JPS6144899B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilized chlorine-containing resin composition characterized by adding a novel low-toxicity or non-toxic stabilizer to the chlorine-containing resin. More specifically, the present invention provides a stabilized resin characterized by adding a low toxicity or non-toxic organometallic salt compound and a keto-aceto-nitrile compound represented by the general formula () below to a chlorine-containing resin. The present invention relates to a chlorine-containing resin composition. Chlorine-containing resins are subjected to various thermoforming processes depending on their purpose of use, but dehydrochlorination is likely to occur due to the influence of heat during such thermoforming processes. This causes discoloration and/or physical deterioration, and further causes deterioration of the color tone and physical properties of the processed product, resulting in a significant decrease in commercial value. Therefore, various stabilizers have been proposed for the purpose of preventing discoloration and deterioration caused by such heat. For example, (1) Cd−Ba, (2) Cd−Ba−Pb, (3) Cd−
Stable combination of Ba-Zn, (4) Ba-Zn, (5) Ca-Zn, or metal chains of (1) to (5) with organic phosphite, phenolic antioxidant, or epoxy compound, etc. It is also well known that agents have already been employed. However, when a stabilizer containing metal soaps as described in (1) to (3) above is added to the resin, it has an excellent effect of preventing discoloration and deterioration due to heat, etc., but such a stabilizer is Toxicity issues arise in hygiene and molded products. On the other hand, when a stabilizer containing metal stabilizers (4) to (5) is added to the resin,
Although there are relatively no problems in terms of hygiene and toxicity, the thermal stability during thermoforming processing is insufficient. Furthermore, various stabilizers have been researched and proposed for the purpose of supplementing this. For example, in Japanese Patent Publication No. 42-8786, non-toxic
Stabilizers made of Ca-Zn metal nitrates and ketoacetic acid compounds have been proposed, but there are problems with processability such as plate-out. The present applicant has also disclosed stabilizers consisting of the above-mentioned metal stabilizers and β-diketone compounds in (4) to (5) in Japanese Patent Publication No. 52-47948,
Publication No. 52-30858, Publication No. 52-126452 (Special Publication
57-9386). In addition, (4) to (5) above
JP-A-53-9847 discloses a stabilizer consisting of a metal complex salt and a metal complex salt of β-diketone. However, it cannot be said that a stabilizer consisting of such a low-toxicity or non-toxic metal compound and a β-diketone compound or a metal complex salt thereof has been able to provide a stabilizing effect that is sufficiently satisfactory for practical use.
In particular, it cannot be said that the technical problems in early to mid-term coloration prevention have been completely solved. Therefore, those skilled in the art would like to see further improvements. As a result of various studies to solve these technical problems, the present inventors have discovered a chlorine-containing resin with excellent stability that satisfactorily satisfies initial discoloration prevention properties, mid-term discoloration prevention properties, and long-term discoloration prevention properties. Found the composition. That is, the present invention provides at least one or more organic metal salts selected from barium, calcium, magnesium, strontium, lithium, potassium, sodium, zinc, or tin organometallic salts to 100 parts by weight of the chlorine-containing resin. , (b) General formula [Wherein, X represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an alkoxy group, an acyloxy group, a mercapto group, an amino group, or an amide group, and Y represents a hydrogen atom, an alkyl group, or a halogenated alkyl group. , aryl group or -
Acyl group represented by CO-R (where R is an alkyl group, a halogenated alkyl group, an aryl group,
0.001 to 5 parts by weight of a keto-acetonitrile compound represented by [representing a substituted aryl group, cycloalkyl group, aralkyl group or heterocyclic group] is added. A resin composition is provided. The organic metal salt (a) used in the present invention is generally called a metal soap, and the organic group constituting the metal salt has 6 to 6 carbon atoms.
