WO1999027009A1

WO1999027009A1 - Heat stabilizer for resins and chlorine-containing resin composition comprising the same

Info

Publication number: WO1999027009A1
Application number: PCT/JP1997/004302
Authority: WO
Inventors: Hiroshige Naito; Hiroshi Naito
Original assignee: Sanwagosei Chemical Co., Ltd.
Priority date: 1997-11-25
Filing date: 1997-11-25
Publication date: 1999-06-03
Also published as: JP3283882B2; WO1999027009A8

Abstract

A heat stabilizer for resins, comprising a compound having an epoxy group and an active metal species in combination in the same molecule and stearoylbenzoylmethane and/or dibenzoylmethane; and a markedly stabilized chlorine-containing resin composition comprising a chlorine-containing resin and the above stabilizer.

Description

Description Heat stabilizer for resin and chlorine-containing resin composition using the same

The present invention relates to a heat stabilizer for resins and a chlorine-containing resin composition using the same. More specifically, the present invention relates to a compound having both an epoxy group and an active metal type in the same molecule, and a compound comprising stearyl benzoyl methane and Z Or a heat stabilizer for resin comprising dibenzoylmethane, and a significantly stabilized chlorine-containing resin composition obtained by adding the heat stabilizer for resin to a chlorine-containing resin.

Background art

Chlorine-containing resins are liable to undergo thermal decomposition, mainly due to dehydrochlorination, during thermoforming, which causes inconveniences such as deterioration of mechanical properties and color tone of processed products.

Therefore, in order to avoid the above-mentioned inconveniences, it is necessary to add one or several kinds of resin heat stabilizers to the resin to suppress the deterioration in the processing step. Conventionally, various types of metal soaps, chelating compounds, ultraviolet absorbers, epoxidized oils and the like have been proposed as this kind of heat stabilizer for resins, and some of them have been put to practical use.

However, these stabilizers often have insufficient heat resistance effects when used in small amounts. In addition, since the site having the stabilizing function is only a part of the molecule, when multiple types of stabilizers are used in combination, the bleeding phenomenon or ubiquity of the oozing out of the surface of the molded product occurs, and the appearance In addition, the deterioration of the overall mechanical properties of the resin molded article due to the dilution of the resin component, for example, a decrease in strength, is caused.

Therefore, the present inventors have proposed, as shown in JP-A-56-47442 and JP-A-7-138453, the following general stabilizers for chlorine-containing resins. Expression ① Proposed a compound having both an epoxy group and an active metal species in the same molecule.

H H

R (CH ₂ ) _m — C-one C-one (CH:

\ /

0

-①

0

/ \

R (CH ₂ ) c-c (CH ₂ )

H H

(Wherein, R is an alkyl group, 1 (CH ₂ ) _m is a chain methylene group, m and n are integers of 68, and M is Ca or Zn, respectively) M ococ III I- If a stabilizer is used, the molding can be performed by adding a smaller amount than conventional products.

It has been found that it is possible to suppress oozing and ubiquity of the stabilizer on the surface of the product, and to exhibit multifunctional thermal stability without deteriorating the mechanical properties of the resin material.

However, even when this compound is used, the prevention of the initial thermal coloring property is still not sufficiently satisfactory, and there is room for improvement.

Disclosure of the invention

The present inventors have conducted various studies in view of the above-mentioned current situation, and as a result, have found that a specific compound represented by the above general formula II or the like containing an epoxy group and an active metal species in the same molecule has a specific property. It has been found that a significantly stabilized chlorine-containing resin composition can be obtained by adding a heat stabilizer for resin to which a / 3-diketone is added to the chlorine-containing resin.

Thus, the present invention has been made based on the above findings, and has the following features. And

It is characterized in that stearoyl benzoylmethane and Z or dibenzoylmethane are added to the compound represented by the general formula (1).

Further, a heat stabilizer for a resin obtained by adding stearoyl benzoylmethane and / or dibenzoylmethane to the compound represented by the general formula (1) is contained in the chlorine-containing resin.

