JP3283882B2 - Heat stabilizer for resin and chlorine-containing resin composition using the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a heat stabilizer for resin and a chlorine-containing resin composition using the same, and more particularly, to a compound having an epoxy group and an active metal species in the same molecule, and stearoyl. The present invention relates to a heat stabilizer for a resin comprising benzoylmethane and / or dibenzoylmethane, and a significantly stabilized chlorine-containing resin composition obtained by adding the heat stabilizer for a resin to a chlorine-containing resin.

BACKGROUND ART Chlorine-containing resins are liable to undergo thermal decomposition mainly due to dehydrochlorination at the time of heat molding, and therefore have the disadvantage of causing deterioration of mechanical properties and color tone of processed products.

Therefore, in order to avoid the above-mentioned inconvenience, it is necessary to add one or several kinds of heat stabilizers for resin to the resin to suppress the deterioration in the processing step. Conventionally, various types of metal soaps, chelate compounds, ultraviolet absorbers, epoxidized oils and the like have been proposed as this kind of resin heat stabilizer, 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 a stabilizing function is only a part of the molecule, when a combination of various types of stabilizers is used, a bleeding phenomenon or ubiquity of the stabilizer oozing out on the surface of the molded product occurs, and the appearance And the deterioration of the overall mechanical properties of the resin molded article due to dilution of the resin component, for example, a decrease in strength.

Therefore, the present inventors have proposed that, as shown in JP-A-56-47442 and JP-A-7-138435, as a stabilizer for a chlorine-containing resin, represented by the following general formula and the like, in the same molecule: A compound having both an epoxy group and an active metal species was proposed.

(Wherein, R is an alkyl group, _- (CH ₂₎ m - is a chain of methylene groups, m and n are 6-8 integer, M denotes a Ca or Zn) prior With stabilizer comprising the compound By adding a smaller amount than the product, it is possible to suppress the oozing out and ubiquity of the stabilizer on the surface of the molded product, and to exhibit multifunctional thermal stability without deteriorating the mechanical properties of the resin material I found something that could be done.

However, even when this compound is used,
Prevention of early thermal coloration is not yet 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, specified a compound represented by the above general formula and the like containing an epoxy group and an active metal species in the same molecule. Β
-It has been found that by adding a heat stabilizer for resin to which a diketone has been added to a chlorine-containing resin, a significantly stabilized chlorine-containing resin composition can be obtained.

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

It is characterized in that stearoylbenzoylmethane and / or dibenzoylmethane are added to the compound represented by the above general formula.

Further, a heat stabilizer for a resin obtained by adding stearoylbenzoylmethane and / or dibenzoylmethane to the compound represented by the above general formula is contained in the chlorine-containing resin.

Further, it is characterized in that stearoylbenzoylmethane and / or dibenzoylmethane are added to the following chemical formula and a compound represented by the following chemical formula.

(In the formula, R is an alkyl group,-(CH ₂ ) _m -is a chain methylene group, and m and n are integers of 6 to 8.) (In the formula, R is an alkyl group,-(CH ₂ ) _m -is a chain methylene group, m and n are integers of 6 to 8.) In addition, stearoylbenzoylmethane and / or Alternatively, the heat stabilizer for resin to which dibenzoylmethane is added is contained in the chlorine-containing resin.

Stearoylbenzoylmethane and / or a compound represented by the above general formula, the above chemical formula and / or the above chemical formula
Alternatively, if dibenzoylmethane is added, the synergistic action of both can remarkably improve, in particular, the initial coloring prevention property.

The amount of stearoylbenzoylmethane and / or dibenzoylmethane added is 0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the compound represented by the general formula or the compound represented by the chemical formula and / or the chemical formula.
It is characterized in that it is restricted to 5 parts by weight.

When the amount of stearoylbenzoylmethane and / or dibenzoylmethane is less than 0.1 part by weight, the effect of preventing coloring cannot be sufficiently exhibited. On the other hand, when the addition amount of stearoylbenzoylmethane or the like exceeds 10 parts by weight, the stability of the chlorine-containing resin is impaired, and the coloring property is increased. In particular, such a problem occurs remarkably in the case of dibenzoylmethane. in addition,
The use of a large amount of expensive stearoylbenzoylmethane or the like is due to reasons such as poor economic efficiency.

Further, the addition amount of the compound represented by the above general formula or the chemical formula and / or the compound represented by the above chemical formula is regulated to 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. It is characterized by doing.

