JP2006199890A - Blooming inhibitor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inhibitor capable of solving a problem of blooming (whitening of a surface in case of being impregnated with water) which is caused by substituting a low toxic heat stabilizer for a lead-based heat stabilizer of a halogen-containing resin and comprises whitening of a surface of a molded product by a deposit due to impregnation of the molded product is with water. <P>SOLUTION: This blooming inhibitor of the halogen-containing resin is given by using a copper-containing calcium hydroxide-based or magnesium hydroxide-based solid solution expressed by formula (1): M<SP>2+</SP><SB>1-x-y</SB>Cu<SB>x</SB>Zn<SB>y</SB>(OH)<SB>2</SB>(M<SP>2+</SP>is Ca and/or Mg; and x and y satisfy each: 0<x<2 and 0≤y<0.1). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an anti-blooming agent for halogen-containing resins. More specifically, the present invention relates to an agent for preventing blooming of a halogen-containing resin having a calcium hydroxide solid solution in which copper is solid-dissolved as an active ingredient (surface whitening due to mass transfer folding from the inside to the molded product surface when immersed in water). .

  The halogen-containing resin is often blended with a heat stabilizer, a lubricant, a plasticizer, and the like. When immersed in water, the phenomenon that the compounding agent breaks out on the surface of the molded body and the surface becomes white is called blooming, which causes problems such as contamination of the product surface, electrical resistance, adhesion, and printability. For this reason, in PVC electric wires and the like, preventing blooming without adversely affecting the thermal stability is essential for maintaining the function and value of the product. However, at present, there are almost no anti-blooming agents that satisfy such requirements.

  In the halogen-containing resin, a heat stabilizer is used in order to prevent decomposition of the resin at the stage of heating and melting and processing. Due to the non-toxic and low toxicity social demands on this heat stabilizer, lead-based stabilizers that have been used in large quantities until now are being banned. The lead-based stabilizer is excellent in all of electrical insulation, thermal stability, and blooming resistance as a thermal stabilizer for PVC electric wires. However, when the lead-based stabilizer is replaced with a low-toxicity Ca / Zn-based composite metal soap, hydrotalcite, or the like, a new problem has been encountered in that blooming becomes extremely strong. If this problem is not solved, it will cause a serious defect in electrical insulation and the like, making it difficult to replace the lead-based stabilizer with the safe stabilizer. Accordingly, an object of the present invention is to provide a safe (low toxicity) halogen-containing resin blooming inhibitor which prevents the blooming property of the low toxicity heat stabilizer and does not lower the heat stability.

（但し、式中、Ｍ^２＋はＣａおよび／またはＭｇを示し、ｘおよびｙはそれぞれ次の範囲、０＜ｘ＜０．２、好ましくは０．００５≦ｘ≦０．１、特に好ましくは０．０１≦ｘ≦０．０６、０≦ｙ＜０．１にある）

（但し、式中、Ａ^ｎ−はｎ価のアニオンを示し、ｘとｙは式（１）と同じ範囲を示し、ｚとｍはそれぞれ次の範囲、０＜ｚ＜０．４、好ましくは０．０１≦ｚ≦０．３３、０≦ｍにある）で表される銅を含有する水酸化カルシウム系または水酸化マグネシウム系固溶体を有効成分として含有する低毒性の含ハロゲン樹脂のブルーミング防止剤を提供する。 The present invention provides the following formula (1) or the following formula (2).

(In the formula, M ²⁺ represents Ca and / or Mg, and x and y are each in the following range, 0 <x <0.2, preferably 0.005 ≦ x ≦ 0.1, particularly preferably 0. .01 ≦ x ≦ 0.06, 0 ≦ y <0.1)

(In the formula, A ^n- represents an n-valent anion, x and y represent the same range as in formula (1), z and m represent the following ranges, 0 <z <0.4, preferably 0.01 ≦ z ≦ 0.33, 0 ≦ m), and a low-toxic halogen-containing resin blooming inhibitor containing a calcium hydroxide-based or magnesium hydroxide-based solid solution containing copper as an active ingredient I will provide a.

