JPS5840580B2 - 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 a hydrate of an epoxy compound.

More specifically, in the halogen-containing resin, based on 100 parts by weight of the resin, a) at least one metal salt selected from carboxylates or ferulates of zinc, calcium, barium, or magnesium, and alkyltin carboxylates from 0.01 to 5 parts by weight and b) a hydrate of an epoxy compound having at least one ester bond or ether bond and at least one epoxy group in the molecule or a fat having at least two epoxy groups in the molecule Hydrates of group or alicyclic hydrocarbons 0.01-5
This invention relates to a stabilized halogen-containing resin composition obtained by adding parts by weight.

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

As a result, the mechanical properties of processed products deteriorate and the color tone deteriorates, resulting in significant disadvantages.

In order to avoid such drawbacks, it is necessary to add one or more types of thermal stabilizers to the synthetic resin to suppress thermal deterioration during the processing steps.

Many metal soaps have been used for this purpose, with generally satisfactory results in terms of thermal stability.

However, among these metal soaps, cadmium soap, lead soap, etc. are highly toxic, and their use is currently severely 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 in which two or more types of non-toxic metal soaps or a combination of them and a non-metal stabilizer are used to achieve a synergistic effect.

However, although a certain degree of thermal stability can be obtained using these methods, the thermal stabilization effect is considerably inferior to that when using cadmium or lead soap, and additional drawbacks arise, so the above-mentioned problems arise. The method is insufficient to satisfy the technical problem as a stabilizer.

For example, a combination of a metal soap such as calcium, zinc, magnesium or barium with a polyhydric alcohol, diphenylnaourea or trisnonylphenyl phosphite has an insufficient stabilizing effect and is not suitable for practical use.

Further, although the combination of the metal soap and epoxidized soybean oil has a certain degree of heat stabilizing effect, it has the drawback of lowering the softening point when blending with a hard resin.

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 roll surface, which impairs the surface shape of the molded product and significantly reduces processing efficiency.

This phenomenon of plate-out is observed in almost the same way in processing steps other than the calendar roll method, and is a drawback when stabilizing halogen-containing resins using metal soaps.

In order to solve the drawbacks associated with conventional stabilizers by using metal soaps other than cadmium and lead plates, the present inventors have conducted many years of research and found that they have excellent stability against deterioration due to light and heat. We succeeded in developing a stabilizer with this property.

That is, the present invention provides a halogen-containing resin, based on 100 parts by weight of the resin, a) at least one metal salt selected from carboxylates of zinc, calcium, barium, or magnesium, ferulates, and alkyltin carboxylates.
, oi ~ 5 parts by weight, and b) a hydrate of an epoxy compound having at least one ester bond or ether bond and at least two epoxy groups in the molecule, or at least two epoxy groups in the molecule. The object of the present invention is to provide a stabilized halogen-containing resin composition in which 0.01 to 5 parts by weight of an aqueous aliphatic or alicyclic hydrocarbon having the following are added.

The hydrate of the epoxy compound according to the present invention has a water solvent and/or
Alternatively, it can be easily obtained by reacting an epoxy compound with water in a water-soluble organic solvent without a catalyst or with an organic or inorganic acid and base as a catalyst.