This regulation is based on the fact that the addition amount of the general formula, the chemical formula and / or the compound represented by the chemical formula is 0.1%.
If the amount is less than the weight part, the coloring prevention effect cannot be sufficiently exhibited. On the other hand, if the amount of the compound represented by the above general formula exceeds 10 parts by weight, the transparency of the chlorine-containing resin composition is reduced, or the mechanical strength is reduced due to a decrease in the elongation rate of the chlorine-containing resin composition. This is for reasons such as.

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 ester plasticizer, and a chlorine plasticizer.

In addition, stearoylbenzoylmethane and / or dibenzoylmethane, which are the main components of the present invention, are known as stabilizers for chlorine-containing resins. For example,
Japanese Patent No. 47948 and Japanese Patent Publication No. 55-15498 disclose a production method and use for a chlorine-containing resin (specifically, 0.001 to 5 parts by weight per 100 parts by weight of a chlorine-containing resin).
Is described. However, if the amount is 0.001 part by weight based on 100 parts by weight of the chlorine-containing resin, the addition effect is hardly exhibited, so that it is necessary to use it together with a large amount of various stabilizers. For this reason, the bleeding phenomenon, ubiquity, and the like occur, and the appearance is deteriorated, and the overall mechanical properties of the resin molded body due to dilution of the resin component, such as a decrease in strength, are caused. On the other hand, if 5 parts by weight is added to 100 parts by weight of the chlorine-containing resin,
After all, a similar problem occurs. On the contrary,
In the configuration of the present invention, the above general formula, the above chemical formula and / or
Alternatively, the amount of the compound represented by the above chemical formula is about 3 parts by weight based on 100 parts by weight of the chlorine-containing resin, and the amount of stearoylbenzoylmethane or the like is the same as in the above general formula,
All 10 compounds represented by the above chemical formula and / or the above chemical formula
It is about 3 parts by weight with respect to 0 parts by weight. Therefore, the addition amount of stearoyl benzoyl methane and the like to 100 parts by weight of the chlorine-containing resin is as extremely small as 0.0009 parts by weight, and such a small addition can significantly improve the thermal stability of the chlorine-containing resin composition. it can.

The addition of stearoylbenzoylmethane and / or dibenzoylmethane can be performed in the form of a powder or a solution. Although the reason is not clear, it has been confirmed by experiments that the stabilizing effect of the chlorine-containing resin composition is more excellent when stearoylbenzoylmethane is added than when dibenzoylmethane is added. are doing.

On the other hand, a compound containing an epoxy group and an active metal species in the same molecule, represented by the above general formula, the above chemical formula and / or the above chemical formula, which are other main components of the present invention,
It can be produced by a known method (for example, see JP-A-56-47442 and JP-A-7-138435).

Further, in the compound represented by the above general formula and the compound represented by the above chemical formula and / or the above chemical formula, it is preferable that calcium and zinc are added in equimolar amounts or calcium is excessively added. The reason for this is not clear, but can be inferred as follows. 9,
10 epoxyoctadecane zinc salt although to generate ZnCl ₂ reacts with unstable chlorine, the presence of 9,10-epoxyoctadecane acid calcium salt, 9,10-epoxyoctadecane zinc salt is reproduced . Therefore, ZnCl
_This is because burning (coloring) due to Zn is suppressed as a result of slow generation of ₂ .

Furthermore, when producing the compound represented by the above general formula, it is desirable to add zinc ion after adding calcium ion. This is because when the compound is produced in the reverse process, the powder of the compound represented by the above general formula exhibits tackiness,
This is because it causes inconvenience to industrial production.

In addition, when producing the compound represented by the above general formula, soybean oil, sunflower oil, safflower oil, linseed oil and the like are used. Since these soybean oils include linolenic acid having a double bond in addition to oleic acid, linoleic acid, etc., when performing a saponification reaction of an epoxidized soybean oil or the like with an aqueous solution of chemical soda, the following chemical formula is used. Epoxidized linolenic acid sodium salt, epoxidized linoleic acid sodium salt represented by the following chemical formula, and the like are produced. However, in such a case,
It has been confirmed by an experiment that the same or better effects are obtained as in the above configuration.

