JPH11193336A - Hydrogen halide trapping agent for use in halogen-containing resin and halogen-containing resin composition containing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inexpensive composition which can trap the hydrogen halide formed from a halogen-containing resin in a low to high temperature range and is excellent in stability against carbonization and moisture absorption during storage by compounding a halogen-containing resin with a calcium- containing hydroxide. SOLUTION: A halogen-containing resin is compounded with 11-150 pts.wt., per 100 pts.wt. halogen-containing resin, hydrogen halide trapping agent being a Ca-containing hydroxide represented by the formula: Ca1-x Mx <2+> (OH)2 wherein M<2+> is at least one member selected among Mg<2+> , Mn<2+> , Fe<2+> , Co<2+> , Ni<2+> , Cu<2+> , and Zn<2+> and is desirably Mg<2+> or Zn<2+> ; and x is in the range: 0<=x<=0.5) and having a BET specific surface area of 10 m<2> /h or above, a mean secondary particle diameter of 5 μm or below. In order to improve the affinity of the Ca-containing hydroxide for the resin, it is desirable to coat the surface of the hydroxide with a higher fatty acid, a higher fatty acid metal salt, an anionic surfactant, a phosphoric ester, a coupling agent, an ester of a polyhydric alcohol with a fatty acid, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydrogen halide scavenger for a halogen-containing resin containing a calcium hydroxide as an active ingredient, and a calcium hydroxide capable of reducing hydrogen halide generated during combustion. And a halogen-containing resin composition. In more detail, the disadvantages of halogen-containing resins such as corrosion of peripheral equipment due to the generation of hydrogen halide during combustion or fire, danger of human life, and the generation of extremely toxic dioxins, etc. The present invention relates to a halogen-containing resin-containing hydrogen halide scavenger which can be prevented by remarkably reducing the generation of hydrogen halide by this, and a halogen-containing resin composition containing the hydrogen halide scavenger.

[0002]

2. Description of the Related Art Halogen-containing resins, for example, polyvinyl chloride (hereinafter also referred to as PVC), which is a representative resin, have various excellent physical properties and are therefore consumed in large quantities in a wide range of fields such as building materials, pipes and packaging materials. ing. The only major disadvantage, however, is that it emits large amounts of hydrogen chloride in the event of combustion or fire. This causes harms such as generation of highly toxic dioxins, corrosion of peripheral devices, and endangering human lives. Various hydrogen halide scavengers have been proposed to overcome such disadvantages of the halogen-containing resins. For example, calcium carbonate, zonotlite (calcium silicate), calcium aluminate, magnesium hydroxide, magnesium oxide, aluminum hydroxide, lithium hydroxide, lithium carbonate, sodium carbonate and the like. Of these, only calcium carbonate is more or less practical.

[0003]

Hydrogen halide scavengers other than calcium carbonate have either worse reactivity, ie, the scavenging rate, than calcium carbonate, or a reaction product of the scavenger and hydrogen chloride at a combustion temperature of about 800 ° C. Has the problem of decomposing. Calcium carbonate has a poor reactivity with hydrogen chloride and a poor hydrogen chloride scavenging property per weight. For this reason, there is a problem that the intrinsic physical properties of the resin are impaired. Lithium hydroxide is exceptionally excellent in the scavenger among the scavengers, but has a problem of deteriorating the halogen-containing resin and a problem of being expensive because it is strongly alkaline in itself. doing. Further, lithium hydroxide has a problem that it is easily dissolved in water and thus elutes from the resin. Further, since it easily absorbs carbon dioxide gas, it has a problem that it changes into lithium carbonate and the trapping rate decreases. Therefore, the development of an inexpensive hydrogen halide scavenger that has a high hydrogen halide trapping rate even at high temperatures, has good storage stability with respect to carbonation and hygroscopicity, and is inexpensive has been long anticipated.