Hydrates of the epoxy compound of the present invention include, for example, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A di-β
-Methyl glycidyl ether, bisphenol A propylene oxide adduct diglycidyl ether, hydrogenated bisphenol A propylene oxide adduct diglycidyl ether, phthalic acid bisphenol A glycidyl ester ether, p-oxybenzoic acid glycidyl ether ester, tetrakis hydroxyphenylethane tetraglycidyl Ether, trishydroxyphenylmethane triglycidyl ether, tetrakishydroxyphenylmethane tetraglycidyl ether, trishydroxyphenylpropane triglycidyl ether, bisphenol F diglycidyl ether, phenol novolac polyglycidyl ether, cresol novolac polyglycidyl ether, resorcinol diglycidyl ether,
Resorcinol di-β-menalclycidyl ether, catechol diglycidyl ether, hydroquinone diglycidyl ether, 2-glycidylphenylglycidyl ether, 2,6-dicrycidyl phenylglycidyl ether, cyclohexene diglycidyl ether, bisphenol A bis(3,4 -Epoxycyclohexylmethyl) dicarbonate, pentaerythritol bis(3゜4
-Epoxy dichlorohexyl) acetal, diglycidyl phthalate, di-β-methylglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, tetraglycidyl trimellitate, trimellitic acid bisphenol A propylene oxide adduct tetraglycidyl ester, di- Glycidylcyclopenkune-1,3-dicarboxylate, diglycidylcyclopropane-1,3-dicarboxylate, α,
ω-Dodecane dioxide, trihydroxydiphenyldimethylethane diglycidyl ether, enalene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene (n=4-200) glycol diglycidyl ether, propylene glycol diglycidyl ether Glycidyl ether, polypropylene (n-2 to 10) glycol diglycidyl ether, neopenal glycol diglycidyl ether, ■, 4-butanediol diglycidyl ether, ■, 6-hexanesiol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol tetraglycidyl ether, polyoxymenalene glycol diglycidyl ether, pentaerythritol propylene oxide adduct tetraglycidyl ether, sorbitol propylene oxide adduct glycidyl ether, trimenalol propane triglycidyl ether, Trinonalol propane diglycidyl ether, malonic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, maleic acid diglycidyl ester, itaconic acid diglycidyl ester, dimer acid diglycidyl ester, 3,4-epoxy- 6-Methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3°4-epoxycyclohexanecarboxylate, Bis(3,4-epoxy-6-
Methylcyclohexylmethyl)adipate, bis(3,
4-epoxycyclopenal) ether, epoxidized polybutadiene, epoxidized soybean oil, alloocymene dioxide, vinylcyclohexene diepoxide, dicyclopentadiene dioxide, limonene dioxide,
Examples include hydrates of butadiene dioxide, dimenalpenkune dioxide, divinylbenzene dioxide, and the like.

Metal salts used in combination with the present invention include carboxylates or ferulates of zinc calcium, barium or magnesium, and alkyltin carboxylates.

Carboxylic acids that can be used to obtain the above carboxylates include, for example, formic acid, acetic acid, propionic acid,
butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid,
Neoacid, 2-ethylhexylic acid, pelargonic acid, capric 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, p-tert
-Bunalbenzoic acid, Dimenalhydroxybenzoic acid, 3,
5-di-tert-buna-4-hydroxybenzoic acid, toluic acid, dimenalbenzoic acid, enalbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N,N-
Dimenalbenzoic acid, acetoxybenzoic acid, salinaic acid,
m-carboxylic acids such as p tert-ocnar salinic acid, oleic acid, elaidic acid, linoleic acid, linoleic acid, naoglycolic acid, mercaptopropionic acid, ocnal mercaptopropionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid Acid, adipic acid, pimelic acid, superic acid, azelaic acid, cepatic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorphthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, Monoesters or monoamide compounds of divalent carboxylic acids such as aconitic acid and naodipropionic acid; di- or monoamide compounds of divalent or tetravalent carboxylic acids such as hemimellitic acid, trimellitic acid, merophonic acid, pyromellitic acid, and mellitic acid; Examples include triester compounds.

Furthermore, as the phenol for obtaining the above-mentioned ferulates, phenols having various substituents can be used, such as tert-bunalphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, ofnalphenol, phenol. , cresol, xylenol, n-bunalphenol, isoamylphenol, ethylphenol, inpropylphenol, inofnalphenol, 2-ethylhexylphenol, tert-nonylphenol,
Examples include decylphenol, tert-ofnalphenol, isohexylphenol, octadecylphenol, natural phenol, methylpropylphenol, cyamylphenol, methylisohexylphenol, and methyl-tertofnalphenol.

Further, examples of the alkyl tin carboxylates used in the present invention include the following.

