JPS60166336A - Liquid stabilizer for halogen-containing resin - Google Patents

Abstract

PURPOSE:To provide the titled low-toxic stabilizer composed of a liquid octyltin mercaptocarboxylic acid ester containing a small amount of dioctyltin mercaptocarboxylic acid salt, and effective to improve the thermal stability and processability of a halogen-containing resin and suppress the initial discoloration. CONSTITUTION:The objective stabilizer is composed of (A) 50-99.5(wt)% monooctyltin tris(mercaptocarboxylic acid ester) of formula I (R1 is CH2 or C2H4; R2 is 8-18C alkyl), (B) 0-49% dioctyltin bis(mercaptocarboxylic acid ester) of formula II and (C) 0.5-5%, preferably 1-3% dioctyltin mercaptocarboxylic acid salt of formula III (R3 is 1-4C alkylene; m is 1-50). The composition may be composed of the components A and C, however, it is preferably a three-component stabilizer composed of 50-94.5%, especially 52-89% component A, 5-45%, especially 10-45% component B, and the above amount of the component C. The amount of the stabilizer to be added to 100pts.wt. of a halogen-containing resin is 0.01-10pts.wt., preferably 0.1-5pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a liquid stabilizer for halogen-containing resins, specifically,
The present invention relates to a liquid octyltin mercaptocarboxylic acid ester stabilizer containing a small amount of dioctyltin mercaptocarboxylate.

When halogen-containing polymers are subjected to thermoforming processing, they tend to undergo thermal decomposition mainly due to dehydrohalogenation, resulting in decreased mechanical properties and color tone of processed products, resulting in significant defects. generate profits. In order to avoid such disadvantages, it is necessary to add one or more kinds of thermal stabilizers to the polymer to suppress thermal deterioration during processing steps. Many metal soaps, organic tin compounds, organic phosphites, epoxy compounds, antioxidants, ultraviolet absorbers, etc. have been used for this purpose. In particular, organotin compounds, particularly organotin mercaptocarboxylic acid esters, are known as excellent stabilizers for halogen-containing resins. However, these stabilizers are insufficient to prevent thermal deterioration of the resin under severe processing conditions, and cannot prevent the resin from discoloring due to thermal deterioration.

In particular, with recent advances in processing technology for halogen-containing resins, there is a strong demand for excellent low-toxicity or non-toxic stabilizers that prevent thermal decomposition during molding at high temperatures, and harsh working conditions throughout various molding processes are required. What is needed is something that can withstand.

In order to meet this demand, less toxic dioctyltin compound-based or dimethyltin-based stabilizers have been developed and put into practical use, but problems remain in long-term workability during molding.

For example, when these dialkyltin bis(mercaptocarboxylic acid ester) is used alone or in combination with a small proportion of monoalkyltin tris(mercaptocarboxylic acid ester) and/or dialkyltin mercaptocarboxylic acid salt, the long-term thermal stability is Although satisfactory results have been obtained, the effect of suppressing initial coloration and thermal coloration is unsatisfactory. In addition, liquid stabilizers that are a combination of these have drawbacks such as the resin composition becoming sticky during processing, contaminating the molded product and damaging the surface shape, reducing processing efficiency.

In addition, although the coloring property is improved to some extent by using a large proportion of monoalkyltin tris (mercaptocarboxylic acid ester) and a small proportion of dialkyltin bis (mercaptocarboxylic acid ester), it is still insufficient, and further improvement is necessary. was there.

As a result of extensive research to solve the above-mentioned problems, the present inventors found that monooctyltin tris(mercaptocarboxylic acid ester) 50-9 expressed by the following general formula (1)
9.5% by weight, 0 to 49% by weight of dioctyltin bis(mercaptocarboxylic acid ester) represented by the following general formula (n) and dioctyltin mercaptocarboxylic acid salt represented by the following general formula (III) A liquid stabilizer consisting of 0.5 to 5% by weight unexpectedly improves the thermal stability of halogen-containing resins, has a large effect on suppressing initial coloring, improves processability, and is non-toxic and low-toxic. It was discovered that the storage stability etc. are also excellent, and the present invention was achieved.

Cal1173n (SRIGOOR2) 3 (I
)(Cs R17)2 Sn (SRICOOR2)z
(II) ((Cs II7) 2 S n 5R3C
OO) m (III) (wherein R+ is -CH2- or -
C2) (represents II-, R2 represents an alkyl group having 8 to 18 carbon atoms, R3 represents an alkylene group having 1 to 4 carbon atoms, m does not represent 1 to 50.) Hereinafter, the present invention The liquid stabilizer for halogen-containing resin will be explained in detail.

The alkyl group represented by R2 in the general formulas (1) and (n) includes isooctyl, 2-ethylhexyl, octyl, nonyl, decyl, isodecyl, lauryl,
Examples include cetyl, valmityl, stearyl, isostearyl, and the like.