Further, as the chlorine-containing resin used in the present invention, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, 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-acryl Acid ester copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride -Chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate copolymer Body, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-vinylimide copolymer such as maleimide copolymer, and the above resin, Polyethylene, polypropylene, polybutene, α-olefin polymers such as poly-3-methylbutene or ethylene-vinyl acetate copolymer, polyolefins such as ethylene-propylene copolymer and copolymers thereof, polystyrene, acrylic resin, polyurethane, Copolymers of styrene and other monomers, acrylonitrile-styrene-butadiene copolymer, acrylate-styrene-butadiene copolymer and methacrylate-styrene-butadiene copolymer blends and the like can be mentioned. . The chlorine-containing resin is emulsion polymerization,
It may be obtained by any of conventionally known polymerization methods such as suspension polymerization, solution polymerization, bulk polymerization and the like.

Further, the chlorine-containing resin composition of the present invention is a technique used for processing the composition of the chlorine-containing resin, such as injection molding, extrusion, extrusion blow molding, calender rolling, rotational molding and similar techniques. Applicable to all.

In addition, the chlorine-containing resin composition of the present invention, if necessary, a crosslinking agent, a filler, a pigment, a foaming agent, an antistatic agent, an antifogging agent, an anti-playout agent, a surface treatment agent, a lubricant,
Flame retardants, fluorescent agents, fungicides, bactericides, photodegradants, non-metal stabilizers, processing aids, release agents and the like can be included.

BEST MODE FOR CARRYING OUT THE INVENTION In this section, the best mode for carrying out the invention will be described, but the present invention is not limited by the following examples.

(First Example) [Example 1] First, a saponification reaction of epoxidized soybean oil (12 kg) was performed using an aqueous caustic soda solution (20%), and sodium 9,10-epoxyoctadecanoate was used as a main component. A compound (hereinafter abbreviated as EMS-Na) was obtained. Next, while heating and stirring the EMS-Na aqueous solution to 50 ° C., a 1/4 mole amount of calcium chloride aqueous solution of the EMS-Na amount was added and stirred (30 minutes),
Next, an aqueous solution of zinc chloride of 1/4 amount of EMS-Na amount was added.
Stirring (1 hour) produced a white precipitate. After this,
The white precipitate (11 kg, hereinafter abbreviated as EMS-Ca-Zn) was obtained by dehydrating and drying the white precipitate.

Thereafter, 100 parts by weight of polyvinyl chloride (Nipolit SL manufactured by Chisso Corporation) as a chlorine-containing resin, 40 parts by weight of di (C _9-10 ) alkyl phthalate as a plasticizer, and the EMS-
Roll-kneading 2.0 parts by weight of Ca-Zn [however, 2 parts by weight of stearoylbenzoylmethane (hereinafter abbreviated as SBM) is contained with respect to 100 parts by weight of EMS-Ca-Zn], and then subjected to press working. Then, a sheet having a thickness of 1 mm was prepared.

Examples 2 to 5 Sheets were 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 Except that dibenzoylmethane (hereinafter abbreviated as DBM) was used instead of SBM and the ratio of di (C _9-10 ) alkyl phthalate and EMS-Ca-Zn was changed, Example 1
A sheet was produced in the same manner as described above.

Comparative Examples 1 to 3 Sheets were 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 sheet 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.

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

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, those with less than 0.1 parts by weight of DBM (Example 8) and those with more than 10 parts by weight of DBM (Example 9)
It can be seen that the degree of coloring has increased. Therefore, the amount of DBM (SBM) added is EMS-Ca-Zn1
The amount is desirably 0.1 to 10 parts by weight based on 00 parts by weight.

(Example 2) (Example 1) After obtaining EMS-Na in the same manner as Example 1 of the first example, while heating and stirring this EMS-Na aqueous solution at 50 ° C, EMS-Na was obtained. An aqueous solution of calcium chloride (1/2 mole) was added and stirred (for 30 minutes) to form a white precipitate, and the white precipitate was dehydrated and dried to obtain calcium 9,10-epoxyoctadecanoate. (Hereinafter abbreviated as EMS-Ca). In parallel with this, the same EMS-Na
While heating and stirring the aqueous solution at 50 ° C., add and stir (30 minutes) an aqueous solution of zinc chloride in an amount of モ ル mol of EMS-Na to form a white precipitate, and further dehydrate this white precipitate. -By drying, zinc 9,10-epoxyoctadecanoate (hereinafter abbreviated as EMS-Zn) was obtained.

After that, polyvinyl chloride 100 as chlorine-containing resin
Parts by weight, 40 parts by weight of di (C _9-10 ) alkyl phthalate as a plasticizer, 1 part by weight of EMS-Ca and 1 part by weight of EMS-Zn [provided that DBM is used for 100 parts by weight of EMS-Ca and EMS-Zn. Is contained in a roll) and then press-formed to form a sheet having a thickness of 1 mm.