Monocarboxylic and dicarboxylic acids of 22 saturated or unsaturated fatty acids, carbocyclic or heterocyclic carboxylic acids with 6 to 12 carbon atoms, hydroxy, alkoxy or oxocarboxylic acids with 2 to 10 carbon atoms For example, hexanoic acid, octanoic acid, 2-ethylhexylic acid, decanoic acid, isodecanoic acid, lauric acid, myristic acid, palmikenic acid, stearic acid, behenic acid, myristoleic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid. , linoleic acid, isostearic acid, 12-hydroxystearic acid, phenylstearic acid, aladinic acid, erucic acid and animal fatty acids, coconut oil fatty acid, tung oil fatty acid, soybean oil fatty acid, cottonseed oil fatty acid,
Tall oil fatty acids and benzoic acid, toluic acid, chlorobenzoic acid, P-t-butylbenzoic acid, xylic acid, ethylbenzoic acid, isopropylbenzoic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid, Hydroatropic acid, furic acid, thenic acid, nicotinic acid, isonicotinic acid, glycolic acid, glyceric acid, lactic acid, malic acid, tartaric acid, citric acid, acetoacetic acid, levulinic acid, salicylic acid, anisic acid, cyclohexanoic acid, or these carboxylic acids mixed acids. Furthermore, as other organic groups, phenols or alkylphenols having 6 to 24 carbon atoms are also useful, such as phenols,
Pyrocatechol, hydroquinone, pyrogallol,
Mention may be made of organic residues such as cresol, P-t-butylphenol, P-octylphenol, nonylphenol or dinonylphenol. Moreover, the tin compound may be represented by an alkyltin compound. For example, monomethyltin laurate, dimethyltin laurate, dibutyltin laurate, dioctyltin laurate, dibutyltin maleate polymer, dibutyltin maleate alkyl ester salt, dioctyltin maleate polymer, dioctyltin maleate alkyl ester salt, Monomethyltin thioglycolic acid alkyl ester salt, dimethyltin thioglycolic acid alkyl ester salt, dimethyltin thiopropionate, dibutyltin thioglycolic acid alkyl ester salt, dibutyltin thiopropionate, monooctyltin thioglycolic acid alkyl ester salt, These include dioctyltin thioglycolic acid alkyl ester salt and dioctyltin propionate. The organometallic salt compound bonded to these organic groups may be an acidic salt or a neutral salt, or may further be a basic salt bonded to equimolar or more of the metal. When such organometallic salt compounds are used in the present invention,
It may be used alone or in combination with other metal salts such as barium, calcium, magnesium, strontium, lithium, potassium, sodium or tin metal salts. In this case, the ratio of zinc salt to other metal salts is usually 1.0:0.1~10
The weight ratio is preferably 1.0:0.2 to 5.0. Furthermore, the above organometallic salt compound is used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the chlorine-containing resin.
5 parts by weight is added. Examples of the keto-acetonitrile compound represented by the general formula (2) used in the present invention include benzoylacetonitrile, methylbenzoylacetonitrile, octylbenzoylacetonitrile,
Allylbenzoylacetonitrile, trifluoromethylbenzoylacetonitrile, 2-chloroethyl-benzoylacetonitrile, 2-hydroxyethyl-benzoylacetonitrile, phenylbenzoylacetonitrile, benzylbenzoylacetonitrile, cinnamylbenzoylacetonitrile, phenacylbenzoylacetonitrile, 4
