JP4351026B2 - Stabilizer composition for chlorine-containing resin and chlorine-containing resin composition - Google Patents

Description

  The present invention relates to a stabilizer composition for a chlorine-containing resin and a chlorine-containing resin composition containing the same.

It is known that a chlorine-containing resin gradually becomes colored, blackened, or embrittled by heating and light irradiation. This is because the chlorine-containing resin dehydrochlorinates with the energy of heat and light to form a polyene structure that is a chromophore (coloring), and further, the main chain is broken or crosslinked (physical property change, embrittlement). is there.
In order to prevent such deterioration of the chlorine-containing resin, a stabilizer is used.

  Conventionally, lead stabilizers such as tribasic lead sulfate, dibasic lead stearate, and lead stearate have been used as stabilizers for chlorine-containing resin compositions. These lead-based stabilizers are excellent heat stabilizers and have advantages such as being relatively inexpensive. However, lead-based stabilizers are highly toxic, and the use of lead compounds is gradually decreasing due to regulations such as the elution regulation of lead from water pipes under the Water Supply Law and the regulation of lead emissions into the environment. Development is urgently needed.

  It is a well-known fact that Ca—Zn stabilizers, Ba—Zn stabilizers, organotin stabilizers such as octyl tin, and the like are used as alternative candidates for lead stabilizers.

  Recently, in addition to these, various proposals have been made to use zeolite as a stabilizer for chlorine-containing resins, and among the techniques using these zeolites, a stabilizer containing zinc-substituted zeolite as an active ingredient is also proposed. (For example, refer to Patent Documents 1 to 13).

  However, as described above, there are many proposals regarding the use of a metal ion-substituted product of zeolite as a heat stabilizer for a chlorine-containing resin, but there are not so many examples of practical use. The reason for this is that when zeolite is added to the resin, the phenomenon of foaming during resin processing is likely to occur, and therefore there remains the problem of reducing the commercial value and the problem of poor long-term thermal stability.

  On the other hand, a stabilizer for a chlorine-containing resin containing hydrocalumite as an active ingredient has also been proposed (see, for example, Patent Document 14). It has not received much attention as an agent.

JP-A-55-164236 JP-A 56-120745 JP 56-14542 A JP 56-72038 A JP 56-43341 A JP-A 56-120745 JP 57-28145 A JP 57-25346 A Japanese Patent Laid-Open No. 62-112646 Japanese Patent Laid-Open No. 1-2221447 JP-A-6-240082 Japanese Patent Laid-Open No. 8-12834 JP-A-10-310418 JP-A-8-127687

  Accordingly, an object of the present invention is to provide a chlorine-containing resin stabilizer composition for chlorine-containing resins, which can impart long-term thermal stability, has no initial coloration, and can improve the foaming phenomenon during resin processing. It is providing the chlorine containing resin composition containing this.

  As a result of intensive studies in such circumstances, the present inventors have found that when an aluminosilicate substituted with a specific metal ion and a material containing a specific hydrocalumite are used as a stabilizer for a chlorine-containing resin, the aluminosilicate is used. Synergistic effects of silicate and hydrocalumite improve the shortcomings of conventional chlorine-containing resin thermal stabilizers, improve long-term thermal stability, improve initial colorability, and improve foaming during resin processing The present invention has been found out to bring about outstanding effects.

［式中、Ｘは１価または２価のアニオンであり、ｍはアニオンの価数を表し、ｎ≦20を表す］で示されるハイドロカルマイトを有効成分として含有することを特徴とする塩素含有樹脂用安定剤組成物である。 That is, the first invention to be provided by the present invention is an aluminosilicate substituted with Zn ions and the following general formula (1):

[Wherein X represents a monovalent or divalent anion, m represents the valence of the anion, and represents n ≦ 20], and contains a hydrocalumite as an active ingredient. It is a stabilizer composition for resins.

  A second invention to be provided by the present invention is a chlorine-containing resin composition characterized by containing the stabilizer composition for chlorine-containing resin of the first invention.

  According to the stabilizer composition for chlorine-containing resin of the present invention, long-term thermal stability is imparted to the chlorine-containing resin, there is no initial coloration, and the foaming phenomenon during resin processing can be improved.

Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.
The stabilizer composition for chlorine-containing resins of the present invention comprises an aluminosilicate substituted with Zn ions and hydrocalumite represented by the general formula (1) as active ingredients.

