JPS6142742B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilizer for chlorine-containing vinyl resins made of a novel boron compound, and provides a stabilizer that can constitute a chlorine-containing vinyl resin composition having excellent thermal stability. As is well known, when chlorine-containing vinyl resins are heated and molded, they undergo thermal decomposition mainly due to dehydrochlorination, which has major drawbacks such as discoloration of molded products and a decrease in mechanical strength. are doing. For this reason, in order to suppress thermal decomposition of the resin, a heat stabilizer is added to the chlorine-containing vinyl resin for molding. There are a wide variety of compounds conventionally used as heat stabilizers. Typical examples include organic tin compounds (alkyltin carboxylates, alkyltin sulfur-containing compounds, etc.), metallic soaps, and inorganic metal compounds (Pd, Cd, Ba, Zn, Ca, Mg, Al, Li, Na, K
metal carboxylates, phenolates, sulfates, oxides, hydroxides, etc.), organic phosphorous esters, epoxy compounds, antioxidants, etc. In practical use, these compounds are used singly or in combination as required. In recent years, strict conditions have been imposed on the molding of chlorine-containing vinyl resins. In terms of processing conditions, strict molding conditions such as high temperatures and long periods of time are required due to mass production, larger molded products, and improved mechanical strength, and furthermore, compounding materials need to be made flame retardant. A bromine-based flame retardant, a butadiene-based reinforcing resin to improve mechanical strength, and an amine-based antistatic agent to prevent static electricity are added to the chlorine-containing vinyl resin. is a material that promotes thermal decomposition, and conventional heat stabilizers cannot sufficiently withstand these harsh conditions.Therefore, there is a strong demand for superior heat stabilizers. In view of these circumstances, the present inventors continued intensive research and found that a specific new boron compound is an excellent heat stabilizer for chlorine-containing vinyl resins.
Conventional technology using boron compounds was published in 1973.
No. 8244, Special Publication No. 11494, Special Publication No. 42-11495
No. 1, JP 51-125443, JP 53-7754, JP 53-111346, etc.
None of them were fully satisfactory. The present invention Regarding the stabilizer for chlorine-containing vinyl resin made of a novel boron compound having the group represented by the following, the present invention also provides a chlorine-containing vinyl resin composition having even better thermal stability. The stabilizer for chlorine-containing vinyl resins of the present invention is a boron compound having a group formed by the reaction of boric acid or boric anhydride with 2,2'-bis(4'-hydroxycyclohexyl)propane. Typical examples of these are shown as general formulas: etc. can be mentioned. (In general formulas (1) to (8), Z is

[Formula] is shown, R ¹ O, R ² O, R ³ O, R ⁴ O, R ⁵ O, R ⁶ O, R ⁷ O,
The groups represented by R ⁸ , O, R ⁹ O, R ¹⁰ O, R ¹¹ O, R ¹² O and R ¹³ O are hydroxyl group, HO-Z-O- group, alkyloxy group, alkenyloxy group, cycloalkyloxy Y ¹ , Y ² , Y ³ , Y ⁴ , which is a group or a group in which the hydrogen atom bonded to these carbon atoms is substituted,
The groups represented by Y ⁵ and Y ⁶ are oxygen, -O-Z-O-
group, alkylenedioxy group, cycloalkylenedioxy group, or a group in which hydrogen atoms bonded to these carbon atoms are substituted. n is a number from 1 to 5. ) To explain the general formula, the groups represented by R ¹ O to R ¹³ O include hydroxyl group, HO-Z-O- group, alkyloxy group having 2 to 22 carbon atoms, alkenyloxy group having 3 to 18 carbon atoms, carbon A cycloalkyloxy group having 5 to 8 carbon atoms, or a group in which the hydrogen atoms bonded to these carbon atoms are substituted with a mercapto group, alkyloxy group, aryloxy group, hydroxyalkyl group, or hydroxyaryl group, having 3 to 30 carbon atoms
An example is an arylalkyloxy group. Specific examples of groups represented by R ¹ O to R ¹¹ O include hydroxy, Ethoxy, propoxy, butoxy, isobutoxy, hexyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, lauryloxy, stearyloxy, hexenyloxy, octenyloxy, oleyloxy, cyclohexyloxy, cyclooctyloxy, methoxyethyloxy, methoxy Butyloxy, methoxyethyloxyethyloxy, phenoxyethyloxy, phenylethyloxy, benzyloxy, methylbenzyloxy, cinnamyloxy,
2-mercaptoethyloxy, 3-mercaptopropyloxy, 4-mercaptobutyloxy, hydroxyethyloxy, hydroxypropyloxy, hydroxybutyloxy, hydroxyhexyloxy, hydroxyethyloxyethyloxy, hydroxycyclohexyloxy,