-chlorobenzoylacetonitrile, acetylbenzoylacetonitrile, octoylbenzoylacetonitrile, stearoylbenzoylacetonitrile, 2-acroylbenzoylacetonitrile, 4-chloro-acetylbenzoylacetonitrile, acetylanisoylacetonitrile, acetoacetyl-benzoylacetonitrile, malonylbis(benzoylacetonitrile), Fumaroylbis(benzoylacetonitrile), chloroacetylbenzoylacetonitrile, trifluoroacetylbenzoylacetonitrile, trifluoroacetoacetyl-benzoylacetonitrile, thiodipropionylbis(benzoylacetonitrile), dibenzoylacetonitrile, P-benzoylacetylbenzoyl-benzoylacetonitrile, terephthaloyl rubis (benzoylacetonitrile), phthaloylbis (benzoylacetonitrile), phenylacetylbenzoylacetonitrile, benzoylacetyl-benzoylacetonitrile, cinnamoylbenzoylacetonitrile, cyclopentanecarbonylbenzoylacetonitrile, cyclohexanecarbonylbenzoylacetonitrile, 1-cyclohexenecarbonyl-benzoylacetonitrile, 2- Examples include tenoylbenzoylacetonitrile, 2-furoylbenzoylacetonitrile, and nicotinoylbenzoylacetonitrile. The above
The keto-acetonitrile compound (b) is added in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, per 100 parts by weight of the chlorine-containing resin. However, the above (a)
The stabilizer having the essential constituents of (b) is one that is added to a chlorine-containing resin to exhibit excellent thermal stability, especially early to mid-term coloration prevention. In the present invention, in addition to the two components (a) to (b), a known stabilizer or stabilizing aid is used in combination to further improve thermal stabilization performance and processability. . Such useful stabilizers or stabilizing aids include phosphites such as trialkyl phosphites, triaryl phosphites, alkylaryl phosphites, trialkyl phosphites, bisphenol phosphites, polyhydric alcohol phosphites, and also alkyl phosphites. Acidic phosphites in which one or two of the organic residues such as , aryl or aralkyl are replaced by hydrogen atoms, such as triisooctylphosphite, triisodecylphosphite, tridecylphosphite, diisodecylmonophenylphosphite , tribenzyl phosphite, trinonylphenyl phosphite, hydrogenated 4,4'-isopropylidene diphenyl phosphite, 4,4'-isopropylidene diphenyl alkyl phosphite, and
These include diphenyl acid phosphite, diisodecyl acid phosphite, dibenzyl acid phosphite, and the like. In addition, examples of phenolic compounds include alkylated phenols, alkylated phenol esters, alkylated phenol ethers, alkylene or alkylidene bisphenols, polyalkylated phenols, and thiobisalkylated phenols, and typical compounds include butylated hydroxy Examples include toluene or 4,4'-thiobis(6-t-butyl-m-cresol), and thiodipropionic acid alkyl ester. Also, inorganic metal salt compounds, such as hydroxides of metals selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, barium, strontium, zinc, aluminum, indium, zirconium and tin;
oxides or carbonates, and also basic inorganic salts, such as phosphoric acid, phosphorous acid, silicic acid, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, or boric acid, and the above metals or chlorides or oxides of the metals. , hydroxides, or mixtures thereof, including calcium hydroxide, aluminum sulfate compounds, hydrotalcites, and zeolites. Examples of the epoxy compound include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, epoxycyclohexane derivatives, and epichlorohydrin derivatives. Other stabilizers or stabilizing aids such as pentaerythritol, dipentaerythritol, mannitol or sorbitol, as well as ester compounds of the polyol and fatty acids. Nitrogen-containing compounds such as β-aminocrotonic acid alkyl ester salt, 2-phenylindole or N.