[0004]

According to the present invention, there is provided the following formula (1): Ca _1-x M ²⁺ _x (OH) ₂ (1) (where M ²⁺ is Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , Co2 ⁺ , Ni
²⁺ , Cu ²⁺ and Zn ²⁺ , preferably Mg ²⁺ and / or Zn ²⁺ , particularly preferably Mg ^2+
2+ , and x is 0 ≦ x ≦ 0.5, preferably 0 <x ≦
0.5, more preferably 0.01 ≦ x ≦ 0.5, particularly preferably a number in the range of 0.05 ≦ x ≦ 0.4). A hydrogen halide scavenger for a halogen-containing resin is provided. Further, in the present invention, the hydrogen halide scavenger is used in an amount of 11 to 150 parts by weight, preferably 40 to 100 parts by weight, particularly preferably 50 to 8 parts by weight based on 100 parts by weight of the halogen-containing resin.
Disclosed is a halogen-containing resin composition characterized in that it is mixed with 0 parts by weight, wherein generation of hydrogen halide during combustion is reduced.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrogen halide scavenger of the present invention is excellent in hydrogen halide scavenging in a range from a low temperature to a high temperature of at least 800 ° C. And the storage stability is relatively good. It is particularly good when surface treatment is performed. In addition, it has features such as being inexpensive. Further, the hydrogen halide scavenger of the present invention, kneading of a halogen-containing resin,
It also has a function of imparting thermal stability in the molding step.

The inventor of the present invention has found that when a halogen-containing resin is burned up to a temperature of about 800 ° C., it has excellent reactivity in the sense that it suppresses the generation of hydrogen halide and exhibits a high hydrogen halide trapping property with a smaller amount of addition. We have been working diligently to develop a hydrogen halide scavenger that is inexpensive and easy to handle. As a result, they have found that calcium hydroxide, which has not been noticed in the past, has a strong reaction and binding property with hydrogen halide even at high temperatures. Although the reactivity of this substance with hydrogen halide is superior to calcium carbonate conventionally used, it has not been sufficient. As a result of research to elucidate the cause, BET
The primary particles (crystal grain size) are large, having a specific surface area of about 2 m ² / g, and the secondary particles in which the primary particles are aggregated have an average secondary particle size of about 1
It was presumed to be as large as 0-50 μm. It has been found that the cause is that calcium hydroxide is converted into a calcium hydroxide-based solid solution, and more preferably, the surface of the solid solution can be removed by treating the surface with a higher fatty acid or the like in order to improve the affinity with the resin.

When, for example, magnesium hydroxide is solid-dissolved in calcium hydroxide, the formation of coarse crystals due to the high solubility of calcium hydroxide in water is suppressed, primary and secondary particles are reduced, and halogenation is reduced. It was estimated that the reactivity with hydrogen increased. In addition, such a solid solution prevents calcium hydroxide from changing to calcium carbonate due to the reaction between calcium hydroxide and carbon dioxide, and reduces the solubility in water, thereby preventing the inherent instability of calcium hydroxide. I found what I could do. The reactivity of calcium carbonate with hydrogen halide is remarkably inferior to that of calcium hydroxide. Further, the hydrogen halide scavenger of the present invention has an advantage that it can be produced at low cost.

The hydrogen halide scavenger of the present invention has the following formula (1) Ca _1-x M ²⁺ _x (OH) ₂ (1) (where M ²⁺ is Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , Co2 ⁺ , Ni
²⁺ , Cu ²⁺ and Zn ²⁺ , preferably Mg ²⁺ and / or Zn ²⁺ , particularly preferably Mg ^2+
2+ , and x is 0 ≦ x ≦ 0.5, preferably 0 <x ≦
0.5, more preferably 0.01 ≦ x ≦ 0.5, particularly preferably a number in the range of 0.05 ≦ x ≦ 0.4). This is a hydrogen halide scavenger for a halogen-containing resin. This calcium-based hydroxide means that M ²⁺
Is a solid solution of calcium hydroxide, or a mixture of the solid solution and an M ²⁺ (OH) ₂ solid solution in which Ca ²⁺ forms a solid solution in M ²⁺ (OH) ₂ . From the standpoint of reactivity with hydrogen halide, M ²⁺
It is more preferable that the amount is larger. However, the trapping and retaining properties of halogen at a high temperature of about 800 ° C. tend to be slightly worse. Therefore, the range of M ²⁺ needs to be 0.5 or less. As M ²⁺ , Mg ²⁺ is
Next, Zn ²⁺ is preferable in that it is inexpensive and white, and is preferable because it does not impair the thermal stability of the resin.