In addition, stearoylpentylmethane and / or dibenzoylmethane are added to the compounds represented by the following chemical formulas (1) and (3).

H H

R— (CH ₂ ) _m- C-C (CH ₂ ) -C = 0

\ /

0 0

C a

I

0 〇

R— (CH ₂ ) C-C C (CH ₂ )-C = 0

H H

(Where R is an alkyl group, 1 (CH ₂ ) is a chain methylene group, and m and n are integers of 68)

H H

R— (CH ₂ ) _m = 0

Z n -③

〇 0

/ \

R- (CH ₂₎ - C one C one _{'(CH 2) - C =} 0

[I

H H

(Wherein, R is an alkyl group, (CH ₂ ) _m — is a chain methylene group, and m and n are 6

(An integer of 8) In addition, the compound represented by the above chemical formulas (1) and (3) contains a heat stabilizer for resin in which stearoylphenol methane and / or dibenzoylmethane is added to the chlorine-containing resin. It is characterized by.

If stearoyl benzoylmethane and / or dibenzoylmethane are added to the compounds represented by the above general formulas (1), (2) and / or (3), the initial action may be particularly enhanced by the joint action of the two. The anti-coloring property can be significantly improved. In addition, the amount of stearoyl benzoyl compound and Z or dibenzoyl methane was added to 100 parts by weight of the compound represented by the above general formula (1) or the compound represented by the above chemical formula (1) and (2) or the compound represented by the above chemical formula (3). 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight.

If the addition amount of stearoyl benzoylmethane and Z or dibenzoylmethane is less than 0.1 part by weight, the coloring prevention effect cannot be sufficiently exerted. On the other hand, if the addition amount of stearoyl benzoyl compound or the like exceeds 10 parts by weight, the stability of the chlorine-containing resin is rather impaired, and the coloring property is increased. In particular, in the case of dibenzoylmethane, such a problem occurs remarkably. In addition, expensive The use of large amounts of stearoyl benzoyl methane and the like is due to reasons such as poor economic efficiency.

Further, the addition amount of the compound represented by the general formula (1) or the compound represented by the chemical formula (1) and / or the chemical formula (3) is set to 0.05 to 10 parts by weight with respect to 100 parts by weight of the chlorine-containing resin. Preferably, it is regulated to 0.1 to 5 parts by weight.

The reason for this restriction is that if the amount of the compound represented by the above general formulas (1), (2) or (3) or (3) is less than 0.1 part by weight, the coloring prevention effect can be sufficiently exerted. Can not. On the other hand, if the amount of the compound represented by the above general formula (1) exceeds 10 parts by weight, the transparency of the chlorine-containing resin composition decreases, or the mechanical strength decreases due to a decrease in the elongation rate of the chlorine-containing resin composition. This is because the size becomes smaller. Further, the chlorine-containing resin is characterized by further containing a plasticizer. Examples of the plasticizer include an ester plasticizer such as a phthalate ester plasticizer and an adipic ester plasticizer, or a polyester plasticizer, a phosphate plasticizer, and a chlorine plasticizer.

Incidentally, stearoyl benzoyl methane and Z or dibenzoyl methane, which are the main components of the present invention, are known as stabilizers for chlorine-containing resins. For example, Japanese Patent Publication No. 52-47948 / 8 and Japanese Patent Publication No. 55-154 / 98 disclose the production method and use of chlorine-containing resin (specifically, chlorine-containing resin). 0.001 to 5 parts by weight to 100 parts by weight) is described. However, the addition of 0.001 part by weight to 100 parts by weight of the chlorine-containing resin has almost no effect, so it must be used together with a large amount of various other stabilizers. Is required. For this reason, the bleeding phenomenon, ubiquity, and the like occur, thereby deteriorating the appearance, and deteriorating the overall mechanical properties of the resin molded product due to dilution of the resin component, for example, lowering the strength. On the other hand, if 5 parts by weight is added to 100 parts by weight of the chlorine-containing resin, the same problem occurs. In contrast, the configuration of the present invention Therefore, the amount of the compound represented by the above general formulas (1), (2) and (3) or (3) is about 3 parts by weight with respect to 100 parts by weight of the chlorine-containing resin, and the amount of stearyl benzoylmethane Is about 3 parts by weight based on 100 parts by weight of all the compounds represented by the above general formulas (1), (2) and (3) or (3). Therefore, the amount of stearoyl benzoyl compound added to 100 parts by weight of the chlorine-containing resin is as small as 0.009 parts by weight, and the chlorine-containing resin composition can be added in such a small amount. Can greatly improve the thermal stability.

