JPS5928228B2 - Gun halogen equipment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stabilized halogen-containing resin composition containing a metal salt and an adduct of dihydric phenol diglycidyl ether and polyhydric alcohol.

Specifically, it is stabilized by adding at least one metal salt and a polyhydric alcohol adduct with a Ξ value or higher of a diglycidyl ether compound derived from catechol, resorcinol, hydroquinone, and naphthohydroquinone to a logen-containing resin. The present invention relates to a halogen-containing resin composition.

In general, halogen-containing resins have poor stability against heat and light, and tend to undergo thermal decomposition mainly due to dehydrohalogenation during thermoforming.

This causes a decline in the mechanical properties and color tone of processed products, resulting in significant disadvantages. Therefore, in order to avoid such drawbacks, it has been necessary to add one or more kinds of thermal stabilizers to the resin to suppress thermal deterioration during processing steps. Many metal soaps are used for this purpose,
As a result, almost satisfactory results were obtained in terms of thermal stability. However, among these metal soaps, cadmium soap, lead soap, etc. are highly toxic, and their use is currently largely restricted. Therefore, it is necessarily necessary to use metal soaps or non-metallic stabilizers other than cadmium or lead soaps to obtain satisfactory thermal stability. For this purpose, methods have been considered that aim for a synergistic effect by combining two or more types of non-toxic metal soaps or a combination of them and a non-metallic stabilizer. Although thermal stability can be obtained, the thermal stabilization effect is considerably inferior to that obtained when using cadmium or lead soap, and additional drawbacks arise, and the above method poses technical problems as a stabilizer. Not enough to satisfy.

For example, the combination of a metal soap such as calcium, zinc, magnesium or barium with a polyhydric alcohol, diphenylthiourea or trisnonylphenyl phosphite,
The stabilizing effect is insufficient and cannot be put to practical use.

Although the combination of the metal soap and epoxidized soybean oil has a certain degree of heat stabilizing effect, it has the disadvantage of lowering the softening point of the resin when it is hard compounded. Furthermore, aminocrotonic acid esters have very poor compatibility with halogen-containing resins, and are particularly insufficiently effective against vinyl chloride resins obtained by suspension polymerization. Furthermore, although dehydroacetic acid improves the initial coloration, it does not have a long-term stabilizing effect. Moreover, it cannot be said that it is practically sufficient during molding.

For example, in the calender roll method, a plate-out phenomenon occurs on the surface of the molded product, which impairs the surface shape of the molded product and significantly reduces processing efficiency. This plate-out phenomenon is observed in almost the same way in processing steps other than the calender roll method, and is a drawback when halogen-containing resins are stabilized using metal soaps. In order to solve the drawbacks associated with conventional stabilizers by using metal soaps other than cadmium and lead, the present inventors have conducted many years of research and found that they have excellent stability against deterioration due to light and heat. We have succeeded in developing a halogen-containing resin composition that has the following properties.

That is, the present invention provides a rogen-containing resin containing (a) 0.01 to 5 parts by weight of at least one metal salt and (b) derivatives of catechol, resorcinol, hydroquinone, and naphthohydroquinone based on 100 parts by weight of the resin. The present invention provides a stabilized halogen-containing resin composition containing 0.01 to 5 parts by weight of a trihydric or higher polyhydric alcohol adduct of a diglycidyl ether compound.

Specifically, the diglycidyl ether compound is obtained by reacting catechol, resorcinol, hydroquinone or naphthohydroquinone with epichlorohydrin or β-methylepichlorohydrin by a known method.

Specifically, catechol diglycidyl ether, catechol di-β-methyl glycidyl ether, 2-methylcatechol diglycidyl ether, 3-ethoxycatechol diglycidyl ether, 3-t-butylcatechol diglycidyl ether, 3t-butylcatechol-di-β-methyl Glycidyl ether, resorcin diglycidyl ether, resorcin di β-methylglycidyl ether, 2
Methyl resorcin diglycidyl ether, 2・t4・
6-Tribromoresorcin diglycidyl ether, 4-
Methylresorcin diglycidyl ether, 4-n-hexylresorcin diglycidyl ether, 2,5-dimethylresorcin diglycidyl ether, 2-methylresorcin di-β-methylglycidyl ether, Hite rainbow quinone diglycidyl ether, hydroquinone di-β- Methyl glycidyl ether, 2-methylhydroquinone diglycidyl ether, 2-t-butylhydroquinone diglycidyl ether, 2-octylhydroquinone diglycidyl ether, 2-tridecylhydroquinone diglycidyl ether, 2,5-dibutylhydroquinone diglycidyl ether, 2・5-di-t-butylhydroquinone diglycidyl ether, 2,5-diethoxyhydroquinone diglycidyl ether, 2-pentadecylhydroquinone diglycidyl ether, 2,6-ditridecylhydroquinone diglycidyl ether, 2,3,6
-trimethylhydroquinone diglycidyl ether, 2
Examples include -methylhydroquinone di-β-methylglycidyl ether, α-naphthohydroquinone diglycidyl ether, α-naphthohydroquinone diβ-methylglycidyl ether, and β-naphthohydroquinone diglycidyl ether.

