X,
Specific examples of Y and Z include oxygen atom, ethylenedioxy, propylenedioxy, butylenedioxy,
hexylene dioxy,

【formula】

[Formula] −OCH ₂ CH ₂ SCH ₂ CH ₂ O−,

【formula】

[Formula] etc. can be mentioned. Examples of preferred boron compounds of the present invention are shown below (a) to
As shown in (t) etc. can be mentioned. Next, an example of manufacturing the boron compound of the present invention is shown in (a) above.
The compounds represented by (b), (c), (f), (g), and (i) will be specifically explained. Production Example (1) Boron Compound (a) 34.0 g (0.549 mol) of boric acid, 85.8 g (1.098 mol) of 2-mercaptoethanol, and 100 g of toluene were heated with stirring. 105℃ under reflux of toluene
The reaction was carried out at 113°C for 2 hours, and 19.0 g of produced water was distilled off. Next, toluene was distilled off under reduced pressure to obtain 99 g of a colorless transparent liquid. The boron content was 5.9%. The following procedure is carried out in the same manner as in Production Example (1). Production example (2) Boron compound (b) Boric acid 23.2g (0.375 mol), 2-hydroxy-2
-Alkylethyl mercaptan (alkyl is a mixture of 12 to 16 carbon atoms, HS% = 13.7%) 90.4g
(0.375 mol) and 100 g of toluene were reacted for 2 hours, and 11.0 g of produced water was distilled off. Toluene was distilled off to obtain 102 g of a pale yellow transparent liquid. The boron content was 4.0%. Production example (3) Boron compound (c) Boric acid 28.6g (0.463mol), 2-octylthioethyl alcohol 88.1g (0.463mol), toluene
100g was reacted for 3 hours and 16.2g of produced water was distilled off. Toluene was distilled off to obtain 100 g of a pale yellow transparent liquid. The boron content was 5.0%. Production Example (4) Boron Compound (f) 14.0 g of water produced by reacting 31.9 g (0.516 mol) of boric acid, 86.7 g (0.516 mol) of methylene bis(thioethyl alcohol), and 100 g of toluene for 3 hours was distilled off. Colorless and transparent viscous liquid 103 obtained by distilling off toluene
I got g. The boron content was 5.5%. Production example (5) Boron compound (g) 41.8 g (0.676 mol) of boric acid, 82.5 g (0.676 mol) of thiobisethyl alcohol, and 100 g of toluene
The reaction was allowed to proceed for a period of time, and 24.3 g of produced water was distilled off. Toluene was distilled off to obtain 99 g of a colorless viscous liquid. boron content
It was 7.3%. Production example (6) Boron compound (i) Boric acid 71.2g (1.151 mol), thiodiethanol
70.3 g (0.576 mol) and 100 g of benzene were reacted for 4 hours, and 35 g of produced water was distilled off. Benzene was distilled off to obtain 105 g of a colorless viscous liquid. Boron content 12.4%
It was hot. The amount of the stabilizer for chlorine-containing resin of the present invention to be used for the chlorine-containing resin is not particularly limited, but the necessary amount is determined as appropriate depending on the molding method of the chlorine-containing resin and the use of the product. It is usually added in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight. When stabilizing a chlorine-containing resin using the stabilizer of the present invention, other known stabilizers may be used as necessary, such as organic tin compounds, metal soaps, inorganic metal compounds, organic phosphite esters, epoxy compounds, It can be used in combination with antioxidants, etc. Specific examples of these include monobutyltin tolulaurate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin maleate, dioctyltin maleate, dibutyltin bis(butyl maleate), bis(dibutyltin benzyl maleate) maleate, dioctyltin bis(iso octyl maleate), monobutyltin sulfide, dibutyltin sulfide, monobutyltin tris(lauryl mercaptide), monobutyltin tris(isooctylmercaptoacetate), dibutyltin bis(isooctyl β-mercaptopropionate), dioctyltin bis( isooctyl mercaptoacetate), dibutyltin β-mercaptopropionate, dioctyltin thioglycolate,
Calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, barium hydroxide,