The addition of stearoyl benzoyl methane and / or dibenzoyl methane can be carried out in the form of a powder or a solution. Although the reason is not clear, the addition of stearoyl benzoyl methane has a more excellent effect of stabilizing the chlorine-containing resin composition than the case of adding dibenzoyl methane. Has been confirmed by experiments.

On the other hand, a compound containing an epoxy group and an active metal species in the same molecule, which is represented by the above-mentioned general formulas (1), (2) and (3) or the above-mentioned chemical formula (3), which is another main component of the present invention, can be obtained by a known method (See, for example, JP-A-56-47442 and JP-A-7-138435).

In addition, in the compound represented by the general formula (1) and the compounds represented by the chemical formulas (1) and (2) or the chemical formula (3), calcium and zinc may be added in equimolar amounts or calcium may be excessively added. desirable. The reason for this is uncertain. Force <, can be inferred as follows. That is, 9, 1 0 - Epoxy O Kuta decanoate zinc salt than is to produce a Z n C 1 ₂ reacts with unstable chlorine, the presence of 9, 1 0-Epokishio Kutadekan acid calcium salt, 9, 1 0 — Regenerated zinc epoxide decanoate. Thus, as a result of Z n C i ₂ production is slow, which is why that burnt by Z n (coloring) is suppressed.

Further, when producing the compound represented by the above general formula (2), calcium ion is added. It is desirable to add zinc ions after the addition. This is because, when the compound is produced in the reverse process, the powder of the compound represented by the general formula (2) exhibits tackiness, which causes inconvenience in industrial production.

In addition, when producing the compound represented by the general formula (1), soybean oil, castor oil, safflower oil, linseed oil and the like are used. Since these soybean oils contain linoleic acid, linoleic acid and the like having a double bond in addition to oleic acid, when saponifying epoxidized soybean oil with an aqueous solution of chemical soda, An epoxidized sodium linoleate represented by the following chemical formula (1) and an epoxidized sodium linoleate represented by the following chemical formula (1) are produced. However, even in such a case, it has been confirmed by experiments that the same or better effects as in the above configuration can be obtained.

CH ₃ (CH ₂ -CH-CH)-(CH ₂ ) ₇ COON a

\ /… ④

〇

CH ₃ (CH ₂ ) CH-CHCH ₂ CH-CH ₂ (CH ₂ ) i COON a

\ / \ /… ⑤ 0 0

Examples of the chlorine-containing resin used in the present invention include polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, and vinyl chloride. -Ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride urethane copolymer, vinyl chloride-acrylyl Acid ester copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride butadiene copolymer, butyl chloride Isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride_vinylidyl chloride Den-vinyl acetate copolymer, vinyl chloride-maleate copolymer, vinyl chloride Vinyl chloride copolymers such as 2-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-maleide copolymers, and the above resins, as well as polyethylene, polypropylene, polybutene, and polystyrene 3-olefins such as methylbutene or polyolefins such as ethylene-vinyl acetate copolymer and ethylene-propylene copolymer, and their copolymers, polystyrene, acrylic resin, polyurethane, and styrene. Copolymer with other monomers, acrylonitrile-styrene-butadiene copolymer, acrylic acid ester-styrene-butadiene copolymer ゃ methacrylic acid ester-styrene butadiene copolymer Examples of such a product include a blend with a polymer. The chlorine-containing resin may be obtained by any of conventionally known polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization and the like. Further, the chlorine-containing resin composition of the present invention The article is applicable to all of the techniques used to process chlorine-containing resin compositions, such as injection molding, extrusion, extrusion blow molding, calendaring—rolling, rotational molding, and the like.