The addition compound of divalent phenol diglycidyl ether and polyhydric alcohol used in the present invention is a generally known addition compound of the diglycidyl ether compound of catechol, resorcinol, hydroquinone, and naphthohydroquinone and a trihydric or higher polyhydric alcohol. It can be obtained by reacting according to the method.

Specifically, the above-mentioned trihydric or higher polyhydric alcohols include, for example, glycerin, 2-methyl-2-methylol-1.
3-propanediol, 2,4 dihydroxy-3-methylolpentane, 1,2,6-hexanetriol, 1
・1.1-trimethylolpropane, 2.2-dimethylol-3-hydroxybutane, 1.l.1-trimethylolethane, 2.4-dihydroxy-2.4-dimethyl 3-methylolpentane, 1.2. 3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1
・2,3-propanetriol, erythritol, pentaerythritol, 1,2,3,4-pentanetetrol, 1,3,4,5 hexanetetrol, dipentaerythritol, xylitol, adonitol, sorbitol, mannitol, heptitol, octitol, glucose, fructose, galactose, satucalose,
Examples include maltose and lactose.

Examples of metal salts used in the present invention include sodium, potassium, lithium, tin, zinc, calcium,
Examples include barium, magnesium or strontium carboxylates, phenolates, and alkyltin compounds. Carboxylic acids that can be used include, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, natonic acid, hydrofuric acid, neoacid, 2-ethylhexylic acid, pelargonic acid, hydropuric acid, undecanoic acid. , lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid,
Monochlorobenzoic acid, Ptert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, Aminobenzoic acid, N-N-dimethylbenzoic acid, acetoxybenzoic acid, salicylic acid, p-Tert-octylsalicylic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid, etc. Monocarboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
sebacic acid, phthalic acid, isophthalic acid, terephthalic acid,
monoester or monoamide compounds of dihydric carboxylic acids such as oxyphthalic acid, chlorphthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, aconitic acid, thiodipropionic acid,
Examples include di- or triester compounds of trivalent or tetravalent carboxylic acids such as hemimellitic acid, trimellitic acid, merophonic acid, pyromellitic acid, and mellitic acid. Examples of phenols for obtaining the above phenolates include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, and ethylphenol. Phenol, isopropylphenol, isooctylphenol, 2-ethylhexylphenol, tert-nonylphenol, decylphenol, tert-octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisohexylphenol, Methyl-Tert
-Octylphenol etc. can be used.

Further, examples of alkyltin compounds used in the present invention include:
The following can be mentioned.