N′-diphenylthiourea. Useful light stabilizers include benzophenones, benzotriazoles, salicylates, or substituted acrylonitrile compounds. In the present invention, chlorine-containing resins include polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-styrene copolymer, etc. Polymers, vinyl chloride-vinylidene chloride copolymers, chlorinated polyethylene, chlorinated polypropylene or copolymers of these with vinyl chloride, vinyl chloride-styrene-maleic anhydride ternary copolymers, and ethylene-vinyl acetate Copolymers, blends of acrylonitrile-butadiene-styrene copolymers, methacrylate ester-butadiene-styrene copolymers, etc. with polyvinyl chloride, block copolymers, graft copolymers, etc. can be mentioned. In the present invention, depending on the purpose of the molded product, for example, plasticizers, fillers, pigments, antistatic agents, antifogging agents, antiplate-out agents, lubricants, flame retardants, antifungal agents, blowing agents, crosslinking agents, etc. A reinforcing agent or a processing aid may be used in combination. The composition of the present invention is useful as a low-toxicity hard or semi-hard composition among the general molded articles of chlorine-containing resin compositions. Next, in order to specifically explain the present invention, the present invention will be disclosed in detail by way of Examples. However, the present invention is not limited to these Examples. Examples 1 to 3 and Comparative Example 1 In order to examine the thermal stabilization effect of the chlorine-containing resin composition to which the stabilizers (a) to (b) of the present invention were added, the following formulations were heated at a temperature of 180°C for 50 minutes. A uniform sheet with a thickness of 0.5 mm was created by roll milling for 1 minute. The colorability and transparency of this sheet were observed. Next, the sheet was tested by the method described below. Test 1 Cut a 20 x 40 mm test piece from the sheet,
The material was placed in a gear oven aging tester heated to a certain temperature for a certain period of time, and tests were conducted to determine coloration due to thermal deterioration and time until black decomposition. The results are shown in Table 1. Test 2 Cut a 50 x 80 mm test piece from the sheet,
Stack 10 sheets of this and use a press molding machine at 185℃ - 100Kg/
It was molded for a certain period of time under conditions of cm ² and tested for coloration and transparency due to thermal deterioration during pressing. The results are also listed in Table 1. <Composition> Vinyl chloride resin (Zeon 103EP-8)*
100 parts by weight Epoxidized soybean oil 3 Barium stearate 0.8 Barium nonyl phenolate 0.8 Zinc stearate 0.4 Keto-acetonitrile compounds (Table 1) *Nippon Zeon products

[Table] Examples 4 to 16 and Comparative Examples 2 to 6 In this example, in order to see the stabilizing effect of the plasticized chlorine-containing resin composition to which the stabilizers (a) to (b) of the present invention were added, the following A sheet of the formulation was prepared under the same conditions as in Example 1, and tested using the same test methods as in Example 1 (Tests 1 and 2).The results are shown in Tables 2 and 3. <Formulation> Vinyl chloride resin (Zeon 103EP) 100 parts by weight Dioctyl phthalate 48 Epoxidized soybean oil 2 Barium stearate 0.4 Barium nonyl phenolate 0.4 Zinc stearate 0.4 Diphenylisodecyl phosphite 0.5 Keto-acetate -Nitrile compounds (Tables 2 and 3) Other stabilizers (Table 3)

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[Table] Examples 17 to 22 and Comparative Example 7 In this example, the following materials were prepared by adding (a) to (b) of the present invention, a white pigment (titanium oxide), and a filler (heavy calcium carbonate). A chlorine-containing resin composition,
A sheet was prepared under the same conditions as in Example 1, and tested using the same test method as in Example 1 (Tests 1 and 2, except for transparency). The results are shown in Table 4. <Composition> Vinyl chloride resin (Zeon 103EP) 100 parts by weight Dioctyl phthalate 48 Epoxidized soybean oil 2 Titanium oxide (anatase type) 10 Calcium carbonate 20 Zinc stearate 0.8 Barium stearate 0.8 Barium nonyl phenolate 0.8 〃 Diphenylisodecyl phosphite 0.5 〃 Keto-acetonitrile compound (Table 4)

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Claims (1)

[Scope of Claims] 1. Based on 100 parts by weight of the chlorine-containing resin, as a stabilizer, (a) at least one type of organic metal salt selected from barium, calcium, magnesium, strontium, lithium, potassium, sodium, zinc, or tin; or two or more types, and (b) general formula [In the formula, X represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an alkoxy group, an acyloxy group, a mercapto group, an amino group, or an amide group, and Y represents a hydrogen atom, an alkyl group, a halogenated alkyl group, An aryl group or an acyl group represented by -CO-R (where R represents an alkyl group, a halogenated alkyl group, an aryl group, a substituted aryl group, a cycloalkyl group, an aralkyl group, or a heterocyclic group)] Keto-acetonitrile compound
0.001 to 5 parts by weight of a stabilized chlorine-containing resin composition.