Namely, dibnaltin laurate, dibnaltin stearate, dibnaltin diolate, dibnaltin basic laurate, dibnaltin dicrotonate, siftyltin bis(butoxydienalene glycol malate), dibnaltin dimethacrylate, dibnaltin disinnamate, dibnaltin bis( oleyl maleate), cyphthyltin bis(stearyl maleate) dibutyltin itaconate, dioctyltin maleate, dioctyltin maleate, cyamyltin bis(cyclohexyl maleate), dimethyltin cyclotonate,
Diethyltin bis(isooctyl citraconate), sifropyrtin bis(benzyl maleate), diynbutyltin bis(propyl maleate), dicyclohexyltin maleate, diocnaltin bis(butyl maleate), dibnaltin bis(ethylcellulobutyl maleate) , bis(diocnaltin laurate) malate, and bis(dioctyltin bunalmalate) malate.

Next, a specific example of synthesis of a hydrate of the above-mentioned epoxy compound will be described.

These methods are merely examples of synthesis, and synthesis is also possible by methods other than those described, and the epoxy hydrate of the present invention is not limited in any way by these synthesis methods.

Synthesis Example 1 Synthesis of Bisphenol A diglycidyl ether hydrate Bisphenol A diglycidyl ether 27. ! 9. 100 g of water and 1.0.9 g of concentrated sulfuric acid as a catalyst were calculated, and the mixture was stirred and reacted under reflux (98~too'c) for about 10 hours.

The insoluble portion was separated by decantation, washed several times with warm water, dried under reduced pressure, and pulverized to obtain white powder 26, IJ with a melting point of 88 to 95°C.

This white powder consists of 1. R, 920cm by spectrum
The absorption by the epoxy group of -1 almost completely disappeared, and 33
00cIrL-1 shows large broad absorption due to hydroxyl groups, and its hydroxyl value is 516 (
Since the calculated value was 577) and oxirane oxygen was 0.05%, it was confirmed to be the target product.

Synthesis Example 2 Synthesis of glycerin triglycidyl ether hydrate Glycerin triglycidyl ether 26.0g, water 50
9 and 0.3 g of concentrated sulfuric acid as a catalyst were weighed and the mixture was stirred under reflux (98-100° C.) for about 10 hours.

At the beginning of the reaction, it was in a suspended state, but as the reaction progressed, it changed to a uniform transparent state.

Next, a calculated amount of potassium hydroxide was added to neutralize the mixture, and after dehydration under reduced pressure, it was dissolved in methanol to remove insoluble matter (K2804), and then methanol was removed to obtain a yellow viscous substance.

This viscous substance is 1. According to the R spectrum, 920CIr
The epoxy absorption of L-1 disappeared and was replaced by 3300cIr.
Hydroxy absorption of L-1 appears, hydroxyl value = 805 (calculated value = 947), oxirane oxygen -0,1
Since it was 9%, it was confirmed to be the target product.

Synthesis Example 3 Synthesis of p-oxybenzoic acid glycidyl ether ester hydrate 64 g of p-oxybenzoic acid glycidyl ether ester
, 200 g of water and 1.7 g of concentrated sulfuric acid as catalyst,
This mixture was heated at 40-45℃ (maximum temperature 50℃) for about 5 hours.
The mixture was stirred and reacted.

The solution was initially cloudy, but as the reaction progressed, it changed to a homogeneous phase.

To complete the reaction, add 2 more times after changing to a homogeneous state.
Allowed time to react.

Thereafter, the mixture was neutralized with t-IJium hydroxide and dehydrated under reduced pressure to obtain a pale yellow transparent highly viscous material.

This viscous substance is 1. R, disappearance of epoxy absorption and appearance of hydroxyl absorption by spectrum, and hydroxyl value -68
6 (calculated value -719) and oxirane oxygen -0.31, confirming that it was the desired product.

Synthesis Example 4 Synthesis of diglycidyl adipate hydrate 25.8 g of diglycidyl adipate, 120 g of water, and 0.4 g of concentrated sulfuric acid as a catalyst were calculated, and this mixture was heated to 50'
The reaction was carried out at C for 10 hours.