Barium stearate, calcium stearate, zinc stearate, calcium laurate,
Magnesium stearate, aluminum stearate, triphenyl phosphite, diphenyldecyl phosphite, di(nonylphenyl)
Hydrodiene phosphorite, epoxidized soybean oil, epoxidized linseed oil, epichlorohydrin and bisphenol A condensed epoxy resin, 2,6
-di-tert-butyl-4-hydroxytoluene,
2-tert-butyl-4-hydroxyanisole,
Bisphenol A, 2,2'-methylenebis(6-
tert-butyl-4-hydroxytoluene), 4,
4'-thiobis(3-methyl-6-tert-butylphenol), dilaurylthiodipropionate,
Thiodipropionic acid, etc. can be shown. Of course, other known stabilizers, plasticizers, flame retardants, lubricants, fillers, antistatic agents, etc. can also be used in combination with the stabilizer of the present invention, if necessary. If a chlorine-containing resin is stabilized by combining the stabilizer of the present invention and a metal soap compound, an excellent resin composition with less initial coloration, which cannot be achieved with a metal soap compound alone, can be obtained. When the stabilizer of the invention is combined with an organic tin compound, a resin composition with low initial coloration and excellent sustained heat stability can be obtained, and furthermore, the mechanical strength of the resin molded product is not reduced. Typical examples of chlorine-containing resins stabilized by the stabilizer of the present invention include vinyl chloride resin, vinylidene chloride resin, chlorinated polyethylene, vinyl chloride/vinyl acetate copolymer resin, and vinyl chloride/ethylene copolymer resin. , vinyl chloride/styrene copolymer resin, vinyl chloride/styrene/acrylonitrile copolymer resin, vinyl chloride/methacrylic acid ester copolymer resin, and vinyl chloride/acrylonitrile copolymer resin, and further acrylonitrile/butadiene/styrene copolymer resin. Polymer resin (hereinafter referred to as
Abbreviated as ABS resin. ) Blend resins of methacrylic acid methyl ester/butadiene/styrene copolymer resins, polyethylene, polypropylene, ethylene/vinyl acetate copolymer resins, acrylonitrile/styrene copolymer resins, etc., and vinyl chloride resins can be shown. There are no particular restrictions on the method of mixing the stabilizer of the present invention with the chlorine-containing resin, and mixing can be easily done using commonly used ribbon blenders, Banbury mixers, super mixers, Henschel mixers, extruders, mixing rolls, etc. I can do it. Next, the effects of the stabilizer of the present invention will be specifically explained with reference to Examples. The stabilizers corresponding to the abbreviations (T) to (Z) in the table of Examples are as follows. (T) Dioctyltin bis(isooctyl mercaptoacetate) (U) Dibutyltin bis(isooctyl β-mercaptopropionate) (V) Monobutyltin tris(isooctyl β-
Mercaptopropionate) (W) Dibutyltin dilaurate (X) Dibutyltin maleate (Y) Calcium stearate (Z) Zinc stearate In the examples, parts mean parts by weight. Example 1 Vinyl chloride resin [Geon103Ep Nippon Zeon Co., Ltd.
A predetermined amount of the boron compound shown in Table 1 was added to 100 parts of Stearic Acid and 0.2 parts of stearic acid, and the mixture was kneaded for 3 minutes using a test roll adjusted to 140°C to produce a 0.5 mm thick sheet. This sheet was cut and placed in a gear oven heated to 175° C., and the sheet was taken out at predetermined intervals to visually observe the degree of coloring to evaluate the oven thermal stability of the sheet.
In addition, the cut sheets were stacked in six sheets and put into a press mold, and a plate was formed using a 40-ton heating press machine at 150℃ for 10 minutes.The degree of coloring of the plate was observed with the naked eye, and the plate was The press thermal stability was evaluated. The evaluation criteria for the oven heat stability of sheets and the press heat stability of plates are: Colorless......A Pale yellow...B Yellow or light brown...C Yellow brown Or reddish brown...D Black......E The evaluation results are shown in Table 1. The evaluation criteria in Tables 1 to 8 below were based on the above.