In addition, the chlorine-containing resin composition of the present invention may further contain, if necessary, a crosslinking agent, a filler, a pigment, a foaming agent, an antistatic agent, an anti-fogging agent, an anti-platelet agent, a surface treatment agent, and a lubricant. , A flame retardant, a fluorescent agent, a fungicide, a bactericide, a photodegradation agent, a non-metal stabilizer, a processing aid, a release agent, and the like.

BEST MODE FOR CARRYING OUT THE INVENTION

This section describes the best mode for carrying out the invention, but the invention is not limited by the following embodiments.

(First embodiment)

(Example 1)

First, a saponification reaction of epoxidized soybean oil (12 kg) was performed using an aqueous solution of caustic soda (20%), and sodium 9,9-10-epoxyoctadecanoate was used as a main component. (Hereinafter abbreviated as EMS-Na) was obtained. Next, while heating and stirring the EMS-Na aqueous solution at 50 ° C, add a 1/4 mol amount of chloridizing aqueous solution of EMS-Na to the aqueous solution and stir (30 minutes). EMS—An aqueous solution of zinc chloride in an amount of 1 Z4 mole of Na was added and stirred (1 hour) to produce a white precipitate. Thereafter, the white precipitate was dehydrated and dried to obtain a white powder (11 kg, hereinafter abbreviated as EMS-Ca-Zn).

Thereafter, a polyvinyl chloride (manufactured by Chisso Corporation second poly-Tsu preparative SL) 1 0 0 parts by weight as the chlorine-containing resin, and di (C _{9 10)} alkyl phthalates rate Bok 4 0 parts by weight of a plasticizer, the EMS — C a -Zn 2.0 parts by weight [However, EMS—C a—Znl OO parts by weight contain stearoyl benzoyl methane (hereinafter abbreviated as SBM) in double parts. Is kneaded with a roll, and then pressed to form a 1 mm thick sheet.

(Examples 2 to 5)

A sheet was produced in the same manner as in Example 1 except that the proportions of EMS—Ca—Zn and SBM were changed.

(Examples 6 to 9)

Other than using dibenzoylmethane (hereinafter abbreviated as D BM) instead of S BM and changing the ratio of di (C ₉ ,.) Alkyl phthalate and EMS—C a —Zn A sheet was produced in the same manner as in Example 1 above.

(Comparative Examples 1 to 3)

A sheet was produced in the same manner as in Example 1 except that either EMS—Ca—Zn or SBM was not added.

For easy understanding, the mixing ratios of the sheets of Examples 1 to 9 and Comparative Examples 1 to 3 are shown in Tables 1 and 2 below.

[Experiment] Each of the above sheets was placed in a gear aging tester (180 ° C) and heated for 30 minutes, and the degree of coloring due to thermal deterioration of the sheet was examined. The results are shown in Tables 1 and 2 below. Shown in

The degree of coloring of the sheet was evaluated in eight steps from completely uncolored to black. Specifically, 0: completely colorless, 1: light yellow, 2: light yellow, 3: yellow, 4: light brown, 5: light brown, 6: brown, 7: black brown, 8: black.

table 1

The unit is parts by weight.

Table 2

The unit is parts by weight. As is clear from Tables 1 and 2, it is recognized that the sheets of the examples have a lower degree of coloring than the sheets of the comparative examples. However, when the DBM is less than 0.1 parts by weight (Example 8) and when the DBM exceeds 10 parts by weight (Example 9), It is recognized that the degree of color has increased. Therefore, the addition amount of D BM (S BM) is desirably 0.1 to 10 parts by weight based on EMS-Ca-ZnlOO parts by weight.