【formula】

【formula】

【formula】

[Formula] H ₂ COH (HCOH) ₄ H ₂ CO−,

【formula】

[Formula] etc. can be listed. Specific examples of groups represented by Y ¹ to ^{Y 3} include oxygen, Ethylenedioxy, propylenedioxy, butylenedioxy, hexylenedioxy

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] etc. can be listed. Examples of preferred boron compounds of the present invention are shown below (a) to
As shown in (z), etc. can be mentioned. Next, a manufacturing example of the boron compound of the present invention will be specifically explained. Production example (1) Boron compound (a) Boric acid 23.2g (0.375 mol), 2,2'-bis(4'-
hydroxycyclohexyl) propane (hereinafter
Abbreviated as BHCHP. ) and 100 g of toluene were heated with stirring. The reaction was continued under refluxing toluene, and the water produced was separated using a water separator. React for 4 hours at 105℃~115℃ and produce 13.3g of water.
was separated. Next, toluene was distilled off under reduced pressure to obtain 99 g of a colorless and transparent solid. As a result of analysis, this boron compound (a) had a boron content of 41% and a melting point of 230-240°C. The following procedure is carried out in the same manner as in Production Example (1). Production example (2) Boron compound (b) Boric anhydride 6.7g (0.096mol), BHCHP46.3g
(0.193 mol), industrial stearyl alcohol (hydroxyl value: 207 mg KOH), 52.2 g (0.193 mol), and 100 g of toluene were reacted at 105°C to 120°C for 3 hours and 30 minutes, and 5.0 g of produced water was separated. Toluene was distilled off to obtain 100 g of a white solid. Boron content 2.1% Melting point 55℃ Production example (3) Boron compound (c) Boric acid 42.3g (0.684mol), BHCHP82.3g
(0.342 mol) 100g of toluene was reacted at 96°C to 118°C for 5 hours, and 24.3g of produced water was separated. Toluene was distilled off to obtain 100 g of a colorless and transparent solid. Boron content 7.4% Melting point 230℃~250℃ Production example (4) Boron compound (h) Boric acid 18.0g (0.290mol), BHCHP34.9g
(0.145 mol), benzyl alcohol 62.8 g (0.580
mol), 100 g of xylene was reacted at 122°C to 146°C for 4 hours, and 15.5 g of produced water was separated. The xylene was distilled off to obtain 99 g of a transparent viscous liquid. Boron content 3.1% Production example (5) Boron compound (k) Boric acid 17.8g (0.287mol), BHCHP46.0g
(0.191 mol), 100g of toluene at 95℃~122℃
The reaction took place for 30 minutes, and 10.1 g of produced water was separated. Furthermore, add 51.8 g (0.478 mol) of benzyl alcohol and add 95
The reaction was carried out for 4 hours at a temperature of 122°C to 122°C, and 5.2 g of produced water was separated. Toluene was distilled off to obtain 99 g of a pale yellow viscous liquid. Boron content 2.1% Production example (6) Boron compound (l) Boric acid 26.6g (0.430mol), BHCHP51.8g
(0.215 mol), 100g of toluene at 96℃~122℃
After reacting for a period of time, 7.6 g of produced water was separated to obtain 171 g of a colorless and transparent viscous liquid (hereinafter, in the production examples, this toluene solution of BHCHP boric acid ester is abbreviated as BB liquid). In addition to this BB liquid, 44.9g of methoxybutanol
(0.430 mol) and reacted at 96°C to 122°C for 1 hour and 30 minutes, separating 7.5 g of produced water. Toluene was distilled off to obtain 106 g of a colorless and transparent viscous liquid. Boron content 4.6g Production example (7) Boron compound (o) 171g of BB liquid and 26.7g of ethylene glycol (0.430
mol) and react at 96℃ to 116℃ for 4 hours to produce water.
15.3g was isolated. Distill toluene and white solid 81
I got g. Boron content 5.6% Melting point 105℃ Production example (8) Boron compound (q) 171g of BB liquid and 13.3g of ethylene glycol (0.215
mol), 56 g (0.430 mol) of 2-ethylhexanol was added and reacted at 104°C to 122°C for 4 hours to produce water.
15.3g was isolated. Toluene is distilled off to form a viscous liquid.
Obtained 123g. Boron content 3.6% Production example (9) Boron compound (t) 33.6 g of 2-mercaptoethanol in 171 g of BB liquid
(0.430 mol) and reacted at 100°C to 119°C for 2 hours and 30 minutes, separating 7.6 g of produced water. Toluene was distilled off to obtain 95 g of a colorless viscous liquid with a mercapto odor. Boron content 4.8% Production example (10) Boron compound (w) 171g of BB liquid and 58.5g of pentaerythritol
(0.430 mol) was added and reacted for 2 hours at 92°C to 111°C, and 15.4g of produced water was separated. Toluene was distilled off to obtain 113 g of a white solid. Boron content 4.1% Melting point 145℃ Production example (11) Boron compound (x) Boric acid 28.1g (0.454mol), BHCHP54.6g
(0.227 mol), 100g of toluene at 105℃~120℃
The reaction took place for 30 minutes, and 8.1 g of produced water was separated. 41.8 g (0.454 mol) of glycerin was further added to the resulting colorless viscous liquid, heated again, and heated at 103°C to 120°C for 3 hours.