[0009] The hydrogen halide scavenger of the present invention can be produced by various methods. Hereinafter, the method for producing the hydrogen halide scavenger of the present invention will be described. For further details, see JP-A-6-72709 and JP-A-6-88075.
Reference is made to the description in Japanese Patent Publication No. CaCl ₂ , Ca (N
Water-soluble Ca salts such as O ₃ ) ₂ and MgCl ₂ , Mg (NO ₃ )
_{2. It} can be obtained by adding an equivalent or more of an alkali such as NaOH or KOH to a mixed solution with an M ²⁺ salt such as bitter and seawater while stirring. It can also be obtained by adding a water-soluble salt of M ²⁺ to Ca (OH) ₂ (slaked lime) produced by reacting CaO (quick lime) with water while stirring. Furthermore, the natural mineral dolomite (CaCO ₃ · M
gCO ₃ ) at about 1000 ° C.
It can also be obtained by a method of generating O and then reacting with water. The calcium-based compound obtained by such a method may be further subjected to post-treatment such as hydrothermal treatment at about 100 to 200 ° C. or conventional wet grinding such as a ball mill. These post-treatments can reduce secondary aggregation. The BET specific surface area is preferably 5 m ² / g
Or more, more preferably 10 m ² / g or more, and the average secondary particle diameter is preferably 5 μm or less, particularly preferably 2 μm or less.
μm or less.

[0010] The hydrogen halide scavenger of the present invention can prevent tertiary aggregation in the resin by increasing the affinity with the halogen-containing resin. Prevention of tertiary agglomeration improves dispersibility in the resin, contributes to suppression of reaction with carbon dioxide, and reduction of solubility in water. The above-mentioned improvement in affinity can be achieved by performing a surface treatment with a conventionally used known surface treating agent. The surface treatment is performed, for example, from the group consisting of higher fatty acids, metal salts of higher fatty acids, anionic surfactants, phosphate esters, coupling agents (silane-based, titanate-based, aluminum-based) and esters of polyhydric alcohols and fatty acids. It is carried out by at least one selected surface treatment agent.

The following are more specific examples of those preferably used as the surface treating agent. Higher fatty acids having 10 or more carbon atoms, such as stearic acid, erucic acid, palmitic acid, lauric acid, oleic acid, and behenic acid; alkali metal salts of the higher fatty acids; sulfate esters of higher alcohols, such as stearyl alcohol and oleyl alcohol; Polyethylene glycol ether sulfate, amide bond sulfate, ester bond sulfate, ester bond sulfonate, amide bond sulfonate, ether bond sulfonate, ether bond alkyl allyl sulfonate, ester bond alkyl allyl sulfonate Anionic surfactants such as salts and amide-bonded alkyl allyl sulfonates; orthophosphoric acid and mono- or diesters such as oleyl alcohol and stearyl alcohol, or a mixture of both, in their acid form or alkali Phosphates such as metal salts or amine salts; vinylethoxysilane, vinyl-tris (2-methoxyethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, beta (3,4 Silane coupling agents such as -epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane; isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate)
Titanate-based coupling agents such as titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, and isopropyl tridecylbenzenesulfonyl titanate; aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate; glycerin monostearate; Esters of fatty acids with polyhydric alcohols such as glycerin monooleate.

The coating treatment of the surface of the calcium hydroxide of the formula (1) with the surface treating agent can be carried out by a known wet or dry method. For example, as a wet method, the surface treatment agent may be added in a liquid or emulsion state to a slurry of a calcium hydroxide and mechanically sufficiently mixed at a temperature up to about 100 ° C. As a dry method, a calcium hydroxide powder is added to a surface treatment agent in a liquid, emulsion, or solid state with sufficient stirring by a mixer such as a Henschel mixer, and the mixture may be sufficiently mixed with or without heating. . The amount of the surface treatment agent can be appropriately selected, but is preferably about 0.1 based on the weight of the calcium hydroxide.
Preferably, it is about 10% by weight.

After the surface treatment, if necessary, means such as washing, dehydration, granulation, drying, pulverization, classification and the like are appropriately selected and carried out to obtain a final product form. The halogen-containing resin used in the present invention means a resin containing at least one of chlorine, bromine and iodine. Specific examples are as follows. Polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride
Propylene copolymer, vinyl chloride-styrene copolymer,
Vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride- Isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, chloride Vinyl-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-chlorinated resin such as various vinyl ether copolymers, tetrafluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, PFA resin (ethylene tetrafluoride-perfluoroalkyl vinyl ether Polymer resin), ethylene trifluoride resin, ethylene tetrafluoride - ethylene copolymers such fluorine-containing resin, chloroprene rubber, brominated butyl rubber, rubbers such as chlorosulfonated polyethylene rubber. Among the halogen-containing resins, polyvinyl chloride, polyvinylidene chloride and the like are used in the largest amount.