[Examples 2 to 4] Di (C _9-10 ) alkyl phthalate, EMS-Ca, EMS-Zn
Alternatively, a sheet was prepared in the same manner as in Example 1 except that the ratio of DBM was changed.

Example 5 A sheet was prepared in the same manner as in Example 1 except that a mixture of 0.5 parts by weight of DBM and 2 parts by weight of SBM was used instead of DBM, and the ratio of EMS-Zn was changed. did.

[Comparative Examples 1 and 2] EMS-Ca or EMS-Zn was not added, and
A sheet was prepared in the same manner as in Example 1 except that the amount of DMS was changed.

[Comparative Example 3] Calcium stearate was used instead of EMS-Ca.
A sheet was prepared in the same manner as in Example 1 except that zinc stearate was used instead of MS-Zn and the amount of DMS added was changed.

For easy 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 deterioration 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 the coloring degree of the sheet is shown by the same reference as in Tables 1 and 2.

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, the total amount of EMS-Ca and EMS-Zn is 0.
In the case of less than 05 parts by weight (Example 4), it is recognized that the degree of coloring is increased. Therefore, EMS-C
The total amount of a 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, EMS-Ca and EMS-Zn
Is 10 parts per 100 parts by weight of polyvinyl chloride resin.
Experiments have confirmed that even when the amount exceeds the weight parts, the degree of coloring increases.

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

Claims (13)

(57) [Claims] 1. A heat stabilizer for a resin, wherein stearoylbenzoylmethane and / or dibenzoylmethane are added to a compound represented by the following general formula (1). (Wherein, R is an alkyl group, - (CH _{2) m} - represents a chain of methylene groups, m and n are 6-8 integer, M is Ca or Zn, respectively) 2. A chlorine-containing resin comprising a compound represented by the following general formula (2) and a heat stabilizer for resin obtained by adding stearoylbenzoylmethane and / or dibenzoylmethane. Chlorine-containing resin composition. (Wherein, R is an alkyl group, - (CH _{2) m} - represents a chain of methylene groups, m and n are 6-8 integer, M is Ca or Zn, respectively) 3. A heat stabilizer for a resin, wherein stearoylbenzoylmethane and / or dibenzoylmethane are added to compounds represented by the following chemical formulas (3) and (4). (In the formula, R is an alkyl group,-(CH ₂ ) _m -is a chain methylene group, and m and n are integers of 6 to 8.) (In the formula, R is an alkyl group,-(CH ₂ ) _m -is a chain methylene group, and m and n are integers of 6 to 8.) 4. A chlorine-containing resin comprising a heat stabilizer for a resin in which stearoylbenzoylmethane and / or dibenzoylmethane is added to the compounds represented by the following chemical formulas (5) and (6). A chlorine-containing resin composition. (In the formula, R is an alkyl group,-(CH ₂ ) _m -is a chain methylene group, and m and n are integers of 6 to 8.) (In the formula, R is an alkyl group,-(CH ₂ ) _m -is a chain methylene group, and m and n are integers of 6 to 8.) 5. The stearoylbenzoylmethane and / or
Alternatively, the addition amount of dibenzoylmethane is determined by the formula (1)
The heat stabilizer for a resin according to claim 1, wherein the amount 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: 6. The stearoylbenzoylmethane and / or
Alternatively, the addition amount of dibenzoylmethane is determined by the general formula (2)
The chlorine-containing resin composition according to claim 2, 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: . 7. The stearoylbenzoylmethane and / or
Alternatively, the addition amount of dibenzoylmethane is determined by the formula (3)
4. The heat stabilizer for resin according to claim 3, wherein the amount 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 chemical formula (4). 8. The stearoylbenzoylmethane and / or
Alternatively, the amount of dibenzoylmethane added is determined by the chemical formula (5)
The resin heat stabilizer according to claim 4, wherein the amount 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 chemical formula (6). Chlorine-containing resin composition. 9. The addition amount of the compound represented by the general formula (2) is regulated to 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. A chlorine-containing resin composition using the resin heat stabilizer according to claim 2. 10. The chemical formula (5) and the chemical formula (6)
The amount of the compound represented by the formula, for the resin containing 100 parts by weight of the chlorine-containing resin is regulated to 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight for resin according to claim 4 or 8, A chlorine-containing resin composition using a heat stabilizer. 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 according to claim 9, wherein the chlorine-containing resin further contains a plasticizer. 13. The chlorine-containing resin composition according to claim 10, wherein the chlorine-containing resin further contains a plasticizer.