Examples of the monooctyltin tris (mercaptocarboxylic acid ester) represented by the general formula (1) used in the present invention include monooctyltin tris (isooctyl mercaptoacetate), monooctyltin tris (isooctyl mercaptoacetate),
2-Ethylhexylmercaptoacetate].), monooctyltin tris (octylmercaptoacetate), monooctyltin].lis (lauryl mercaptoacetate), monooctyltin tris (tetradecylmercaptoacetate-1.), monooctyl Tin tris (010-16 alkylmercaptoacetate), monooctyltin tris (stearylmercaptoacetate), monooctyltin tris (inoctylmercaptopropionate), monooctyltin tris (2-ethylhexylmercaptopropionate) , monooctyltin tris (laurylmercaptopropionate), monooctyltin tris (tetradecylmercaptoprobionate), monooctyltin tris (stearylmercaptopropionate), and the like.

The content of monooctyltin tris (mercaptocarboxylic acid ester) in the liquid stabilizer for halogen-containing resins of the present invention is 50 to 99.5% by weight.

Dioctyltin bis(mercaptocarboxylic acid ester) represented by the general formula (II) used in the present invention
Examples include dioctyltin bis(isooctylmercaptoacetate), dioctyltinbis(2-ethylhexylmercaptoacetate-1~), dioctyltinbis(octylmercaptoacetate), dioctyltinbis(laurylmercaptoacetate), and dioctyltinbis(laurylmercaptoacetate). Tin bis(tetradecyl mercaptoacetate), dioctyltin bis(CIO~16 alkyl mercaptoacetate),
Dioctyltin bis(stearyl mercaptoacetate)
, dioctyltin bis(isooctylmercaptopropionate), dioctyltinbis(2-ethylhexylmercaptopropionate), dioctyltinbis(laurylmercaptopropionone-1-), dioctyltinbis(stearylmercaptopropionate-1-) propionate), etc.

The content of dioctyltin bis(mercaptocarboxylic acid ester) in the liquid stabilizer for halogen-containing resins of the present invention is as follows:
It is 0 to 49% by weight.

Examples of the dioctyltin mercaptocarboxylate salt represented by the general formula (III) used in the present invention include dioctyltin mercaptoacetate, dioctyltin α-mercap I propione]-, ]dioctyltin β-mercapto Examples include propionate dioctyltin mercaptobutyrate.

The content of dioctyltin mercaptocarboxylate in the liquid stabilizer for halogen-containing resins of the present invention is 0.5 to 5% by weight, preferably 1 to 3% by weight.

If 0.5% by weight is ungrooved, the effect of suppressing coloring is small, and if it exceeds 5% by weight, no further improvement in the effect of suppressing coloring is seen, but rather the resin tends to stick during processing, so it is not practical. do not have.

Furthermore, the stabilizer of the present invention exhibits excellent effects even when it is composed of two components, monooctyltin tris(mercaptocarboxylic acid ester) and dioctyltin mercaptocarboxylate; It is preferable to use a three-component system using ) because the thermal stability and coloring suppression effect are significantly improved. In this case, the content of each component is 50 to 94.5% by weight of monooctyltin tris(mercaptocarboxylic acid ester), preferably 52 to 89% by weight, and 5 to 45% by weight of dioctyltin bis(mercaptocarboxylic acid ester). , preferably 10-45% by weight, 0.5-5% by weight of dioctyltin mercaptocarboxylate, preferably 1-3M%
It is desirable to do so.

The stabilizer of the present invention can be prepared by mixing the above-mentioned components separately, or by reacting monooctyltin chloride or oxide (and dioctyltin chloride or oxide) with a mercaptocarboxylic acid ester, and then adding dioctyltin chloride to the mercaptocarboxylic acid ester. Alternatively, it can be easily produced by adding and reacting an oxide and a mercaptocarboxylic acid, and in either case, a highly effective stabilizer can be obtained.

The liquid stabilizer for halogen-containing resin of the present invention has a resin 100
0.01 to 10 parts by weight, preferably 0.01 to 10 parts by weight.
1 to 5 parts by weight is blended depending on the purpose.

Phthalate plasticizers or other ester plasticizers, polyester plasticizers, phosphate plasticizers, epoxy plasticizers, chlorine plasticizers, and other plasticizers can be used together with the stabilizer of the present invention. It can be used as appropriate.

Since the use of an antioxidant together with the stabilizer of the present invention can increase the antioxidant properties of the polymer composition, it can be used as appropriate depending on the purpose of use. These antioxidants include phenolic antioxidants, sulfur-containing compounds, and the like.

If an ultraviolet absorber is added together with the stabilizer of the present invention, the photostability can be improved, so it is possible to appropriately select and use these depending on the purpose of use. These include benzophenones, benzotriazoles, salicylates, substituted acrylic nitriles, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazines, and the like.

Others as necessary, such as metal soaps, pigments, fillers, etc.
Foaming agents, antistatic agents, antifogging agents, play-1-out prevention agents, surface treatment agents, lubricants, n-flame agents, fluorescent agents, antifungal agents, bactericidal agents, metal deactivators, photodegradants, nonmetals stabilizer, rII
JI acid ester, thiourea derivative, processing aid, mold release agent,
A reinforcing agent etc. can be used together.