  ADVANTAGE OF THE INVENTION According to this invention, the blooming property which is a fault of the low toxicity stabilizer replaced with a toxic lead-type stabilizer can be improved notably. Moreover, the blooming-preventing agent of the present invention is mainly composed of calcium and / or magnesium, and copper, copper and zinc, or aluminum is added as a constituent element, and therefore has low toxicity and high safety. Furthermore, the blooming inhibitor of the present invention also has an effect of improving the thermal stability of the halogen-containing resin.

（但し、式中、ｘおよびｙは式（１）と同じ範囲であり、好ましいｘの範囲は、０．００５≦ｘ≦０．１、特に好ましくは０．０１≦ｘ≦０．０６にある）で表される水酸化カルシウム系固溶体である。 The blooming inhibitor of the present invention represented by the formula (1) is a compound having the same crystal structure as calcium hydroxide or magnesium hydroxide, and the former is a compound invented by the present inventor (Japanese Patent Laid-Open No. 6-72709). is there. The manifestation of the effect as an antiblooming agent of the present invention is due to calcium hydroxide or magnesium hydroxide in which an appropriate amount of copper is dissolved. Therefore, although aluminum and zinc are not essential, there are effects such as reduction of initial coloring. When there is too little solid solution copper, the blooming prevention effect is lowered, and when it is too much, the blooming prevention effect and the heat stabilization effect tend to be lowered. Therefore, the preferable range of x is 0.005 ≦ x ≦ 0.1, and particularly preferably 0.01 ≦ <x ≦ 0.06. The blooming inhibitor of the formula (2) is a compound in which copper and aluminum or further zinc is dissolved in calcium hydroxide, and the crystal structure belongs to hydrocalumite. The expression of the effect as an antiblooming agent is considered to be due to calcium hydroxide and / or magnesium hydroxide in which an appropriate amount of copper is dissolved in the same manner as the compound of formula (1). Among them, the most effective is the following formula (3) of a combination of Ca and Cu.

(However, in the formula, x and y are in the same range as in formula (1), and the preferred range of x is 0.005 ≦ x ≦ 0.1, particularly preferably 0.01 ≦ x ≦ 0.06. ) Is a calcium hydroxide solid solution.

The antiblooming agent of the present invention preferably has a small primary particle and secondary particle. Specifically, the BET specific surface area indicating the size of the primary particles is preferably 5 m ² / g or more, particularly preferably 10 m ² / g or more. At the same time, the secondary particle size obtained from the particle size distribution measurement is an average secondary particle size of 50% cumulative, preferably 2.0 μm or less, particularly preferably 1.0 μm or less.

  The antiblooming agent of the present invention can be used as it is, but it is preferable to perform a surface treatment with a surface treatment agent such as an anionic surfactant in order to improve the compatibility with the halogen-containing resin. Examples of the surface treatment agent include higher fatty acids, alkali metal salts of higher fatty acids, phosphate esters, silane, titanate and aluminum coupling agents, esters of polyhydric alcohols and fatty acids, anionic surfactants (acetylsulfosuccinate). Acid-based, alkyl sulfate-based, sulfate ester-based, acylmethyl tauric acid-based, alkylbenzene sulfonic acid-based, polycarboxylic acid-based, sarcosine-based), and alkali metal salts of olefin-maleic acid copolymers. .

  The surface treatment of the blooming inhibitor of formula (1) and formula (2) with the surface treatment agent can be carried out by a method known per se. For example, the surface treatment agent is added in liquid or emulsion form to the solid solution slurry of formula (1) and mechanically well mixed at a temperature up to about 100 ° C. Alternatively, the surface treatment agent powder is added to the solid solution of the formula (1) or the formula (2) as it is or after being diluted or dispersed in an appropriate solvent, and is mixed well with heating or non-heating. The addition amount of the surface treatment agent can be appropriately selected, but is preferably 0.1 to 10% by weight based on the weight of the solid solution.

  The anti-blooming agent of the present invention is produced by using an aqueous solution of Ca, Cu, Mg, Zn, Al, such as an aqueous solution of chloride, nitrate, acetate, and an alkali, such as sodium hydroxide, equivalent to or more than these metals. It can be produced by a method of coprecipitation with an aqueous solution, or a method of adding an aqueous solution of Cu or Cu and Mg and / or Zn or further an aqueous salt of Al to calcium hydroxide with stirring. The preferred manufacturing method is the former. Thereafter, the solid solution produced by the above method can be used as a final product by appropriately selecting each step of surface treatment, filtration, washing with water, dehydration, drying, pulverization, and classification.