  The aluminosilicate substituted with Zn ion as the first component is a zinc-substituted zeolite in which cations such as sodium ion and potassium ion in the zeolite structure are ion-exchanged with zinc ions. Examples of the aluminosilicate before ion exchange include synthetic zeolites such as A-type zeolite and X-type zeolite, natural zeolites such as mordenite, analcite, sodalite, clinoptilolite, erionite, and chabasite. Among them, the zinc-substituted zeolite obtained by exchanging the cation of A-type zeolite or X-type zeolite with Zn ion has a high synergistic effect with hydrocalumite, which will be described later. This is particularly preferable in that the chlorine-containing resin is not initially colored and the foaming phenomenon during resin processing can be improved.

  In the present invention, the aluminosilicate substituted with Zn ions preferably has an average particle size of 6 μm or less, preferably 1 to 4 μm, which is obtained from a laser diffraction method, because the resin dispersibility becomes good.

  In the present invention, the aluminosilicate substituted with Zn ions may contain 6.6% by weight or more, particularly 8.7 to 20% by weight, as a ZnO, in a chlorine-containing resin with a small addition amount. It is particularly preferable in that long-term thermal stability is imparted, there is no initial coloring, and the foaming phenomenon during resin processing can be improved.

  Furthermore, in the present invention, the aluminosilicate substituted with Zn ions has the above-mentioned properties, and free alkali is removed as much as possible. At least the equilibrium pH is 8.5 or less, preferably The use of 7.0 to 8.2 is particularly preferred in that the synergistic effect with hydrocalumite described later is high, and in particular, the initial coloring of the chlorine-containing resin can be effectively suppressed. The equilibrium pH refers to the pH of the supernatant after 10 g of the aluminosilicate is dispersed in 100 ml of pure water and stirred for 1 hour at room temperature (25 ° C.).

Such an aluminosilicate substituted with Zn ions can be produced by using a known method. For example, an aluminosilicate substituted with Zn ions having the above characteristics from A-type zeolite or X-type zeolite. Is obtained by the general formula: (1 ± 0.2) Na ₂ O.Al ₂ O _3. (1.9 ± 0.5) SiO _2. (0.5-6) H ₂ O Sodium A-type zeolite or general formula; (1 ± 0.2) Na ₂ O.Al ₂ O _3. (2.5 ± 0.5) SiO _2. (6.5 ± 0.5) H ₂ O A slurry in which 100 parts by weight of sodium X-type zeolite is dispersed in 500 to 2000 parts by weight of water is prepared, and then an aqueous solution containing 6.7 to 25 parts by weight of zinc compounds such as zinc chloride and zinc sulfate as ZnO is prepared. Add to the slurry and stir at 20-80 ° C. with stirring. It can be easily obtained by sufficiently performing an ion exchange reaction between Na ions and Zn ions therein, followed by solid-liquid separation, drying or / and calcination, and pulverization and classification as desired (Japanese Patent Laid-Open No. 57-57). No. 25346, Japanese Patent Publication No. 61-17767).

  In the aluminosilicate substituted with Zn ions, the crystal water itself does not pose any problem at the molding temperature of the chlorine-containing resin. However, the water adhering to the aluminosilicate is the molding process of the chlorine-containing resin. Since it is likely to be one of the causes of foaming, it is preferable that the drying or baking is sufficiently performed to the extent that moisture does not evaporate in the vicinity of the adhering water or the molding processing temperature. In this case, drying or baking may be performed at 100 ° C. or higher, preferably 110 to 500 ° C. for 0.5 hour or longer, preferably 1 to 24 hours.

In the present invention, the second component hydrocalumite is a typical inorganic anion exchanger represented by the general formula (1), wherein X represents a monovalent or divalent anion, and other anions When present, it has anion exchange properties.
Hydrocalumite varies depending on the production method and the object, but the molar ratio of Ca / Al is almost 2, and n indicating the amount of crystal water is often up to 15, but the present invention includes up to 20. sell.
Examples of X representing an anion include OH ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , NO ₂ ⁻ , H ₂ PO ₂ ⁻ , HCO ₃ ⁻ , HPO ₃ ²⁻ , HPO ₄ ²⁻ , CH ₃ COO ⁻ , Cl ^−. , [(CHCOO) ₂ ] ²⁻ , [C ₆ H ₄ (COO) ₂ ] ²⁻ , CO ₃ ²⁻ , SO ₄ ^2−, or the like.

Typical examples thereof include the following compounds.