(Second embodiment)

(Example 1)

After obtaining EMS-Na in the same manner as in Example 1 of the first embodiment, while heating and stirring this EMS-Na aqueous solution at 50 ° C, 1 Z2 molar amount of EMS-Na amount A white precipitate is formed by adding an aqueous solution of calcium chloride and stirring (for 30 minutes), and the white precipitate is dehydrated and dried to obtain 9,10-calcium 9,10-epoxyoctadecanoate (hereinafter referred to as calcium salt). , EMS-Ca). In parallel with this, while heating and stirring the same EMS-Na aqueous solution as above at 50, add the aqueous solution of EMS-Na amount / 2 moles of zinc chloride and stir (30 minutes) Then, a white precipitate was formed, and the white precipitate was dehydrated and dried to obtain 9,10-epoxybenzodecanoic acid zinc salt (hereinafter abbreviated as EMS-Zn).

Thereafter, a polyvinyl chloride 1 0 0 parts by weight as the chlorine-containing resin, di as a plasticizer - and (C ₉ ₁₀₎ alkyl phthalates rate Bok 4 0 parts by weight, and the EMS-C a 1 part by weight EMS—Zn 1 part by weight (provided that EMS—Ca, EMS—ZnlO contains 0 part by weight and 2 parts by weight of DBM) are roll-kneaded and then pressed, A sheet with a thickness of i mm was created.

(Examples 2 to 4)

Di (C ₉ - ₁₀₎ alkyl phthalates rate, EMS-C a, the other to change the ratio of the EMS-Z n or D BM was prepared sheet in the same manner as in Example 1.

(Example 5)

Instead of D BM, a mixture of 0.5 parts by weight of D BM and 2 parts by weight of S BM was used, and the ratio of EMS-Zn was changed. -Was made.

(Comparative Examples 1, 2)

Sheets were prepared in the same manner as in Example 1 except that either EMS-Ca or EMS-Zn was not added and the amount of DMS was changed.

(Comparative Example 3)

Sheets were prepared in the same manner as in Example 1 except that calcium stearate was used instead of EMS-Ca, zinc stearate was used instead of EMS-Zn, and the amount of DMS 'added was changed. Was prepared.

For easier understanding, the mixing ratios of the sheets of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Tables 3 and 4 below.

[Experiment]

The degree of coloring due to thermal degradation of the sheet was examined in the same manner as in the experiment of the first embodiment, and the results are shown in Tables 3 and 4 below. In addition, the numerical value of the degree of coloring of the sheet is shown on the same basis as in Tables 1 and 2. Table 3

The unit is parts by weight. Table 4

The unit is parts by weight. As is clear from Tables 3 and 4, it is recognized that the sheets of the examples have a lower degree of coloring than the sheets of the comparative examples. However, when the total amount of EMS-Ca and EMS-Zn is less than 0.05 parts by weight (Example 4), it is recognized that the degree of coloring is increased. Therefore, the total amount of EMS-Ca and EMS_Zn is preferably at least 0.05 part by weight based on 100 parts by weight of the polyvinyl chloride resin. Although not shown in Tables 3 and 4, the total amount of EMS-Ca and EMS-Zn exceeded 10 parts by weight with respect to 100 parts by weight of polychlorinated vinyl resin. In this case, too, it has been confirmed by experiments that the degree of coloring increases.

The invention's effect

As described above, according to the present invention, an excellent effect that the thermal stability is remarkably improved, and particularly the initial thermal coloring property can be remarkably suppressed.

Claims

The scope of the claims

1. A heat stabilizer for resins, wherein stearoyl benzoylmethane and Z or dibenzoylmethane are added to a compound represented by the following general formula (1).

H H

R (CH ₂ ) _m- C-C (CH ₂ ) -C = 0

\ /

0 0

M (1)

I

0 0

/ \

R (CH ₂ ) one c-one c (CH ₂ ) one c = 〇

H H

(Where R is an alkyl group, 1 (CH ₂ ) _m — is a chain methylene group, m and n are integers of 68, and M is Ca or Zn, respectively)

2. The chlorine-containing resin contains a heat stabilizer for a resin in which stearoyl benzoylmethane and / or dibenzoylmethane is added to a compound represented by the following general formula (2). Chlorine-containing resin composition.