The reaction solution changed into a homogeneous phase as the reaction progressed.

The mixture was neutralized with sodium hydroxide, dehydrated under reduced pressure, and the methanol-insoluble portion was removed to obtain a colorless transparent viscous substance.

This viscous substance is 1. R, disappearance of epoxy absorption and appearance of hydroxyl absorption by spectrum, and hydroxyl value -630
(calculated value -674) and oxirane oxygen = 0.06%, so it was confirmed that it was the desired product.

Synthesis Example 5 Synthesis of diglycidyl phthalate hydrate 32 g of diglycidyl phthalate 1 80 g of water and 50 g of dioxane were calculated, and this mixture was added with BF3.(
Et)201.5TrLl was added, and the mixture was stirred and reacted at 50°C for 11 hours.

The reaction solution changed from a heterogeneous phase to a transparent homogeneous phase as the reaction progressed.

The product was confirmed to be the desired product based on IR spectrum, hydroxyl value, and oxirane oxygen measurements.

The hydroxyl value was 633 (calculated value = 685), and the oxirane oxygen content was 0.18%.

Examples of the halogen-containing polymer 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,
Epichlorohydrin 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 Polymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer Polymer, Vinyl chloride Vinyl chloride = IJ Butene vinyl acetate terpolymer, Vinyl chloride immediate acrylate ester copolymer, Vinyl chloride-maleate ester copolymer, Vinyl chloride-methacrylate ester copolymer halogen-containing synthetic resins such as vinyl chloride-acrylonyl-IJ copolymer, internally plasticized polyvinyl chloride, or these halogen-containing resins and polyethylene, polypropylene,
α-olefin polymers with polybutene, poly-3-methylbutene, or polyolefins such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, and their copolymers, polystyrene, acrylic resins, styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-
Butadiene-styrene copolymer, acrylic ester-
Examples include butadiene-styrene copolymers, blends with methacrylic acid ester-butadiene-styrene copolymers, block copolymers, and graft copolymers.

The polymer composition of the present invention contains a phthalate plasticizer or other ester plasticizer, a polyester plasticizer, a phosphate plasticizer, an epoxy plasticizer, a chlorine plasticizer, or another plasticizer. It can be used as appropriate depending on the purpose.

Adding an antioxidant to the polymer composition of the present invention can increase the oxidative deterioration prevention properties of the polymer composition, so it can be used as appropriate depending on the purpose of use.

These antioxidants include phenolic antioxidants, phosphite antioxidants, amine antioxidants, sulfur-containing compounds, etc.
It is disclosed in Japanese Patent No. 78692.

If an ultraviolet absorber is added to the polymer composition 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 benzophenone, benzotriazole,
Salicylate series, substituted acrylonitrile series, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazine series, piperidine series, etc. are available, and are specifically disclosed in JP-A-49-78692. has been done.

Other materials may be added as necessary, such as pigments, fillers, foaming agents, antistatic agents, antifogging agents, plate-out prevention agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, antifungal agents, bactericidal agents, and metallurgical agents. Activators, photodegradants, nonmetallic stabilizers, boric acid esters, naourea derivatives, processing aids, mold release agents, reinforcing agents, etc. can be stored.

Next, a concrete explanation will be given using examples.

However, the invention is not limited to the following examples.

Example 1 In order to examine the effects of the composition of the present invention such as thermal stability, samples were prepared by calendering and hot pressing according to the following formulation, and the thermal stability by a heat aging tester, the transparency by hot pressing, and the Initial colorability was measured.

The results are shown in Table 1. Regarding the initial coloring, the yellowness was determined using a Hunter colorimeter according to the formula below and compared.