After reacting for 30 minutes, 16.2 g of produced water was separated. Toluene was distilled off to obtain 100 g of a white solid. Boron content: 48% Melting point: 92°C The amount of the stabilizer for chlorine-containing vinyl resin of the present invention to be used is not particularly limited, but the necessary amount may be determined as appropriate depending on the molding method of the chlorine-containing vinyl 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, per 100 parts by weight of the chlorine-containing vinyl resin. When stabilizing a chlorine-containing vinyl resin using the stabilizer of the present invention, other known stabilizers may be used as necessary, such as organic tin compounds, metallic soaps, inorganic metal compounds, organic phosphite esters, and epoxy compounds. , antioxidants, etc. can be used in combination. Specific examples of these include monobutyltin trilaurate, dioctyltin dilaurate, dibutyltin maleate, dioctyltin maleate,
Dibutyltin bis(butyl maleate), bis(dibutyltin benzyl maleate) maleate, dioctyltin bis(isooctyl maleate), monobutyltin sulfide, dibutyltin sulfide, monobutyltin tris(lauryl mercaptide), monobutyltin tris (isooctylmercaptoacetate), dibutyltin bis(isooctyl β-mercaptopropionate), dioctyltin bis(isooctylmercaptoacetate),
Dibutyltin β-mercaptopropionate, dioctyltin thioglycolate, tribasic lead sulfate, dibasic lead phosphite, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide,
Barium hydroxide, dibasic lead stearate, lead stearate, cadmium stearate, barium stearate, calcium stearate, zinc stearate, calcium laurate, magnesium stearate, aluminum stearate, triphenylphosphite, diphenyldecylphosphite Phite, di(nonylphenyl)hydrodiene osphite, epoxidized soybean oil, epoxidized linseed oil, epichlorohydrin and bisphenol A condensation type 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), dilaurylthiopropionate, thiodipropionic acid, etc. 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. By combining the stabilizer of the present invention and a metal soap compound to stabilize a chlorine-containing vinyl resin, an excellent stabilizer composition with less initial coloration that cannot be achieved with a metal soap compound alone can be obtained. When combined with an organic tin compound, a stabilizer composition with low initial coloring and excellent sustained thermal stability can be obtained, and furthermore, it does not reduce the mechanical strength of resin molded products. Typical examples of chlorine-containing resins stabilized by the stabilizer of the present invention include vinyl chloride resin, vinyl chloride/vinyl acetate copolymer resin mainly composed of vinyl chloride, vinyl chloride/ethylene copolymer resin, and chlorine-containing resin. Vinyl/styrene copolymer resin, vinyl chloride/styrene/acrylonitrile copolymer resin, vinyl chloride/acrylonitrile copolymer resin,
It can include methacrylic acid ester copolymer resins and vinyl chloride/acrylonitrile copolymer resins, and also includes acrylonitrile/butadiene/styrene copolymer resins (hereinafter abbreviated as ABS resins) mainly composed of vinyl chloride resins, and methacrylic acid. Methyl ester/butadiene/styrene copolymer resin (hereinafter abbreviated as BS resin) refers to a blend resin of polyethylene, polypropylene, ethylene/vinyl acetate copolymer resin, acrylonitrile/styrene copolymer resin, etc., and vinyl chloride resin. I can do it. There are no particular restrictions on the method of mixing the stabilizer of the present invention with the chlorine-containing vinyl resin, and it can be easily mixed 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 (F) to (N) in the table of Examples are as follows. (F) Dibutyltin bis(isooctylmercaptoacetate) (G) Dibutyltin bis(isooctyl β-mercaptopropionate) (H) Monobutyltin tris(isooctylmercaptoacetate) (I) Dibutyltin dilaurate (J) Dibutyltin Maleate (K) Calcium stearate (L) Zinc stearate (M) Tribasic lead sulfate (N) Dibasic lead stearate In the examples, parts mean parts by weight. Example 1 Vinyl chloride resin [Geon 103EP manufactured by Zeon Corporation
To 100 parts of dioctyl phthalate (hereinafter abbreviated as DOP) and a stabilizer shown in Table 1 were added and kneaded for 4 minutes using a test roll adjusted to 150°C to produce a 0.5 mm thick sheet. This sheet was cut and placed in a gear opener heated to 175° C., and the sheet was taken out every 20 minutes to visually observe the degree of color deterioration to evaluate the open thermal stability of the sheet. The evaluation criteria are as follows: colorless is represented by A, pale yellow is represented by B, yellow or light brown is represented by C, tan is represented by D, black is represented by E, and the evaluation results are shown in Table 1. Indicated.