H H

R— (CH ₂ ) C-C (CH ₂ ) C = 0

\ No I

0 〇

M (2)

0 〇

Nore. And

(Where R is an alkyl group, 1 (CH ₂ ) is a chain methylene group, and m and n are integers of 68) HH

R— (CH ₂ ) _m- one C-one C-one (CH ₂ ) „one C = 0

\ / I

o o

Z n-(4)

0 0

C I

R- (CH ₂ ) _m- C-C-I '. (CH ₂ ) „-C == 0

H H

(Wherein, R is an alkyl group, 1 (CH ₂ ) _m — is a chain methylene group, and m and n are integers from 6 to 8)

4. The compound represented by the following chemical formula (5) and the following chemical formula (6) is characterized in that a chlorine-containing resin contains a heat stabilizer for resin in which stearoyl benzoylmethane and Z or dibenzoylmethane are added. And a chlorine-containing resin composition.

H H I I

R— (CH ₂ ) _m one C one C one (C Η ₂ ) π-C = 0

\ / I

0 0

C a-(5)

0 0

C I

R-(CH ₂ ) _m- C-C-(CH ₂ ) „-C = 0

I I

H H

(Wherein, R is an alkyl group, 1 (CH ₂ ) _m — is a chain methylene group, and m and n are integers of 68) R- (CH ₂ ) one = 0

Z n (6)

0 0

R-(CH ₂ ) _m- C-C (CH ₂ )-C = 〇

H H

(Wherein, R is an alkyl group, 1 (CH ₂ ), is a chain methylene group, m and n are integers of 68) 5. The amount of the stearoyl benzoyl methane and / or dibenzoyl methane 2. The resin according to claim 1, wherein the content is regulated to 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the compound represented by the formula (1). For heat stabilizer.

6. The addition amount of the stearoyl benzoyl methane and / or dibenzoyl methane is 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the compound represented by the general formula (2). 3. The chlorine-containing resin composition according to claim 2, wherein the content is regulated to 5 to 5 parts by weight.

7. The amount of the stearoyl benzoylmethane and Z or dibenzoylmethane added is set to 0.1 to 1 part by weight based on 100 parts by weight of the compound represented by the chemical formula (3) and the chemical formula (4). 4. The heat stabilizer for resin according to claim 3, wherein the heat stabilizer is regulated to 0 parts by weight, preferably 0.5 to 5 parts by weight.

8. The addition amount of the stearoyl benzoyl methane and Z or dibenzoyl methane is set to 1 to 10 parts by weight with respect to 100 parts by weight of the compound represented by the chemical formulas (5) and (6). 5. The chlorine-containing resin composition using a resin heat stabilizer according to claim 4, wherein the content is regulated to 0.5 parts by weight, preferably 0.5 to 5 parts by weight.

9. The addition amount of the compound represented by the general formula (2) is 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing resin. 7. A chlorine-containing resin composition using the heat stabilizer for resin according to claim 2, wherein the chlorine-containing resin composition is regulated.

100. The addition amount of the compounds represented by the chemical formulas (5) and (6) is 0.05 to 10 parts by weight, preferably 0 to 100 parts by weight of the chlorine-containing resin. 9. The chlorine-containing resin composition using the resin heat stabilizer according to claim 4, wherein the chlorine-containing resin composition is regulated to 1 to 5 parts by weight.

11. The chlorine-containing resin composition according to claim 2, wherein the chlorine-containing resin further contains a plasticizer.

12. The chlorine-containing resin composition using a resin heat stabilizer according to claim 9, wherein the chlorine-containing resin further contains a plasticizer.

10. The chlorine-containing resin composition according to claim 10, wherein the chlorine-containing resin further contains a plasticizer.