Examples of halogen-containing resins stabilized by the stabilizer of the present invention include the following. For example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer , vinyl chloride-7”t+pyrene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer , vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-
Chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer , halogen-containing synthetic resins such as vinyl chloride-acrylonitrile copolymers, internally plasticized polyvinyl chloride, and halogen-containing synthetic resins described in "2" and α-olefin polymers such as polyethylene, polypropylene, polybdenum, poly-3-methylbutene, Ethylene-vinyl acetate copolymer, ethylene-
Polyolefins such as propylene copolymers and their copolymers, polystyrene, acrylic resins, copolymers of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers Examples include a blend product with a combination, an acrylic ester-butadiene-styrene copolymer, and a methacrylic ester-butadiene-styrene copolymer.

Examples of the present invention will be given below to clarify the effects of the present invention.

Example 1 Liquid stabilizers (stabilizers A1 to A14) were produced by mixing the components shown in Table 1.

The abbreviations of the compounds listed in the component column of Table 1 indicate the following compounds.

Oct Sn ([0TG) 3 F Monooctyltin tris(isooctyl mercaptoacetate) Oct 2 Sn (IOTG) 2 Nidioctyltin bis(isooctyl mercaptoacetate) Oct Sn (IOMP) 3 : Monooctyltin tris(isooctyl mercaptopropionate) Oct 2 Sn (IOMP) 2 Nidioctyltin bis(isooctylmercaptopropionate) (Oct 2 Sn 5CII2 COO) m Nidioctyltin mercaptoacetate (Oct 2 Sn 5CH2Cl12 Coo )
m Nidioctyltin β-mercaptopropionate Using the above liquid stabilizer, a sheet having a thickness of 1lIIl was prepared by kneading roll processing according to the following formulation, and a heat deterioration test at 190°C and an initial colorability test were conducted. Another 180
A mill test was conducted at 0.degree. C., and a thermal coloring test was conducted after 15 minutes. The results are shown in Table 1.

(Composition) PVC (Geon 103 EP8) 100 parts by weight Polyethylene wax 0.2 Stearyl alcohol 0.5 Dioctyltin malate polymer 0.2 Stabilizer (81-
A14) 1.8 The evaluation method for the thermal coloring and initial coloring tests was on a 10-point scale, ranging from 1 (good) to 10 (bad).

Example 2 A liquid stabilizer ( Stabilizer B) was prepared.

Example 3 Stable liquid by mixing 80 parts of monooctyltin tris(tetradecyl mercap; acetate), 18 parts of dioctyltin bis(te1-radecylmercaptoacetate), and 2 parts of dioctyltin mercaptopropionate. (Stabilizer C) was prepared.

Example 4 82 parts of monooctyltin tris (C1 (1=Ct6 alkyl mercabutoacetate), dioctyltin (for C to C
A liquid stabilizer (Stabilizer D) was prepared by mixing 15 parts of IG alkyl mercaptoacetate) and 3 parts of dioctyltin mercaptoacetate.

Example 5 By mixing 55 parts of monooctyltin tris(2-ethylhexylmercaptopropionate), 43 parts of dioctyltin bis(2-ethylhexylmercaptopropionate) and 2 parts of dioctyltin mercaptobutyrate. A liquid stabilizer (Stabilizer E) was produced.

Example 6 A test was conducted in the same manner as in Example 1 using the following formulation. The results are shown in Table 2.

(Formulation) PVC (Ge, +n 103 EP8D) 100 parts by weight Impact modifier (Metablen W-529) 5 Calcium stearate 0.2 Zinc stearate 0.1 Stabilizer (Table 2) 1 Table 2 Nooctyltin tris (isooctyl mercaptoacetate
1-) 0.32 parts, 0.65 parts of dioctyltin bis(isooctylmercaptoacetate), and 1-0.03 parts of dioctyltin mercaptoacetate.

Example 7 A test was conducted in the same manner as in Example 1 using the following formulation. The results are shown in Table 3.

(Composition) PVC (Geon 103 EP) 100 parts by weight Impact modifier (Kane Ace FM) 15 Processing aid (Kane Ace PA-20) 1 Stearic acid monoglyceride 0
．． 5 Polyethylene wax 0.2 Stabilizer (Table 3) ■, 5 Table 3

Claims (1)

[Scope of Claims] 50 to 99.5% by weight of monooctyltin tris(mercaptocarboxylic acid ester) represented by the following general formula (1),
0 to 49% by weight of dioctyltin bis(mercaptocarboxylic acid ester) represented by the following general formula (II) and 0.5 to 5% by weight of dioctyltin mercaptocarboxylate represented by the following general formula (III) A liquid stabilizer for halogen-containing resins. C8H17Sn (SRICOOR2)3 (I) (C
8HI7) z Sn (SRICOOR2) 2 (
II) ((CsH+7)psnsR3cOo)m (I
ll) (In the formula, R1 represents -CH2- or -C2H4-, R2 represents an alkyl group having 8 to 18 carbon atoms, and R3
represents an alkylene group having 1 to 4 carbon atoms. m is 1 to 5
Indicates 0. )