[Table] Example 2 100 parts of vinyl chloride resin (Geon 103EP)
A predetermined amount of the stabilizer shown in the table was added and kneaded for 4 minutes using a test roll at 170°C to produce a 0.5 mm thick sheet. This sheet was cut into six sheets, placed in a press mold, and heated at 150℃ for 20 minutes using a 40-ton heating press.
A plate was molded under the condition of 20 kg/cm ² , and the degree of color deterioration of the plate was observed with the naked eye, and the press thermal stability of the plate was evaluated based on the same evaluation criteria as in Example 1. The results are shown in Table 2.

【table】

[Table] Example 3 Vinyl chloride resin [Geon 103EP-8 Nippon Zeon
Co., Ltd.] and 30 parts of MBS resin [Kane Ace B-12, manufactured by Jyobuchi Chemical Co., Ltd.] were added with the prescribed amount of the stabilizer shown in Table 3. A sheet was prepared by kneading for a minute, and the thermal stability of the sheet was evaluated based on the same evaluation criteria as in Example 1 with the gear open at 185°C. The results are shown in Table 3.

[Table] Example 4 70 parts of vinyl chloride resin (Geon 103EP-8),
ABS resin (Toyoratsu 100 manufactured by Toray Industries, Ltd. 30 parts and 4 parts)
A predetermined amount of the stabilizer shown in Table 1, Table 5, and Table 6 was added, and the thermal stability of the sheet and press plate was evaluated in the same manner as in Examples 1 and 2 based on the same evaluation criteria as in Example 1. The test conditions in each table are as follows.

【table】

【table】 The determination results are shown in Tables 4, 5, and 6.

【table】

【table】

[Table] Example 5 50 parts of vinyl chloride resin (Geon 103EP-8),
A predetermined amount of the stabilizer shown in Table 7 was added to 50 parts of ABS resin (Toyorak 100), and the same procedure as in Examples 1 and 2 was carried out.
The sheet was prepared by kneading at 160℃ for 3 minutes, and the thermal stability of the sheet was determined by opening the gear at 210℃.
The thermal stability of the plates was evaluated based on the same evaluation criteria as in Example 1 under pressing conditions of 10 Kg/cm ² and 180 minutes. The results are shown in Table 7.

[Table] Example 6 Twelve sheets produced in Example 5 were stacked together and a plate with a thickness of 6 mm was produced using a hot press at 180° C. for 30 minutes at a pressure of 5 kg/cm ² . A plate of 90 mm x 10 mm and a thickness of 5.8 mm was cut using a plastic sample preparation device [manufactured by Toyo Seiki Co., Ltd.] to prepare an impact sample with a V-notch having an opening of 45 degrees and a depth of 1 mm. According to the test method of JIS K-7111, the impact strength was measured at a room temperature of 27° C. using a universal impact tester [manufactured by Toyo Seiki Co., Ltd.]. The results are shown in Table 8.

【table】

Claims (1)

[Claims] 1. General formula A stabilizer for chlorine-containing vinyl resins comprising a boron compound having a group represented by: