JP2005048062A - Stabilizer composition for chlorine-containing resin and chlorine-containing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stabilizer composition for a chlorine-containing resin imparting the chlorine-containing resin with long-term thermal stability, causing no initial discoloration of the resin and capable of ameliorating foaming phenomena during resin processing as well, and to provide a chlorine-containing resin composition containing the stabilizer composition. <P>SOLUTION: The chlorine-containing resin composition contains as active ingredients an aluminosilicate substituted with a Zn ion and an inorganic phosphite containing at least one metal element selected from Ca and Ba. <P>COPYRIGHT: (C)2005,JPO&NCIPI

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 an inorganic phosphite as an active ingredient has also been proposed (see, for example, Patent Documents 14 to 16). It has not received much attention as a stabilizer for the contained resin.

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 54-114556 A JP-A-55-84341 JP 58-138745 A

  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 a situation, the present inventors have used an aluminosilicate substituted with a specific metal ion as a stabilizer for a chlorine-containing resin and a material containing a specific inorganic phosphite. The synergistic effect of the aluminosilicate and inorganic phosphite improves the shortcomings of conventional chlorine-containing resin thermal stabilizers, improves long-term thermal stability, improves initial colorability, The present invention has been completed by finding that it has an excellent effect on the improvement of the foaming phenomenon.

  That is, the first invention to be provided by the present invention contains an aluminosilicate substituted with Zn ions and an inorganic phosphite containing at least one metal element selected from Ca and Ba as active ingredients. This is a stabilizer composition for chlorine-containing 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 contains an aluminosilicate substituted with Zn ions and an inorganic phosphite containing at least one metal element selected from Ca and Ba as active ingredients. Is.

  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 these, the zinc-substituted zeolite obtained by exchanging the cation of A-type zeolite or X-type zeolite with Zn ions has a high synergistic effect with inorganic phosphite described later, and effectively produces long-term heat in the chlorine-containing resin. It is particularly preferable in that it provides stability, does not cause initial coloring of the chlorine-containing resin, and can further improve the foaming phenomenon during resin processing.

  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 is obtained by removing free alkali as much as possible in addition to having the above characteristics, and at least an equilibrium pH of 8.5 or less, It is particularly preferable to use 7.0 to 8.2 having a high synergistic effect with the inorganic phosphite described later, and particularly capable of effectively suppressing the initial coloring of the chlorine-containing resin. 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, an inorganic phosphite containing at least one metal element selected from Ca and Ba as the second component (hereinafter abbreviated as “inorganic phosphite”) is, for example, calcium phosphite. , Barium phosphite, calcium barium phosphite, and the like, and these can be used alone or in combination of two or more.

  In the present invention, the inorganic phosphite is particularly preferably an average particle size determined by a laser diffraction method of 20 μm or less, preferably 1 to 10 μm, since the resin dispersibility becomes good.

In addition, the inorganic phosphites that are industrially available often include water of crystallization as shown by the general formula; MPHO ₃ .H ₂ O (wherein M represents Ba or / and Ca). The crystal water itself has no particular problem in the temperature range where the molding temperature of the chlorine-containing resin is 200 ° C. or less. However, the crystal water itself has a temperature exceeding this, or is kneaded for a long time at a high temperature. Since there is a possibility of releasing water, the inorganic phosphite in the present invention effectively suppresses the foaming phenomenon during resin processing even under these severe conditions when an anhydride from which crystal water has been removed is used. Furthermore, there is no initial coloring of the chlorine-containing resin, and long-term thermal stability can be imparted to the chlorine-containing resin.

  For example, the inorganic phosphite anhydride is obtained by heat-treating an inorganic phosphite hydrate with a temperature of 200 ° C. or higher, preferably 250 to 350 ° C. for 0.5 hour or longer, preferably 1 to 2 hours. Can be manufactured more easily.

  In the present invention, the inorganic phosphate may be a reaction product obtained by bringing a calcium compound and / or a barium compound into contact with a waste liquid containing phosphorous acid.

  In this case, the waste liquid containing phosphorous acid includes, for example, a waste liquid produced as a by-product when sodium hypophosphite is produced, a waste liquid that uses phosphorus trichloride as a chlorinating agent or a reactive agent for organic compounds, Examples thereof include nickel-phosphorus alloy plating waste liquid, electroless nickel plating waste liquid, electroless nickel plating aging liquid, or waste liquid from a plating plant using sodium hypophosphite as a reducing agent. Among these, in this invention, it is preferably used with respect to the waste liquid from a plating factory, and can be used suitably especially with respect to an electroless nickel plating aging liquid.