6〉, excellent 6-12. Good to somewhat good 12-15. Normally 15-20. Slightly inferior〉20. Poorly blended polyvinyl chloride resin di-2-enalhexyl phthalate Zn-octoate Ba-nonylfertostearic acid sample 100 parts by weight 50 parts by weight i, o parts by weight 1.0 parts by weight 0.5 parts by weight i, o Parts by weight Example 2 In order to examine the effects of the composition of the present invention on thermal stability, etc., a test similar to that of Example 1 was conducted using the following hard formulation.

The results are shown in Table 2 below. Blend> Polyvinyl chloride resin 100 parts by weight Ca-stearate Zn-stearate tetra C1 □ 15 mixed alkyl bisphenol A/diphosphite lubricant (stearyl citrate ester) Sample 1.0 parts by weight 1.0 0.5 0 .5 1, O Example 3 In order to examine the effects of the composition of the present invention on thermal stability, etc., a test was conducted in the same manner as in Example 1 using the following formulation.

The results are shown in Table 3 below. Blend> Polyvinyl chloride resin 1.00 parts by weight Epoxidized soybean oil 3.0 Ca-stearate Zn-stearate tetra C12-1. Mixed alkyl bisphenol A/diphosphite stearic acid sample 0.15 parts by weight 0.3 0.5 0.5 1.0 Example 4 Polyvinyl chloride-acrylonitrile-butadiene-snarene copolymer of the compound according to the present invention (ABS resin) In order to examine the effect of thermal stability on blended products, samples were prepared and tested using the same procedure as in Example 1 with the following formulation.

The results are shown in Table 4 below.

Good combination.

Polyvinyl chloride resin ABS resin Di-2-ethylhexyl phthalate Ba-nonyl ferrate Zn-octoate Epoxidized soybean oil sample 80 Part by weight 0 0 0.7 0.7 2.0 1.0 Example 5 The present invention In order to examine the combined effect of adding other additives to the composition, a test similar to Example 1 was conducted using the following formulation.

The results are shown in Table 5 below.

Blend> Polyvinyl chloride resin 100 parts by weight G2-
Ethylhexyl phthalate Epoxidized soybean oil Ca-benzoate Mg-stearate Zn-stearate Glycerin Triglycine ether hydrate Other additives (
Table 5) 48 Parts by weight 2.0〃 0.7〃 0.7〃 0.7〃 1, Q〃 0.3〃 Example 6 In order to examine the effects of the composition of the present invention on thermal stability, etc., the following Depending on the formulation, the mixture is kneaded on a mixing roll at 210°C for 3 minutes to prepare a plate-shaped sample.

This sample plate was sandwiched between chrome-plated steel plates and weighed 100 kg/
ff1. Pressed at 250°C for 5 minutes.

The condition of the obtained sheet was observed, and the results are shown in Table 6.

Blend> Polyvinyl fluoride resin 100 parts by weight Ca-
Stearate 0.1 Sample
l, Q tt Example 7 In order to examine the effects of the composition of the present invention on thermal stability, etc., a performance test was conducted in the same manner as in Example 1 using the following tin formulation.

The results are shown in Table 7. <Formulation> Polyvinyl chloride resin diocnaltin bis(bunamalate) Stearic acid sample (Table 7) 00 parts by weight 1.5 0.5 1.0 Also, talc, asbestos, calcium carbonate, clay,
The epoxy hydrate according to the present invention is added as a stabilizer to a polyvinyl chloride resin composition containing fillers such as titanium whitener and pigments such as aluminum powder, copper powder, and bronze powder. The composition used showed an excellent stabilizing effect.

Claims (1)

[Scope of Claims] 1. In the halogen-containing resin, based on 100 parts by weight of the resin, a) at least one metal salt selected from carboxylates of zinc, calcium, barium, or magnesium, ferulates, and alkyltin carboxylates; 0
．． 01 to 5 parts by weight and b) a hydrate of an epoxy compound having at least one ester bond or ether bond and at least two epoxy groups in the molecule, or having at least two epoxy groups in the molecule A stabilized halogen-containing resin composition containing 0.01 to 5 parts by weight of a hydrate of an aliphatic or alicyclic hydrocarbon.