  Examples of the halogen-containing resin referred to in the present invention include the following. Polyvinyl chloride (vinyl chloride), polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, vinyl chloride and vinyl acetate, ethylene, propylene, styrene, isobutylene, vinylidene chloride, styrene-maleic anhydride, styrene-acrylonitrile, chlorinated propylene, Chlorinated resins such as vinylidene chloride, vinyl acetate, acrylyl triester, maleic acid ester, methacrylic triester, acrylonitrile and copolymers with various vinyl ethers. Blends of these chlorinated resins with each other or with other synthetic resins not containing chlorine, block copolymers, graft copolymers, etc.

  The field to which the blooming inhibitor of the present invention is particularly preferably applied is a so-called soft PVC resin such as an electric wire film, a sheet, and leather containing a large amount of a plasticizer. The heat stabilizer used in combination is a non-toxic to low-toxic heat stabilizer such as hydrotalcites and / or Ca / Zn composite metal soap.

  For the mixing and kneading of the blooming inhibitor of the present invention with other additives such as halogen-containing resins, plasticizers, and heat stabilizers, a conventional method capable of uniformly mixing the two can be employed. For example, any mixing and kneading means such as a single-screw or twin-screw extruder, a roll, and a Banbury mixer can be adopted. There is no particular limitation on the molding method, and any molding means such as injection molding, extrusion molding, blow molding, press molding, rotational molding, calender molding, sheet forming molding, transfer molding, laminate molding, and vacuum molding can be employed.

  Hereinafter, the present invention will be specifically described by way of examples.

A mixed aqueous solution of calcium chloride and cupric nitrate (Ca = 0.98 mol / liter, Cu = 0.02 mol / liter) and an aqueous solution of 2 mol / liter sodium hydroxide into a 3 liter overflow reactor. In addition, 1 liter of water (about 30 ° C.) was added in advance, and the mixture was stirred with a chem stirrer and supplied at 100 ml / min and about 100 ml / min with a metering pump, respectively. To 35 ° C.), the flow rate of the aqueous sodium hydroxide solution was finely adjusted, and the coprecipitation reaction was carried out for about 30 minutes. About 200 g of the reactant slurry in terms of dry matter is placed in a stainless steel container and stirred and heated to 65 ° C., and about 100 ml (about 70 ° C.) of an aqueous solution in which 4.5 g of sodium stearate (purity 90%) is dissolved in advance. ) Was added with stirring to carry out a surface treatment. Thereafter, filtration, washing with water, drying and pulverization were performed. This powder was dissolved in hydrochloric acid, and the chemical composition was examined by chelate titration method. As a result, it was Ca _0.98 Cu _0.02 (OH) ₂ . The BET specific surface area measured by the liquid nitrogen adsorption method was 12 m ² / g, and was placed in isopropyl alcohol in advance by laser diffraction method and subjected to ultrasonic treatment for 5 minutes. .9 μm.

115 g of quicklime is added to 2 liters of warm water (about 40 ° C.) with stirring. After about 20 minutes of digestion reaction, 200 ml of 0.4 mol / liter cupric nitrate aqueous solution is gradually added to the reaction while stirring. I let you. After heating the reaction product to about 60 ° C., a little more than an equivalent amount of sodium hydroxide was added to 3.0 g of 98% pure lauric acid, and 100 ml of an aqueous solution dissolved in water at about 60 ° C. was stirred. In addition, surface treatment was performed. Thereafter, the mixture was passed through a 100 mesh sieve, filtered, washed with water, dried and pulverized. The chemical composition of the obtained powder was Ca _0.96 Cu _0.05 (OH) ₂ , the BET specific surface area was 10 m ² / g, and the average secondary particle size with a cumulative 50% was 1.0 μm.

In Example 1, magnesium chloride and cupric chloride (Mg = 0.94 mol / liter, Cu = 0.06 mol / liter) were used as the metal salt aqueous solution, and the pH was maintained at about 10.2 to 10.5. The reaction was performed in the same manner as in Example 1 except that the reaction was carried out. The chemical composition of the obtained powder was Mg _0.94 Cu _0.04 (OH) ₂ , the BET specific surface area was 30 m ² / g, and the average secondary particle size with a cumulative 50% was 1.2 μm.