  The plating aging solution here refers to the oxidation of sodium hypophosphite used as a reducing agent when electroless nickel plating is performed with a bathing plating solution, and the plating function gradually decreases with the formation of sodium phosphite. In addition, it refers to a bath solution to be discarded that does not exhibit a plating function in a building bath despite the fact that it replenishes the plating solution and contains a considerable amount of nickel ions.

  The waste liquid containing phosphorous acid may contain other components as long as this reaction is not hindered. Examples of components other than phosphorous acid include inorganic acids such as sulfuric acid and salts thereof, and organic acids such as acetic acid, malic acid, lactic acid, citric acid, tartaric acid, and amino acids and salts thereof. Further, it is desirable that a waste liquid containing a large amount of metal ions such as nickel ions, such as an electroless nickel plating waste liquid, is pre-treated in advance in the process of the present invention to separate and remove these metal ions.

  As the calcium compound and barium compound added to the waste liquid containing phosphorous acid, for example, these carbonates, sulfates, chlorides, hydroxides and the like can be used.

  The reaction product obtained by bringing the calcium compound and / or barium compound into contact with the waste liquid containing phosphorous acid is mainly composed of inorganic phosphite. , Calcium or / and barium hypophosphite, phosphate, sulfate and other inorganic substances, calcium or / and barium acetate, malate, lactate, citrate, tartrate, amino acid salt, etc. Compounds such as organic acid salts are by-produced. In the present invention, the by-product calcium compound and / or barium compound acts as a stabilizing aid for the third component described later, and can further improve various physical properties such as thermal stability of the chlorine-containing resin. Calcium produced as a by-product in addition to the inorganic phosphite in the reaction product obtained by contacting the waste liquid containing phosphorous acid with the calcium compound and / or barium compound in the present invention because it is useful as a component. The compound or / and barium compound may be positively contained, and the content of the by-product calcium compound and / or barium compound is not particularly limited, but in many cases, 1 in the reaction product. When it is ˜20% by weight, preferably 1 to 10% by weight, an excellent effect as a stabilizer of the inorganic phosphite is exhibited, and the cost is reduced. There is an advantage.

As a specific reaction operation for obtaining inorganic phosphite from waste liquid containing phosphorous acid, the waste liquid containing phosphorous acid contains calcium compound and / or barium compound equivalent to or more than HPO ₃ ^2- By adding and reacting at 10 to 70 ° C. with stirring in the vicinity of pH 6 to 10 neutral, the solubility of the inorganic phosphite in the treatment liquid is reduced, and the desired inorganic phosphite is obtained with high yield. be able to. In addition, since the pH increases with the addition of sulfate, carbonate, and hydroxide, it is preferable to perform the above reaction so that the mineral acid is appropriately added to the treatment liquid and the pH is within this range (at this time) JP-A-8-337881, JP-A-9-176661, JP-A-9-100107, JP-A-10-195670, JP-A-10-195669, JP-A-10-158851, JP-A-10-158851 10-147882 and JP-A 2000-345357.)

  Furthermore, in the present invention, as the inorganic phosphite, in the case of calcium phosphite, calcium phosphite by-produced when producing sodium hypophosphite from yellow phosphorus, sodium hydroxide and slaked lime can be used. This by-product is mainly composed of calcium phosphite, but in addition to that, there are many calcium compounds such as slaked lime and calcium carbonate, calcium hypophosphite, and calcium phosphate produced by partial carbonization. It is contained in an amount of 10 to 30% by weight. This calcium compound other than calcium phosphite acts as a stabilizing aid for the third component described later, and is useful as a component that can further improve various physical properties such as thermal stability of the chlorine-containing resin.

  In the present invention, the reaction product obtained from the waste liquid containing the phosphorous acid and the calcium phosphite by-produced when producing the sodium hypophosphite are often hydrated, After completion of the reaction, an inorganic phosphite anhydride can be obtained by heat treatment at a temperature of 200 ° C. or higher, preferably 250 to 350 ° C. as described above.

  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 inorganic phosphite of the second component is the kind of chlorine-containing resin used. However, in many cases, the blending ratio of the aluminosilicate substituted with Zn ions and the inorganic phosphite is 90:10 to 10:90, preferably 30:70 by weight. The initial coloration is conspicuous in the thermal stability test outside of the above range, and in particular, the long-term thermal stability of the chlorine-containing resin is deteriorated, and the so-called “zinc burn” tends to occur. 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（２）

（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、下記一般式（３）

（式中、Ｍ₁及びＭ₂はＣａ²⁺、Ｍｇ²⁺、Ｚｎ²⁺から選ばれる少なくとも１種以上であり、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、ｍはアニオンの価数を表し、ｎは２０以下を示す。）で表されるハイドロカルマイト類、又は下記一般式（４）

（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 (1)

(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 (2)

(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 and 0 ≦ m <2)), hydrotalcites represented by the following general formula (3)