In the present invention, the hydrocalumite represented by the general formula (1) is particularly preferable when X in the formula is CO ₃ ^{2− because the} long-term thermal stability can be improved.
In the present invention, the hydrocalumite preferably has an average particle size determined by a laser diffraction method of 20 μm or less, and preferably 1 to 10 μm, since the resin dispersibility becomes good.

As a method for producing the hydrocalumite, a known production method may be followed. For example, a method of crystallizing using a raw material comprising sodium aluminate, a soluble calcium salt and / or alkali metal salt, and slaked lime ( JP-A-07-33430), or a method in which a CaO—Al ₂ O ₃ -based compound, a soluble calcium salt and / or slaked lime are reacted in a liquid and then crystallized (JP-A-07-33431). What is obtained is industrially advantageous, but is not limited thereto.

  Further, in the present invention, the hydrocalumite is a fatty acid such as stearic acid or oil acid or a metal salt thereof, silicon hydroxide or silicon oxide or silicon hydroxide and silicon for the purpose of improving resin dispersibility. It may be surface-treated with an oxide or the like.

  In the stabilizer composition for chlorine-containing resin of the present invention, the blending ratio of the aluminosilicate substituted with Zn ion of the first component and the hydrocalumite of the second component depends on the type of chlorine-containing resin used. In many cases, the blending ratio of the aluminosilicate substituted with Zn ions and the hydrocalumite is 90:10 to 10:90, preferably 30:70 to 70:30. Outside this range, initial coloration is conspicuous in the thermal stability test, and in particular, the long-term thermal stability of the chlorine-containing resin is deteriorated, and so-called “zinc burn” tends to occur, which is not preferable.

  The stabilizer composition for chlorine-containing resin of the present invention can be a useful stabilizer by itself by containing the first component and the second component. However, depending on the use and type of the resin, the stabilizer composition may be used. Various physical properties such as thermal stability of the chlorine-containing resin can be improved more effectively by adding a stabilizing aid as the third component in an addition amount within a range not impairing the effects of the invention. Examples of such stabilizing aids include oxides and hydroxides containing one or more metals selected from lithium, potassium, sodium, calcium, barium, magnesium, strontium, zinc, tin, cesium, and aluminum. , Inorganic salts such as chlorates, perchlorates, hypochlorites, silicates, carbonates, phosphates, hypophosphites, nitrites, sulfates, their complex salts and basic salts, Organic salts containing these metals, β-diketones, polyhydric alcohols, epoxy compounds, organic phosphites, sulfonyl compounds, N-containing non-metal stabilizers, and the like, these stabilizing aids are It can be used by 1 type (s) or 2 or more types.

（式中、Ａ¹はＣＯ₃ ^2-、ＳＯ₄ ^2-、ＯＨ^-、ＣｌＯ₄ ^-、ＮＯ₃ ^-から選ばれる少なくと１種以上アニオンを表し、ａは０＜ａ、ｂは２ａ≦ｂ、ｔは０＜ｔを示す。）、又は、下記一般式（１０）

（式中、Ｍ₁ はＺｎ、Ｓｒ、Ｂａ及びＣａの少なくとも１種以上の２価金属元素、Ｍ₂ はＡｌ及びＦｅの少なくとも１種以上の３価金属元素、Ａ¹はＣＯ₃ ^2-、ＳＯ₄ ^2-、ＯＨ^-、ＣｌＯ₄ ^-、ＮＯ₃ ^-から選ばれる少なくと１種以上アニオンを表し、ｘは、０＜ｘ≦０．５、ｚは０≦ｚ＜０，５、０．５≦ｙ＋ｚ＜１、０≦ｍ＜２を示す。）で表されるハイドロタルサイト類、又は下記一般式（１１）

（式中、ＸはＣＯ₃ ^2-、ＳＯ₄ ^2-、ＯＨ^-、ＣｌＯ₄ ^-、ＮＯ₃ ^-から選ばれる少なくと１種以上アニオンを表し、ｎはアニオンＸの価数であり、ｍは３以下の数を示す。）で表されるリチウムアルミニウム複合酸化物の無機アニオン交換体が挙げられる。 As the complex salt containing the metal, for example, the following general formula (9)

(In the formula, A ¹ represents at least one anion selected from CO ₃ ²⁻ , SO ₄ ²⁻ , OH ⁻ , ClO ₄ ⁻ and NO ₃ ⁻ , where a is 0 <a and b is 2a ≦ b. , T represents 0 <t), or the following general formula (10)