[Table] Example 2 Vinyl chloride resin [Geon103Ep-8 Nippon Zeon
Co., Ltd.] and the prescribed amount of the stabilizer shown in Table 2 was added to 100 parts of the stabilizer shown in Table 2, and kneaded for 3 minutes at 160°C in the same manner as in Example 1 to prepare a sheet. Stability was evaluated. In addition, the cut sheets were stacked in six sheets and placed in a press mold, and a plate was formed using a 40-ton heating press machine at 155℃ for 15 minutes.The degree of coloring of the plate was observed with the naked eye, and the plate was Press heat stability was also evaluated. The results are shown in Table 2.

【table】

[Table] Example 3 Vinyl chloride resin [Geon103Ep-8 Nippon Zeon
Co., Ltd.] and added the prescribed amount of the stabilizer shown in Table 3 to 100 parts of the stabilizer shown in Table 3, and kneaded it at 140°C for 3 minutes in the same manner as in Example 1 to prepare a sheet.The sheet was heated in a gear oven at 190°C. Stability was evaluated. In addition, the cut sheets were stacked in six sheets and placed in a press mold, and a plate was formed using a 40-ton heating press machine at 180℃ for 30 minutes.The degree of coloring of the plate was observed with the naked eye, and the plate was Press heat stability was also evaluated. The results are shown in Table 3.

[Table] Example 4 Vinyl chloride resin [Geon103Ep-8 Nippon Zeon
Co., Ltd.] and the prescribed amount of the stabilizer shown in Table 4 was added to 100 parts of the stabilizer shown in Table 4, and kneaded for 3 minutes at 175°C in the same manner as in Example 1 to prepare a sheet. Stability was evaluated. In addition, the cut sheets were stacked in six sheets and placed in a press mold, and a plate was formed using a 40-ton heating press machine at 180℃ for 20 minutes.The degree of coloring of the plate was observed with the naked eye, and the plate was Press heat stability was also evaluated. The results are shown in Table 4.

【table】

[Table] Example 5 Vinyl chloride resin [Geon103Ep-8 Nippon Zeon
Co., Ltd.] and added the prescribed amount of the stabilizer shown in Table 5, Table 6, and Table 7 to 100 parts, and heated at 150°C in the same manner as in Example 1.
A sheet was prepared by kneading for 3 minutes, and the thermal stability of the sheet was evaluated in a gear oven at 190°C. The results are shown in Tables 5, 6, and 7.

【table】

【table】

[Table] Example 6 Vinyl chloride resin (Geon103Ep-8 Nippon Zeon
A predetermined amount of the stabilizer shown in Table 8 was added to 50 parts of ABS resin (Toyoratsu 100 manufactured by Toray Industries, Inc.), and the mixture was kneaded at 160°C for 3 minutes in the same manner as in Example 1 to form a sheet. 210
The thermal stability of the sheet was evaluated in a gear oven at °C. In addition, the cut sheets were stacked in six sheets and placed in a press mold, and a plate was formed using a 40-ton heating press machine at 180°C for 180 minutes, and the degree of coloring of the plate was observed with the naked eye. Press heat stability was also evaluated. The results are shown in Table 8.

【table】

Claims (1)

[Claims] A group represented by the primary formulas () to () -OR ¹ SR ² () -OR ¹ SR ¹ O- () -OR ¹ SR ³ SR ¹ O- () (in the formula, R ¹ is an alkylene group, or a group in which the hydrogen atom bonded to the carbon atom of this group is substituted with a hydroxyl group, mercapto group, or alkyl group.R ²
is a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, an arylalkyl group, an alkylaryl group, or an arylalkenyl group. R ³ is an alkylidene group or a group in which the hydrogen atom bonded to the carbon atom of this group is substituted with an alkyl group. )
A stabilizer for chlorine-containing resins comprising at least one boron compound.