2 liters of a mixed aqueous solution of calcium chloride, cupric chloride and aluminum chloride (Ca = 0.95 mol / liter, Cu ²⁺ = 0.2 mol / liter) is stirred into 1.3 liter of 2 mol / liter sodium hydroxide. In addition, it was coprecipitated at about 30 ° C. Thereafter, the mixture was heated to 70 ° C., about 100 ml of an aqueous solution (about 70 ° C.) in which 3 g of sodium stearate (purity 90%) was dissolved was surface-treated, and then filtered, washed with water, dried and pulverized. The chemical composition of this powder is Ca _0.75 Cu _0.05 Al _0.2 (OH) ₂ (OH) _0.2 · 0.4H ₂ O as a result of chemical analysis and thermal analysis, and the BET specific surface area is The average secondary particle diameter of 18 m ² / g, cumulative 50% was 1.1 μm.

[Blooming test] The mixture was uniformly mixed according to the following formulation, kneaded at 160 ° C for 5 minutes using an open roll, then pressed at 170 ° C for 5 minutes using a press molding machine, and molded into a sheet having a thickness of about 1 mm.
Polyvinyl chloride (TK-1000) 100 parts by weight DOP 25 parts by weight DINP 25 parts by weight Heavy calcium carbonate 30 parts by weight Ca-Zn composite metal soap stabilizer 3 parts by weight Carbon black 0.4 parts by weight Blooming inhibitor 0. 05-0.2 parts by weight A test piece of 5 cm square was cut out from this sheet, put into a beaker having a capacity of 200 ml, 200 ml of tap water was added, placed in an oven at 70 ° C., and allowed to stand for 24 hours. The test piece was taken out and the surface whitening degree was visually evaluated. The results are shown in Table 1.

  In the above formulation, a test piece was prepared in the same manner except that only carbon black was omitted, and this was placed in an oven at 190 ° C., and the thermal stability (time until blackening) was measured. The results are shown in Table 1.

“Comparative Example 1”
The same procedure as in Example 1 was performed except that the concentration of the mixed aqueous solution of calcium chloride and cupric nitrate was changed to Ca ²⁺ = 0.7 mol / liter and Cu ²⁺ = 0.3 mol / liter in Example 1. . The chemical composition of the produced powder was Ca _0.7 Cu _0.3 (OH) ₂ , the BET specific surface area was 6 m ² / g, and the average secondary particle size was 1.5 μm with a cumulative 50%. The evaluation results of this powder are shown in Table 1.

  As can be seen from Table 1, the antiblooming agents of the present invention produced in Examples 1 to 3 have no whitening at all and have an excellent antiblooming function.

Claims (4)

Following formula (1)

(Wherein M ²⁺ represents Ca and / or Mg, and x and y are in the following ranges, 0 <x <0.2 and 0 ≦ y <0.1, respectively) An anti-blooming agent for a halogen-containing resin, comprising a calcium hydroxide solid solution contained as an active ingredient. In the formula (1), the following formula (2) further containing Al

(In the formula, A ⁿ⁻ represents an n-valent anion, and x, y, z, and m are in the following ranges, 0 <x <0.2, 0 ≦ y <0.1, 0 <z <, respectively. An anti-blooming agent for halogen-containing resins containing, as an active ingredient, a calcium hydroxide solid solution containing copper represented by 0.4 and 0 ≦ m). Following formula (3)

(Wherein, x and y are in the following ranges, 0 <x <0.2, 0 ≦ y <0.1), and M ^{2+ in} formula (1) is Ca. The blooming inhibitor for halogen-containing resins according to 1. Antiblooming agents of formula (1) and formula (2) are higher fatty acids, alkali metal salts of higher fatty acids, phosphate esters, silane, titanate and aluminum coupling agents, esters of polyhydric alcohols and fatty acids, The surface treatment with at least one kind of surface treating agent selected from an anionic surfactant and an alkali metal salt of an olefin-maleic acid copolymer according to claim 1, 2, and 3. Anti blooming agent.