(Wherein M ₁ is at least one divalent metal element of Zn, Sr, Ba and Ca, M ₂ is at least one trivalent metal element of Al and Fe, A ¹ is CO ₃ ²⁻ , Represents at least one anion selected from SO ₄ ²⁻ , OH ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , x is 0 <x ≦ 0.5, z is 0 ≦ z <0,5, 0. 5 ≦ y + z <1, 0 ≦ m <2)), or the following general formula (11)

(Wherein X represents at least one anion selected from CO ₃ ²⁻ , SO ₄ ²⁻ , OH ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , n is the valence of anion X, and m is And an inorganic anion exchanger of a lithium aluminum composite oxide represented by the following formula:

  Examples of the organic acid salt include carboxylic acid metal salts, metal salts of phenols, and organic phosphate metal salts.

  Examples of the carboxylic acid metal salt include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, neodecanoic acid, capric acid, undecanoic acid, lauric acid, and tridecane. Acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5- Di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N, N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, p-tertiary octylsalicylic acid, elaidic acid, oleic acid, li Monovalent carboxylic acids such as oxalic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, octyl mercaptopropionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Divalent carboxylic acids such as sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, thiodipropionic acid Acids or their monoesters or monoamide compounds; di- or triester compounds of trivalent or tetravalent carboxylic acids such as butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, merophanic acid, pyromellitic acid, etc. Organic mosquito Metal salts of Bonn acid.

  Examples of the metal salts of the phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol. , Metals such as isooctylphenol, 2-ethylhexylphenol, tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisofuxylphenol, methyl tertiary octylphenol Salt.

  Examples of the organic phosphoric acid metal salt include mono- or dioctyl phosphoric acid, mono- or dododecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, and phosphonic acid. Examples thereof include metal salts such as stearyl esters.

  The metal salts of the above carboxylic acids, phenols and organophosphoric acids are acidic, neutral salts, basic salts, or overbased complexes in which a part or all of the base of the basic salt is neutralized with carbonic acid. There may be.

  Examples of the β-diketones include acetylacetone, dehydroacetic acid, benzoylacetone, dibenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, ethyl acetoacetate, and the like. These are metal salts containing the above-described metals. There may be.

  Examples of the polyhydric alcohols include pentaerythritol, dipentaerythritol, sorbitol, mannitol, trimethylolpropane, ditrimethylolpropane, pentaerythritol or stearic acid partial ester of dipentaerythritol, bis (dipentaerythritol) adipate. Glycerin, diglycerin, tris (2-hydroxyethyl) isocyanurate, polyethylene glycol, polyvinyl alcohol and the like.

  Examples of the epoxy compound include bisphenol type and novolak type epoxy resins, epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized safflower. Oil, epoxidized tall oil fatty acid octyl, epoxidized linseed oil fatty acid butyl, epoxy methyl stearate, -butyl, -2-ethylhexyl or -stearyl, tris (epoxypropyl) isocyanurate, 3- (2-xenoxy) -1, 2-epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarbo Shireto, bis (3,4-epoxycyclohexyl) adipate, and the like.

  Examples of the organic phosphites include diphenyl decyl phosphite, triphenyl phosphite, tris-nonyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, tris (dinonyl phenyl) phosphite, tri Lauryltrithiophosphite, trilaurylphosphite, bis (neopentylglycol) -1,4-cyclohexanedimethylphosphite, distearylpentaerythritol diphosphite, diisodecylpentaerythritol diphosphite, tris (lauryl-2-thioethyl) phosphite Tetratridecyl-1,1,3-tris (2'-methyl-5'-tert-butyl-4'-oxyphenyl) butanediphosphite, tetra (C12-C15 mixed) Alkyl) 4,4'-isopropylidenediphenyl phosphite, tris (4-oxy-2,5-di-tert-butylphenyl) phosphite, tris (4-oxy-3,5-di-tert-butylphenyl) phosphite, 2-ethylhexyl diphenyl phosphite, tris (mono- and di-mixed nonyl phenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenyl polyphosphite, diphenyl bis [4,4'-n-butylidene bis 3-butyl-5-methylphenol)] thiodiethanol diphosphite, bis (octylphenyl) bis [4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol)]-1,6- Hexanediol diphosphite, phenyl-4,4'-isopropylidenediphenol pentaerythritol Diphosphite, phenyl diisodecyl phosphite, tetratridecyl-4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, tris (2,4-di-tert-butylphenyl) phosphite , Tristearyl phosphite, octyl diphenyl phosphite, diphenyl tridecyl phosphite, phenyl di (tridecyl) phosphite, tris (2-cyclohexylphenyl) phosphite, ditridecyl di (2-cyclohexyl phenyl), hydrogenated bisphenol A. Diphosphite, di (2,4-di-tert-butylphenyl) cyclohexyl phosphite, 2,4-di-tert-butylphenyl diisodecyl phosphite, tris (butoxyethoxyethyl) phosphite, poly-4,4'-isopropyl Dendiphenyl neodol 25 alcohol phosphite, diphenyl acid phosphite, bis (2-cyclohexylphenyl) acid phosphite, bis (2,4-di-tert-butylphenyl) acid phosphite, bis (nonyl phenyl) acid phosphite , Dibenzyl acid phosphite, polydipropylene glycol phenyl phosphite, 4,4'-isopropylidenediphenyl alkyl phosphite, and the like. These organic phosphites are metal salts containing the above-mentioned metals. May be.