Namely, monobutyltin trichloride, monomethyltin trichloride, monooctyltin trichloride, dimethyltin cyclolade, dibutyltin cyclolade, dioctyltin cyclolade, methylstanoitsucic acid, butylstanoitsucic acid, octylstannoitsucic acid, dimethyltin oxide, dibutyltin oxide, dioctyltin oxide, dimethyltin sulfide, dibutyltin sulfide,
Dioctyltin sulfide, synchrohexyltin sulfide, monobutyltin oxide sulfide, methylthiostanoitsucic acid, butylthiostanoitsucic acid, octylthiostanoitsucic acid, dibutyltin laurate, dibutyltin stearate, dioctyltin diolate, dibutyltin Basic laurate, dibutyltin dicrotonate,
Dibutyltin bis(butoxydiethylene glycol malate), dibutyltin dimethacrylate, dibutyltin disinnamate, dioctyltin bis(oleyl maleate), dibutyltin bis(stearyl maleate) dibutyltin itaconate, dioctyltin maleate, diamyltin bis(cyclohexylmamate) dimethyltin dicrotonate, diethyltin bis(isooctyl citraconate), dipropyltin bis(benzyl maleate), diisobutyltin bis(propyl maleate), synchrohexyltin maleate,
Dioctyltin bis(butyl maleate), dibutyltin dimethoxide, dibutyltin dilauroxide, dioctyltin ethylene glycoxide, pentaerythritol dibutyltin oxide condensate, dibutyltin bis(lauryl mercaptite), dimethyltin bis(stearylcaptide),
Monobutyltin tris (lauryl mercaptite), dibutyltin-β mercaptopropionate, dioctyltin-
β-mercaptopropionate, dibutyltin mercaptoacetate, monobutyltin tris(isooctylmercaptoacetate), monooctyltin tris(2-ethylhexylmercaptoacetate), dibutyltin bis(isooctylmercaptoacetate), dioctyltin bis(
isooctylmercaptoacetate), dioctyltin bis(2-ethylhexylmercaptoacetate), dimethyltin bis(isooctylmercaptoacetate), dimethyltin bis(isooctylmercaptopropionate)
, monobutyltin tris(isooctylmercaptopropionate), bis[monobutyldi(isooctoxycarbonylmethylenethio)tin]sulfuride, bis[dibutylmono(isooctoxycarbonylmethylenethio)tin]sulfide, monobutylmonochlorotinbis (isooctyl mercaptopropionate), monobutyl monochlorotin bis (isooctyl mercaptoacetate), monobutyl monochlorotin bis (lauryl mercaptite)
, dibutyltin bis(ethylcelsorobemalate), bis(dioctyltin laurate) malate, bis(dioctyltinbutylmalate) malate, and the like.

Next, specific examples of adduct compounds of diglycidyl ether derivatives and trivalent or higher polyhydric alcohols according to the present invention are shown below.

(However, the ratio in the compound name shall represent the molar ratio.) That is, one catechol diglycidyl ether (1:2
)-1,1,1-trimethylolethane adduct, catechol diglycidyl ether mono(1:2) pentaerythritol adduct, catechol di-β methylglycidyl ether mono(1:2)-sorbitol adduct, 2-methylcatechol Diglycidyl ether-(1:2)-mannitol adduct, 3-t-butylcatechol diglycidyl ether (1:2)-1,2,3-butanetriol adduct, resorcin diglycidyl ether (1:2) -Glycerin adduct, resorcin di-β-methylglycidyl ether-(1:2)-sorbitol adduct, 2-methylresorcin diglycidyl ether-(1:2)-2.
4-dihydroxy 3-methylolpentane adduct, 2.
4,6-Tribromoresorcin diglycidyl ether-
(1:2)-1,1,1-trimethylolpropane adduct, 4-methylresorcin diglycidyl ether (1:
2) -1,2,3-butanetriol adduct, 2,5-
Dimethyl resorcin diglycidyl ether (1:2)
- Dipentaerythritol adduct, resorcin diglycidyl ether (1:1) - Pentaerythritol adduct, hydroquinone diglycidyl ether (1:2)
-erythritol adduct, hydroquinone di-β-methylglycidyl ether-(1:2)-pentaerythritol adduct, 2-methylhydroquinone diβ-methylglycidyl ether-(1:2)-sorbitol adduct,
2-Tridecylhydroquinone diglycidyl ether-
(1:2)-1,2,3-butanetriol adduct, 2
・5-di-tbutylhydroquinone diglycidyl ether (1:2)-1,2,3-pentanetriol adduct, 2,3,6-trimethylhydroquinone diglycidyl ether (1:2)-sutucarose adduct, α-Naphthohydroquinone diglycidyl ether-(1:2)-
1,1,1-trimethylolpropane adduct, α-naphthohydroquinone diglycidyl ether (1:2)-
Pentaerythritol adduct, α-naphthohydroquinone diβ-methylglycidyl ether-(1:2) sorbitol adduct, β-naphthohydroquinone diglycidyl ether-(1:2)-glycerin adduct, catechol diglycidyl ether mono(2) :1)-pentaerythritol adduct, 3-t-butylcatechol di-β-methylglycidyl ether-(2:1)-xylitol adduct, catechol diglycidyl ether-(3:1)-dipentaerythritol adduct, Resorcinol diglycidyl ether (2:1)-glycerin adduct, hydroquinone diglycidyl ether (2:1) sorbitol adduct, hydroquinone diglycidyl ether (1:1)
- pentaerythritol adducts, etc.

Next, synthesis examples of these adduct compounds will be briefly described, but these synthesis methods are just examples, and synthesis is also possible by methods other than those described, and the polyhydric alcohol adduct of the present invention can be synthesized using these methods. There are no limitations whatsoever depending on the synthesis method.