(Wherein M ₁ and M ₂ are at least one selected from Ca ²⁺ , Mg ²⁺ and Zn ²⁺ , and A ¹ is CO ₃ ²⁻ , SO ₄ ²⁻ , OH ⁻ , ClO ₄ ^−. , NO ₃ ^-. it represents less when at least one anion selected from, m represents the valency of the anion, hydrocalumite such n is represented by showing a 20 or less), or the following general formula (4)

(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-cyclohexylphenyl), 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 ions of the first component, an inorganic phosphite of the second component, and a third component added as necessary. Stabilization aids may be used separately added to the chlorine-containing resin, and aluminosilicate substituted with Zn ion as the first component, inorganic phosphite as the second component, added if necessary The third component stabilizing aid may be added to the chlorine-containing resin as a uniform mixture. When preparing this homogeneous mixture, the aluminosilicate substituted with Zn ion of the first component, the inorganic phosphite of the second component, and the third component added if necessary A predetermined amount of the agent 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 includes, for example, various household items such as raincoats, umbrellas, rain pants, rain boots, hats, various keyboards, laminates, handbags, wallets, sheet processing products such as stationery, 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, watchbands, packing materials, wall materials, flooring 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 inorganic phosphite>
Calcium phosphite sample A;
82 g (1 mole) of phosphorous acid was dissolved in 191 ml of water. Next, 76.2 g of slaked lime was added to 305 g of water and sufficiently dispersed using a homomixer. The slurry containing the slaked lime was added to the phosphorous acid aqueous solution, and the reaction was performed at 80 ° C. with stirring for 3 hours. After completion of the reaction, the mixture was separated by filtration to recover calcium phosphite. Next, the recovered calcium phosphite was washed with water, dried at 120 ° C. for 5 hours, and pulverized to obtain 140 g of calcium phosphite. Table 3 shows the main physical properties of the obtained calcium phosphite. In the chemical composition, the Ca content is ICP analysis, the PO ₃ content is ion chromatography, and the H ₂ O content is reduced when a calcium phosphite sample having a weight of W ₀ is heat-treated at 300 ° C. for 1 hour in a heating furnace. The weight W ₁ thus obtained was obtained and obtained from the value obtained by dividing W ₁ by W ₀ . The average particle size was determined by a laser diffraction method.

・ Calcium phosphite sample B
140 g of the calcium phosphite sample A was heat-treated at 300 ° C. for 1 hour, and this was designated as calcium phosphite sample B. Further, the obtained calcium phosphite sample B was obtained in the same manner as the calcium phosphite sample A to obtain the chemical composition and average particle diameter, and the results are shown in Table 3.

・ Calcium phosphite sample C
An aqueous slurry containing 62 kg of yellow phosphorus and 44.3 kg of slaked lime was prepared, and then 60 kg of sodium hydroxide was added and reacted with the inside of the reaction system as a nitrogen gas atmosphere. After completion of the reaction, the filter cake was separated and recovered from a solution in which sodium hypophosphite monohydrate was dissolved by filtration through a belt filter.
Next, since soluble salts such as sodium hypophosphite and sodium phosphite were adhered to the filter cake, the pulp was repulped into a 10% slurry, and then filtered again to wash away the soluble salts.
Next, the washed filter cake was dried at 120 ° C. for 5 hours and then pulverized to obtain a calcium phosphite sample C. The physical properties are shown in Table 3.
The chemical composition, H ₂ O content, and average particle size were determined in the same manner as the calcium phosphite A sample.

上記組成の無電解ニッケルめっき廃液１ｔ（比重１．２、ｐＨ４．５）にＮｉ粉末１０Ｋｇを加え、５０ｗｔ％ＮａＯＨを滴下しながらｐＨを８に維持し、反応が始まるまで昇温し、１時間熟成した。無電解めっき反応終了後、常法により濾過分離し、１４．５ｋｇのニッケル金属を分離回収した（除去率９９．９％）。
次いで、分離後の母液１．２ｔに５０ｗｔ％硫酸３６６ｋｇと消石灰粉末１８０ｋｇを添加した（ｐＨ ９）。次いで５０℃に昇温し、そのまま攪拌しながら２時間熟成を行った。次いで、反応液を常法により濾過分離し、濾過ケーキを分離し回収した。次いで、この回収した濾過ケーキを１２０℃で５時間乾燥し、次いで粉砕処理して亜リン酸カルシウム試料Ｄとし、その諸物性を表３に示した。
なお、化学組成、Ｈ₂Ｏ含有量及び平均粒径は前記亜リン酸カルシウムＡ試料と同様な方法で求めた。 ・ Calcium phosphite sample D
A used electroless nickel plating aging solution having the composition shown in Table 2 was used.