  Examples of the sulfonyl compound include 4-chlorosulfonylbenzoic acid, 3,5-dichloro-2-hydroxybenzenesulfonyl chloride, 3-fluorosulfonylbenzenesulfonyl chloride, α-toluenesulfonyl chloride, 4,4′-methylenebis ( Benzenesulfonyl chloride), O-benzenesulfonyl chloride, m-benzenesulfonyl chloride, 4,4'-methylenebisbenzenesulfonyl chloride, 4,4'-biphenyldisulfonyl chloride, chloromethylsulfonyl chloride, 3-chloropropanesulfonyl chloride, trichloro Methanesulfonyl chloride, 4-sulfamoyl benzoic acid, 4-chloro-3-sulfamoyl benzoic acid, 4-aminosulfoni -1-hydroxy-2-naphthoic acid, p-toluenesulfonyl-N-diethylamide, α-N-tosyl-L-arginine, N ′-(4,5-dimethyloxazol-2-yl) sulfanilamide N '-(2-thiazolyl) sulfanilamide, dansyl-L-leucine, formamidine sulfinic acid, and the like.

  Examples of the N-containing nonmetal stabilizer include urea, thiourea, guanidine, amine, amino acid, thiazole, imidazole, amide, and imide derivatives. Furthermore, as urea derivatives, in addition to urea, mono or dialkyl ureas such as N, N-distearyl urea, N, N-bis (carboethoxyisopropenyl) urea, aminoureas such as semicarbazide, and aryls such as monophenylurea Examples thereof include urea, substituted phenylureas such as P-phenethylurea, and acylureas such as monoureido and diureido. Further, acyl ureas are preferably cyclic, and these include parapanic acid, parbituric acid, dialuric acid, alloxan, uracil, hydantoin, 5-methylhydantoin and the like. Examples of thiourea derivatives include monophenylthiourea, N, N'-biphenylthiourea, O-tolylthiourea, N, N'-di-O-tolylthiourea, diphenylbisthiourea, diphenyl-P- in addition to thiourea. Examples thereof include phenylene thiourea, diphenyl-m-phenylene dithiourea, and diphenyl thiocarbazone. Examples of guanidine derivatives include cyanoguanidine and O-tolylguanidine in addition to guanidine. Examples of amine derivatives include α- or β-naphthylamine, phenylene or naphthylenediamine, phenyl β-naphthylamine, aldol-α-naphthylamine, and further diethylenetriamine, triethylenetetramine, hexamethylenetetramine, α-phenylindole. Melamine, melamine isocyanate, guanidine and the like. Examples of amino acid derivatives include aminocrotonic acid alkyl or aryl esters such as β-ethylaminocrotonate 1,3-butanediolbis (aminocrotonate), hydrazone, and the like. Examples of thiazole derivatives include thiazole and dibenzothiazole sulfide, and examples of imidazole derivatives include imidazole and 2-mercaptobenzimidazole. Examples of amide or imide derivatives include succinimide, glutarimide, phthalimide, O-sulfobenzimide, N-phenyl-β-mercaptopropionamide, nitrilotriacetic acid trialkylamide or anilide, methyl-3-aminophenylsulfone, 4 , 4'-diaminodiphenylsulfone, S-triazine compound, pyrimidine compound, purine compound, formaldehyde-phenol-methylamine condensate, substituted amine-dibasic acid condensate, ethanolamine-unsaturated acid condensate, Examples include melamine-formal condensate and urea-formal resin.