Synthesis Example 1 Synthesis of hydroquinone diglycidyl ether-(1:2)-pentaerythritol adduct To an aqueous solution in which 136y of pentaerythritol was dissolved in 30y of water, 0.37% of potassium hydroxide was added as a catalyst and the temperature was raised to 80°C.

Here, hydroquinone diglycidyl ether 11.6y
was slowly added to a solution of dioxane 307 with stirring. After the addition is complete, the reaction solution is heated to reflux temperature (95°C).
The temperature was raised to 100%, and the reaction was allowed to proceed for 16 hours. Next, 50 ml of methanol was added to the residue after desolvation under reduced pressure, and unreacted pentaerythritol as an insoluble substance was separated and removed. When the liquid f was desolvated, the target object, pale yellow solid 21.27, was obtained.
Melting point = 81~86°C1 hydroxyl value -88.3 (calculated value -
9.09), oxirane oxygen -0.15%. Examples of the halogen-containing resin used in 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 monovinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride monovinylidene chloride copolymer, Vinyl chloride styrene x-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride monochlorinated propylene copolymer, chloride Vinyl monochloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride acrylonitrile copolymer, Halogen-containing synthetic resins such as internally plasticized polyvinyl chloride, α-olefin polymers such as polyethylene, polypropylene, polybutene, and poly-3-methylbutene, or polyolefins such as ethylene monoacetate pinyl copolymer and ethylene-propylene copolymer; These copolymers, polystyrene, acrylic resins, copolymers of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene- Styrene copolymer, methacrylic acid ester-butadiene-
Examples include styrene copolymers, blends of these resins, block copolymers, graft copolymers, and the like.

The chlorine-containing resin composition of the present invention includes phthalate plasticizers, other ester plasticizers, polyester plasticizers, phosphoric ester plasticizers, epoxy plasticizers, chlorine plasticizers, and other plasticizers. Agents and the like can be used as appropriate depending on the purpose.

Furthermore, it goes without saying that other additives may be added to the composition of the present invention to further improve its performance. Examples of these other additives include antioxidants, light stabilizers, etc. agent, nucleating agent, filler, epoxy stabilizer, organic chelator, pigment, antistatic agent, antifogging agent, plate-out inhibitor, surface treatment agent, lubricant, flame retardant, fluorescent agent, antifungal agent, sterilizer agents, photodegradants, non-metallic stabilizers, borate esters, processing aids, mold release agents, and the like. As these other additives, conventionally well-known compounds can be used. For example, as antioxidants, phenolic, amine,
Phosphite-based and sulfur-based antioxidants are used, and specifically, those disclosed in JP-A-4978692 are used.

As the light stabilizer, benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, various metal salts or metal chelates, triazine-based, and piperidine-based light stabilizers can be used.
The material disclosed in Japanese Patent No. 9-178692 can be used. Next, the present invention will be specifically explained using examples.

However, the invention is not limited to the examples listed below. Example 1 In order to examine the stabilizing effect of the composition of the present invention, samples were prepared by calender processing and heat press processing according to the following formulation, and the thermal stability and heat press tests were performed using a heat aging tester at 190°C. Transparency and initial colorability due to processing were measured.

The results are shown in Table 1. Example 2 In order to demonstrate the excellent stabilizing effect of the composition of the present invention, Example 1 was prepared using the following formulation.
A performance test was conducted using the same method.

The results obtained are shown in Table 2 below. Example 3 In order to examine the stabilizing effect of the compound according to the present invention on a polyvinyl chloride-acrylonitrile-butadiene-styrene copolymer (ABS resin) blend product, a sample was prepared using the same procedure as in Example 1 with the following formulation. I conducted a test.

The results are shown in Table 3 below. Example 4 In order to examine the stabilizing effect of the composition of the present invention, a performance test was conducted in the same manner as in Example 1 using the following tin formulation.

The results are shown in Table 4. Example 5 In order to examine the effect of adding other additives to the composition of the present invention in combination, the same test as in Example 1 was conducted using the following formulation.

Claims (1)

[Claims] 1. For 100 parts by weight of the halogen-containing resin (a
) 0.01 to 5 parts by weight of at least one metal salt and (b
) Trihydric or higher polyhydric alcohol adducts of diglycidyl ether compounds derived from catechol, resorcinol, hydroquinone and naphthohydroquinones 0.01-5
A stabilized halogen-containing resin composition obtained by adding parts by weight.