The halogenated scavenger of the present invention with respect to the halogen-containing resin is used in an amount of about 11 parts by weight per 100 parts by weight of the halogen-containing resin.
-150 parts by weight, preferably about 50-80 parts by weight, more preferably about 40-100 parts by weight. In the halogen-containing resin composition of the present invention, in addition to the halogenated scavenger of the present invention, other conventional additives can be used in combination.
Examples of such additives include heat stabilizers, lubricants, processing aids, antioxidants, ultraviolet absorbers, pigments, antistatic agents, foaming agents, plasticizers, crosslinking agents, vulcanizing agents, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples.

[0016]

Example 1 600 g of quicklime was added to 5 liters of water at 60 ° C. with stirring, and stirring was continued for 30 minutes. Obtained Ca
The (OH) ₂ slurry was filtered through a 100 mesh sieve. MgCl ₂ was stirred into 5 liters (about 50 ° C.) of a slurry of Ca (OH) ₂ adjusted to a concentration of 2 mol / l.
Was added to 1 liter of ion bittern containing 2 mol / l, and stirring was continued for about 20 minutes. The reaction product was filtered, washed with water, slurried again, heated to about 50 ° C., 300 ml of a warm aqueous solution of about 50 ° C. containing 15 g of sodium oleate was added with stirring, and stirring was continued for about 15 minutes, Surface treatment was performed. Thereafter, the mixture was filtered, dried, and pulverized by an atomizer pulverizer. The measured powder X-ray diffraction of this object, Ca (OH) ₂ and the same pattern as Ca (OH) ₂ was shifted to higher angle than was shifted to a lower angle side than Mg (OH) ₂ Mg (OH ₂ ) showed the same but weaker pattern. Therefore, the result is Ca (O
It is shown that the compound in which Mg was dissolved in H) ₂ was mostly occupied, and the compound in which Ca was dissolved in Mg (OH) ₂ was slightly present. According to the result of the chemical analysis by the chelate method, the chemical composition was as follows. Ca _0.81 Mg _0.19 (OH) ₂ BET specific surface area 15.2 m ² / g, average secondary particle diameter was 3.16 μm as measured by a laser diffraction method after ultrasonic dispersion treatment using isopropyl alcohol as a solvent.

This product is uniformly mixed with the following formulation: 100 parts by weight of polyvinyl chloride, 50 parts by weight of dioctyl phthalate, 0.5 parts by weight of zinc stearate, and 60 to 100 parts by weight of the hydrochloric acid scavenger of the present invention. , About 160
The mixture was kneaded at 3 ° C. for 3 minutes to prepare a sheet having a thickness of about 0.8 mm. A 0.5-1.0 g sample was taken from this sheet and precisely weighed. About this sample, IEC STA
The amount of HCl generated was measured according to NDARD 754-1. The outline is as follows. The temperature was raised at a rate of 20 ° C./min to 800 ° C. while flowing dry air at a flow rate of 110 ml / min.
For 3 minutes, and the generated HCl was added to a triple gas absorption tube for 0.1 minute.
After absorption in a 1 mol / L NaOH aqueous solution,
The aOH aqueous solution is recovered, silver nitrate is added, and silver chloride is precipitated and separated. After that, excess silver nitrate is titrated with ammonium thiocyanate to determine HCl. Sample 1
Table 1 shows the values converted to mg per g. In addition, IE
In the C standard, the amount of HCl generated is 90 mg / g or less.

[0018]

Embodiment 2 A mixed aqueous solution of calcium chloride, magnesium chloride and zinc chloride (Ca ²⁺ = 0.9 mol / liter, M
g ²⁺ = 0.05 mol / l, Zn ²⁺ = 0.05 mol / l) 5 liters to 3 mol / l NaOH
4 liters of the aqueous solution was added at about 30 ° C. and reacted. 7.
200 ml of an aqueous solution containing 4 g of sodium laurate was added to the reaction product to perform a surface treatment. Thereafter, the mixture was filtered, washed with water, dried, and pulverized with an atomizer.
The powder X-ray diffraction result of this product was a pattern of only Ca (OH) ₂ . However, it shifted slightly higher than the Ca (OH) ₂ pattern. Therefore, it can be seen that a compound in which Mg and Zn are dissolved in Ca (OH) ₂ is formed. The chemical composition of this product was as follows. Ca _0.90 Mg _0.05 Zn _0.05 (OH) ₂ BET specific surface area was 11.2 m ² / g, and average secondary particle diameter was 1.07 μm. This material was operated in the same manner as in Example 1 to melt-knead into polyvinyl chloride, prepare a sheet, and add HCl.
The amount of generation was measured. Table 1 shows the results. However,
The compounding amount of this product was different from that of Example 1 in that the compounding amount of Example 1 was changed to 50 parts by weight.