  As the stabilizing aid for the third component, those having a solid property may be those having an average particle size of 20 μm or less, preferably 1 to 10 μm, which is obtained from the laser diffraction method in consideration of resin dispersibility. Particularly preferred.

  In addition, the stabilizer composition for chlorine-containing resins according to the present invention may contain a known additive blended in a chlorine-containing resin described later as a third component.

  The stabilizer composition for chlorine-containing resin of the present invention comprises an aluminosilicate substituted with Zn ion of the first component, hydrocalumite of the second component, and stabilization of a third component added as necessary. Auxiliaries may be used separately added to the chlorine-containing resin. The aluminosilicate substituted with Zn ions of the first component, the hydrocalumite of the second component, and a third component added if necessary. You may add and use to a chlorine containing resin as a uniform mixture of the component stabilization aid. When preparing this homogeneous mixture, an aluminosilicate substituted with Zn ions of the first component, a hydrocalumite of the second component, and a stabilizing aid for the third component added as necessary. A predetermined amount is mixed, and it is preferably prepared by a dry method using mechanical means in which a strong shearing force acts. In the dry method, apparatuses such as a high speed mixer, a super mixer, a turbo sphere mixer, a Henschel mixer, a nauter mixer, and a ribbon blender can be used. These uniform blending operations are not limited to the illustrated mechanical means. If desired, the particle size may be adjusted by grinding with a jet mill or the like.

The chlorine-containing resin composition according to the present invention contains the stabilizer composition.
The amount of the stabilizer composition depends on the type of the chlorine-containing resin composition to be used, but in many cases, it is 1 to 10 parts by weight, preferably 1 to 5 parts by weight with respect to 100 parts by weight of the chlorine-containing resin. is there.
The chlorine-containing resin used in the present invention is not particularly limited in its shape, size, components, properties, manufacturing method, molding method, etc., as long as it contains chlorine element in the resin. For example, vinyl chloride homopolymer produced by known methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or vinyl chloride and ethylene, propylene, styrene, vinyl acetate, isobutylene, (meth) acrylic One or more copolymers selected from acid esters, maleic anhydride, maleic esters, phenylmaleimide, cyclohexylmaleimide, acrylonitrile, butadiene, vinylidene chloride, various vinyl ethers, polyvinylidene chloride, polyvinyl bromide, chlorinated poly Examples include vinyl chloride, polyvinylidene chloride, chlorinated polyethylene, graft polymer of ethylene / vinyl acetate copolymer and vinyl chloride, and graft polymer of urethane resin having unsaturated group and vinyl chloride. And mixtures of other thermoplastics

  In addition, the chlorine-containing resin composition of the present invention further contains known additives that are usually blended in chlorine-containing resins, such as plasticizers, ultraviolet inhibitors, fillers, crosslinking agents, antistatic agents, antifogging agents, Plate-out prevention agent, surface treatment agent, lubricant, flame retardant, pigment, processing aid, antioxidant, light stabilizer, foaming agent, fluorescent agent, bactericidal agent, mold release agent, non-metal stabilizer, processing aid, A coupling agent, a reinforcing agent, an organic chelator, a surfactant, an antiblocking agent, and the like can be used in combination, and the blending amount thereof may be a conventionally known addition amount.

  The method for producing the vinyl chloride resin composition of the present invention is not particularly limited, and the chlorine-containing resin stabilizer composition of the present invention and the known additive blended as necessary are directly added to the resin and mixed. Can be used. In addition, as described above, the stabilizer composition for chlorine-containing resin of the present invention is a chlorine-containing resin obtained by uniformly mixing the first component, the second component, and the third component added as necessary. The first component, the second component, and the third component added as necessary may be individually added to the chlorine-containing resin.

  Moreover, shaping | molding of the chlorine containing resin composition of this invention is not specifically limited, It can carry out by a well-known shaping | molding method. For example, T-die extrusion molding, profile extrusion molding, injection molding, calendar molding, or the like can be used.