10 kg of Ni powder is added to 1 t of electroless nickel plating waste liquid having the above composition (specific gravity 1.2, pH 4.5), and the pH is maintained at 8 while dropping 50 wt% NaOH. Aged. After completion of the electroless plating reaction, 14.5 kg of nickel metal was separated and recovered by a conventional method (removal rate 99.9%).
Next, 366 kg of 50 wt% sulfuric acid and 180 kg of slaked lime powder were added to 1.2 t of the mother liquor after separation (pH 9). Next, the temperature was raised to 50 ° C., and aging was performed for 2 hours while stirring as it was. Next, the reaction solution was separated by filtration in a conventional manner, and the filter cake was separated and collected. Next, the recovered filter cake was dried at 120 ° C. for 5 hours and then pulverized to obtain a calcium phosphite sample D. The physical properties are shown in Table 3.
The chemical composition, H ₂ O content, and average particle size were determined in the same manner as the calcium phosphite A sample.

Examples 1-4 and Comparative Examples 1-10
The blends shown in Tables 5 to 6 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 4. Moreover, the presence or absence of foaming during the molding process was also observed visually, and the results were also shown in Tables 7-8 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）、亜リン酸カルシウムは亜リン酸カルシウム試料Ｂを使用した。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) Calcium phosphite sample B was used as the vinyl chloride resin (new Daiichi PVC Co., Ltd. ZESTpvc1000Z) and calcium phosphite. The same zinc-substituted A-type zeolite as in Examples 1 to 4 was used.

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)

<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 170 ° 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 Table 8 below, and 1 is shown when no discoloration is observed, and 10 is shown when the whole is discolored black. The larger this value, the lower the thermal stability. It shows that. The evaluation results are shown in Table 9.

(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 9. .
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 when the mixture of calcium phosphite and zinc-substituted A-type zeolite is added exhibits excellent stability in both initial colorability and long-term thermal stability. It can be seen that good thermal stability is obtained regardless of the production history of calcium phosphite.
On the other hand, when various alkali metal and alkaline earth substituted A-type zeolites are added instead of the zinc-substituted A-type zeolite, the initial colorability is inferior. When a zinc compound is added, the initial colorability is excellent, but the long-term thermal stability is poor, and the so-called “zinc burn” phenomenon appears.

Example 5
The following vinyl chloride resin (Shin Daiichi Vinyl Co., Ltd. ZESTpvc1000Z) 100 parts by weight Lubricant; 1 part by weight of stearic acid Stabilizer; Zinc-substituted A-type zeolite 1.4 parts by weight; Calcium phosphite sample B The resin composition was kneaded continuously at 160 ° C. for 60 minutes on a hot roll, and then peeled from the roll to form a sheet having a thickness of 1 mm. The obtained sheet is cut into a strip shape to create a heat-stable test piece (2.5 cm × 3.5 cm). This test piece is put in an oven at 200 ° C. and taken out from the oven every 10 minutes. The degree of discoloration was observed as in Examples 1-4. The results are shown in Table 10.
Further, after the test piece was sandwiched between two glass plates and immersed in a glycerin bath at 200 ° C. for 5 minutes, the state of firing of the test piece was observed in the same manner as in Examples 1 to 4. The results are shown in Table 10.

  From the results in Table 10, it can be seen that those using anhydrous calcium phosphite as calcium phosphite have no firing even under more severe conditions, and can impart excellent thermal stability to the chlorine-containing resin.

Claims (11)

  A stabilizer composition for a chlorine-containing resin, comprising an aluminosilicate substituted with Zn ions and an inorganic phosphite containing at least one metal element selected from Ca and Ba as active ingredients. .   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 diameter of 6 µm or less.   The stabilizer composition for a chlorine-containing resin 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 a chlorine-containing resin according to claim 1, wherein the inorganic phosphite has an average particle size of 20 μm or less.   6. The stabilizer composition for chlorine-containing resin according to claim 1, wherein the inorganic phosphite uses an anhydride.   The stabilizer composition for a chlorine-containing resin according to any one of claims 1 to 6, wherein the inorganic phosphite uses a reaction product obtained by bringing a calcium compound or a barium compound into contact with a waste liquid containing phosphorous acid.   The stabilizer composition for chlorine-containing resin according to claim 5, wherein the inorganic phosphite is calcium phosphite.   The said calcium phosphite is a stabilizer composition for chlorine containing resins of Claim 8 using the calcium phosphite byproduced when manufacturing sodium hypophosphite.   9. The stabilizer composition for chlorine-containing resin according to claim 1, wherein a blending ratio of the aluminosilicate substituted with the Zn ions and the inorganic phosphite is 90:10 to 10:90 in weight ratio.   A chlorine-containing resin composition comprising the stabilizer composition for chlorine-containing resin according to any one of claims 1 to 10.