Comparative Example 1 The BET specific surface area was 11.5 m ² / g, and the average secondary particle diameter was 0.1.
A sheet was prepared in the same manner as in Example 1 except that the amount of 15 μm fine particle calcium carbonate was changed to 100 parts by weight, and the amount of HCl generated was measured. Table 1 shows the results.

Example 3 0.5 L of a 1 mol / L magnesium chloride aqueous solution (about 30 ° C.) was added to 5 L (about 30 ° C.) of a slurry of 2 mol / L Ca (OH) ₂ with stirring, and the reaction was carried out. I let it. After stirring was continued for about 20 minutes, the mixture was filtered, and water was added again to form a slurry. The slurry was heated to about 50 ° C and 150 ml of an aqueous solution of about 50 ° C in which 74 g of sodium stearate was dissolved was added to perform surface treatment. After that, it was filtered, dried and pulverized. The powder X-ray diffraction pattern was only Ca (OH) ₂ . Where Ca
The shift was slightly higher than the (OH) ₂ pattern. Therefore, it can be seen that a compound in which Mg was dissolved in Ca (OH) ₂ was formed. The chemical composition by chelate analysis was as follows. Ca _0.95 Mg _0.05 (OH) ₂ BET specific surface area is 6 m ² / g, average secondary particle diameter is 3.4
μm. A sheet was prepared and the amount of HCl generated was measured in the same manner as in Example 1 except that the blending amount of this product was changed to 80 parts by weight. Table 1 shows the results.

Comparative Example 2 The amount of the HCl scavenger of the present invention used in Example 1 was 40
A sheet was prepared in the same manner as in Example 1 except that the parts by weight were used, and the amount of generated HCl was measured. Table 1 shows the results.

[0022]

[Table 1] HCl trapping properties of various additives Type of additive Addition amount HCl generation amount (Parts by weight) (mg / g) Example 1-1 A 100 9.9 1-2 A 80 50.8 1-3 A 60 67.3 Example 2 B 50 82.5 Comparative Example 1 CaCO ₃ 100 120 Example 3 C 80 88.4 Comparative Example 2 A 40 148

[0023]

According to the present invention, a halogen-containing compound having a feature of being able to efficiently capture hydrogen halide generated from a halogen-containing resin in a range from a low temperature to a high temperature, having excellent storage stability and being inexpensive. A hydrogen halide scavenger for a resin and a halogen-containing resin composition containing the scavenger are provided.

Claims (6)

[Claims] 1. The following formula (1): Ca _1-x M ²⁺ _x (OH) ₂ (1) (where M ²⁺ is Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni
²⁺ , Cu ²⁺ and Zn ²⁺ , wherein x represents a number in the range of 0 ≦ x ≦ 0.5). Of a halogen-containing resin. 2. In the Ca-based hydroxide of the formula (1), x
Is a number in the range of 0.05 ≦ x ≦ 0.4, the hydrogen halide scavenger of the halogen-containing resin according to claim 1, wherein 3. The hydrogen-containing scavenger according to claim 1, wherein the Ca-based hydroxide of the formula (1) has a BET specific surface area of 10 m ² / g or more. 4. In the Ca-based hydroxide of the formula (1), M
^The halogen-containing resin composition according to claim 1, wherein ²⁺ is Mg ²⁺ and / or Zn ²⁺ . 5. The following formula (1) Ca _1-x M ²⁺ _x (OH) ₂ (1) (where M ²⁺ is Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni
²⁺ , Cu ²⁺ and Zn ²⁺ , wherein x is a number in the range of 0 ≦ x ≦ 0.5) with respect to 100 parts by weight of the halogen-containing resin. 11-15
A halogen-containing resin composition, which is added in an amount of 0 part by weight. 6. A Ca-based hydroxide of the formula (1) comprising a higher fatty acid, a metal salt of a higher fatty acid, a phosphate, a silane,
Titanate-based and aluminum-based coupling agents,
Characterized in that it has been surface-treated with at least one surface treating agent selected from the group consisting of esters of polyhydric alcohols and fatty acids, anionic surfactants and sodium salts of olefin-maleic acid copolymers. The halogen-containing resin composition according to claim 5, wherein