  The chlorine-containing resin composition of the present invention is, for example, various household items such as raincoats, umbrellas, rain pants, rain boots, hats, various keyboards, laminates, handbags, wallets, stationery and other sheet processing products, sandal bands, slippers, etc. Footwear products, belts, upholstery products such as cushion floors, toys such as dolls and floats, leather products for vehicles, furniture, bags, clothing, etc., extruded products such as gas pipes, hoses and tubes, machines Parts, watch bands, packing materials, wall materials, floor materials, window frames, wallpaper and other building materials, automotive interior materials, wire covering materials, agricultural materials, food packaging materials, paints, hoses, pipes, sheets, toys, etc. However, the present invention is not particularly limited thereto, and can be used for any use of conventional chlorine-containing resins.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
<Preparation of aluminosilicate substituted with Zn ion>
Crystalline type A sodium zeolite, the _{formula; Na 2 O · Al 2 O} 3 · 2SiO 2 · 4.5H 2 O ( Nippon Chemical Industrial Co., Ltd., trade name; Zeosuta) was dispersed 1000g of pure water 5000ml A slurry was prepared. On the other hand, an aqueous zinc nitrate solution in which 568 g of zinc nitrate (Zn (NO ₃ ) ₂ .H ₂ O) was dissolved in 5000 ml of water was prepared, and this aqueous zinc nitrite solution was added to the slurry with stirring, and the mixture was stirred at 50 ° C. for 3 hours. After stirring, the mixture was allowed to stand for one day and night, and separated by filtration to recover zeolite. Next, 1031 g of the recovered zeolite was washed with 5000 ml of pure water, then dried at 120 ° C. for 10 hours, and then pulverized to prepare an aluminosilicate sample substituted with Zn ions.
Table 1 shows various physical properties of the aluminosilicate substituted with Zn ions (hereinafter abbreviated as “zinc-substituted A-type zeolite”).
The contents of ZnO, Na ₂ O, Al ₂ O ₃ and SiO ₂ were determined by ICP analysis, and the H ₂ O content was a weight-substituted W ₀ zinc-substituted A-type zeolite sample at 800 ° C. for 1 hour in a heating furnace. The weight W ₁ decreased when the heat treatment was performed was obtained, and the value obtained by dividing W ₁ by W ₀ was defined as the H ₂ O content. The average particle size is determined by laser diffraction, and the equilibrium pH is measured by measuring the pH of the supernatant liquid with a pH meter after 10 g of zinc-substituted A-type zeolite is dispersed in 100 ml of pure water and stirred for 1 hour at room temperature (25 ° C.). Asked.

<Preparation of hydrocalumite>
Hydrocalumite sample A (nitrite hydrocalumite);
Water was added to 10 kg of sodium aluminate of Na ₂ O: 19 wt% and Al ₂ O ₃ : 20 wt% to make 100 kg (solution A). Water was added to 4.35 kg of slaked lime and 2.94 kg of calcium nitrite monohydrate to make 100 kg (Liquid B).
Subsequently, when the liquid B was added to the liquid A at room temperature with an injection pump for about 1 hour, a gel-like precipitate was formed. After completion of the addition, the slurry was heated to 60 ° C. and crystallized at normal pressure for 4 hours. The obtained precipitate was filtered and washed by a conventional method and then dried to obtain 12 kg of a white solid. The obtained white powder was pulverized to obtain a white powder of 150 mesh or less.
Sample A is X-ray diffraction, infrared absorption spectrum measurement, TG-DTA measurement and chemical composition analysis. Nitrous acid type hydrocalumite [3CaO ・ Al ₂ O ₃・ Ca (NO ₂ ) ₂・ 10H ₂ O] It was confirmed that
The average particle size determined by laser diffraction analysis was 9.2 μm.

-Hydrocalumite sample B (carbonated hydrocalumite);
59.28 g of Ca (OH) ₂ was dispersed in 1000 ml of ion-exchanged water to prepare a slaked lime slurry (C solution).
40.40 g of NaAlO ₂ · 0.5 NaOH was dissolved in 600 ml of ion-exchanged water (solution D).
15.00 g of NaHCO ₃ was dissolved in 200 ml of ion exchange water (solution E).
While stirring the liquid C, the entire amount of the liquid D was added to and mixed with the liquid C in about 1 minute and stirred. Next, the entire amount of solution E was added to the solution in about 1 minute, and the mixture was stirred for about 15 minutes. While stirring the resulting slurry, the temperature was raised to about 80 ° C., and the reaction was carried out for 6 hours. After completion of the reaction, the reaction mixture was cooled to 40 ° C. and then filtered with suction. The filter cake was put into a juicer mixer, 1000 ml of ion exchange water and 1 ml of oleic acid were added, and then mixed for 15 minutes. After completion of mixing, the slurry was subjected to suction filtration, and then dried and pulverized.
Sample B was found to be carbonated hydrocalumite [3CaO · Al ₂ O ₃ · CaCO ₃ · 10H ₂ O] by X-ray diffraction, infrared absorption spectrum measurement, TG-DTA measurement and chemical composition analysis. It was.
The average particle size determined by laser diffraction analysis was 3.5 μm.

Examples 1-4 and Comparative Examples 1-7
The compounds shown in Tables 3 to 4 below were kneaded on a hot roll at 160 ° C. for 4 minutes and 30 seconds, and then peeled off from the sheet to prepare a sheet having a thickness of 1 mm. The stabilizers used in the comparative examples were those having various physical properties shown in Table 3. The presence or absence of foaming during molding was also observed visually, and the results are shown in Table 7 below.

注）塩化ビニル樹脂（新第一塩ビ（株） ＺＥＳＴｐｖｃ1000Z）

Note) Vinyl chloride resin (New Daiichi PVC Co., Ltd. ZESTpvc1000Z)

注）塩化ビニル樹脂（新第一塩ビ（株） ＺＥＳＴｐｖｃ1000Z）、なお、比較例で使用した安定剤の亜鉛置換Ａ型ゼオライトは実施例１〜４と同じものを使用した。

Note) Vinyl chloride resin (Shinichi First Vinyl Co., Ltd. ZESTpvc1000Z), and the same zinc-substituted A-type zeolite as that used in Examples 1 to 4 as the stabilizer used in the comparative example were used.

<Evaluation>
(1) Thermal stability The obtained sheet | seat was cut | disconnected in strip shape, and the heat-stable test piece (2.5 cm x 3.5 cm) was created. The test piece was placed in an oven at 180 ° C. and removed from the oven every 10 minutes to observe the degree of discoloration.
The degree of discoloration is visually evaluated in 10 stages based on the following Table 6, and 1 is shown when no discoloration is observed, and 10 is shown when the whole is discolored black. The larger this value, the poorer the thermal stability. It shows that. The evaluation results are shown in Table 7.

(2) Foaming property The test piece was sandwiched between two glass plates and immersed in a 170 ° C glycerin bath for 5 minutes, and then the state of firing of the test piece was observed and evaluated as follows. The results are shown in Table 7. .
Large foaming; many bubbles are seen
Medium; bubbles are seen
Small: There are slight bubbles.
No; no bubbles are seen.

As described above, from the examples and comparative examples, the chlorine-containing resin in the case of adding a mixture of zinc-substituted A-type zeolite and hydrocalumite exhibits excellent stability in both initial colorability and long-term thermal stability, In particular, it is understood that long-term thermal stability can be further improved when a mixture of zinc-substituted A-type zeolite and carbonated hydrocalumite is used.
In contrast, it can be seen that when various alkali metal and alkaline earth-substituted A-type zeolites are added instead of the zinc-substituted A-type zeolite, the initial colorability and long-term thermal stability are poor.

Claims (8)

Aluminosilicate substituted with Zn ion and the following general formula (1)

[Wherein X represents a monovalent or divalent anion, m represents the valence of the anion, and represents n ≦ 20], and contains a hydrocalumite as an active ingredient. Stabilizer composition for resin. The stabilizer composition for chlorine-containing resin according to claim 1, wherein the aluminosilicate substituted with Zn ions is A-type zeolite or X-type zeolite. The stabilizer composition for a chlorine-containing resin according to claim 1 or 2, wherein the aluminosilicate substituted with Zn ions has an average particle size of 6 µm or less. The stabilizer composition for chlorine-containing resins according to any one of claims 1 to 3 , wherein the aluminosilicate substituted with Zn ions has an equilibrium pH of 8.5 or less. The stabilizer composition for chlorine-containing resins according to any one of claims 1 to 4 , wherein X in the formula of the hydrocalumite represented by the general formula (1) is CO ₃ ^2- . The said hydrocalumite is a stabilizer composition for chlorine containing resins in any one of Claims 1 thru | or 5 using that whose average particle diameter is 20 micrometers or less. The stabilizer composition for a chlorine-containing resin according to any one of claims 1 to 6 , wherein a blending ratio of the aluminosilicate substituted with the Zn ions and the hydrocalumite is 90:10 to 10:90 in a weight ratio. . A chlorine-containing resin composition comprising the stabilizer composition for chlorine-containing resin according to any one of claims 1 to 7.