JPH04208246A - Metal soup and thermoplastic resin composition containing the same - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition remarkably improved in moldability and heat stability by blending a basic metal soap of the group II produced by a dry type direct method with a thermoplastic resin. CONSTITUTION:A fatty acid carboxylic acid, preferably 12-20C fatty acid monocarboxylic acid is subjected to direct heat reaction with an excess oxide or hydroxide of the group II metal (preferably Mg, Ca, Sr or Zn) of periodic table more than reaction equivalent amount to provide the metal soap having a metal content more excessive than theoretical amount. The excessive ratio of metal content is 0.1-1.0mol, preferably 0.1-0.8mol. The metal soap is blended with a thermoplastic resin such as chlorine-containing resin, polyolefin resin or ABS resin at an amount of 0.01-5 pts.wt., preferably 0.03-3.0 pts.wt. based on 100 pts.wt. thermoplastic resin.

Description

[Detailed description of the invention] [Industrial application field]

The present invention is a metal soap produced by the so-called dry direct method, in which an aliphatic carboxylic acid and an oxide or hydroxide of a Group I metal of the periodic table are directly reacted by heating. This invention relates to a metal soap in excess of the amount, and further relates to a thermoplastic resin composition in which the processing moldability and thermal stability of the thermoplastic resin are significantly improved by adding this metal molding to the thermoplastic resin. It is.

[Conventional technology]

Conventionally, various metal soaps have been used along with phenolic antioxidants, organic phosphoric acid antioxidants, etc. to improve thermal stability, processability, etc. during the molding process of thermal 6J plastic resins. . Typical metal soaps currently used include calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, lithium stearate, and the like. However, even when using these conventional metal soaps, there are problems such as eye stain in the mold, plate-out phenomenon on the mold wall or processing machine wall, and clogging phenomenon in the screen during molding. At present, problems such as the extrusion (embossment) phenomenon of additives that occur on the surface of products have not yet been sufficiently resolved.

[Problems to be solved by the invention]

Therefore, as a means to solve these problems, attempts have been made to add various lubricants, but satisfactory results have not yet been obtained. Therefore, currently, when such a problem occurs,
The operation of the molding machine was temporarily stopped, the area was cleaned, and then restarted. Due to such measures, continuous molding cannot be performed for a long time, which not only reduces work efficiency but also leads to a decline in the quality of the molded product in some cases, so measures should be taken to resolve this issue as soon as possible. It was requested that the establishment of

[Means to try to solve the problem]

As a result of intensive research in order to solve these problems, the inventors of the present invention have found that a metal soap of group Ⅰ of the periodic table produced by a dry direct method has a metal content that is equal to the theoretically calculated amount. By developing a metal soap with a higher excess content (a type of basic metal soap, hereinafter referred to as basic metal soap), and adding this metal soap to a thermoplastic resin instead of the conventional metal soap, the above-mentioned problems can be achieved. The present invention has been completed by successfully eliminating the troubles, improving processing and forming properties, and preventing deterioration in product quality.

[Structure of the invention]

The basic metal soap of the present invention is produced by heating an aliphatic monocarboxylic acid (hereinafter referred to as fatty acid) and an oxide or hydroxide of a metal of group Ⅰ of the periodic table (hereinafter referred to as metal inorganic compound). A type of known method for producing metal soaps obtained by direct reaction, the so-called dry direct method (also known as the melting method)
The basic metal soap of the present invention differs from known metal soaps in that while known metal soaps react with a fatty acid and a reaction equivalent amount of a metal inorganic compound, the basic metal soap of the present invention reacts with a fatty acid and a reaction equivalent amount of a metal inorganic compound. It is obtained by adding a metal inorganic compound in excess of the reaction equivalent and completely incubating the reaction product so that it becomes transparent, and the metal content, melting point, and acid value of the product are naturally different. be. The excess ratio of the metal content of the basic metal soap of the present invention is 0.
The amount is 1 to 1.0 mol, preferably 0.1 to 0.8. If it is less than 0.1 mol, there is not much difference in performance from conventional metal soaps, and if it is more than 1.0 mol, the melt of the product will not become transparent and unreacted metal inorganic compounds will remain, which is not preferable. The fatty acid that is the raw material for the basic metal soap of the present invention has 1 carbon number.
One or more natural or synthetic saturated or unsaturated monocarboxylic acids having from 2 to 30 L, which may have a side chain, hydroxyl group, ketone group, aldehyde group, eboxy group, etc. in the structure. Typical examples include lauric acid, myristic acid, palmitic acid, stearic acid, alagic acid, heptadecylic acid, behenic acid, oleic acid, and elaidin. Examples include erucic acid, linoleic acid, liluic acid, ricinoleic acid, hydroxystearic acid, montanic acid, isostearic acid, epoxystearic acid, and the like. Further, a part thereof may be replaced with a carboxylic acid or dicarboxylic acid other than the aliphatic monocarboxylic acid. The metal constituting the basic metal soap of the present invention is one or more metals of group Ⅰ of the periodic table, specifically ①a alkaline earth metals and nb zinc group metals, preferably Mg,
They are Ca and Zn. The thermoplastic resin composition of the present invention is a composition obtained by adding the above-mentioned basic metal soap to a thermoplastic resin, and exhibits moldability that cannot be obtained with conventional thermoplastic resin compositions containing metal soap. . That is, the metal soap of the present invention containing an excessive amount of metal has a melting point significantly higher than that of conventional metal soaps and soaps, as shown in the examples below, and therefore has a lubricating effect in thermoplastic resins molded at high temperatures. In addition, it can be expected to improve the mold release effect (1). In addition to the basic metal soaps produced by the direct dry method of the present invention, basic metal soaps can also be produced by the wet precipitation method.
When the basic metal soap produced by this wet precipitation method is thermally melted, the metal inorganic compound in the basic part is separated and a precipitate is formed. Furthermore, if basic metal soap produced by this wet precipitation method is added to a thermoplastic resin and molded, not only will the eye stain phenomenon in the mold not be improved at all, but on the contrary, it will cause problems on the screen. It has the disadvantage that clogging phenomenon occurs strongly and promotes trouble, and it cannot be compared in terms of performance with the basic metal soap of the present invention. The thermoplastic resin used in the present invention refers to a resin having good thermoplasticity, such as chlorine-containing resins such as polyvinyl chloride, chlorinated polyvinyl chloride, chlorinated polyethylene, vinyl chloride/vinyl acetate copolymers, and the like. Copolymers and polymer blends of resins and other resins, =7- Polyolefin resins include low-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene and copolymers with each other, α-olefin, or other resins. Coalescing and polymer blends. Copolymers and polymer blends of various polyamide resins and other resins. Copolymers and polymer blends of various polyester resins and other resins. Various ABS resins and copolymers of other resins, and polymers. Blends. Examples include various polyacetal resins and copolymers with other resins, polymer blends, and other various engineering plastics.The amount of basic metal soap used in the composition of the present invention is based on 100 parts by weight of the thermoplastic resin. , 0.01 to 5 parts by weight, preferably 0.03 to 3.0 parts by weight. For example, plasticizers, fillers, stabilizers, antioxidants (phenol-based, organic phosphorus-based, etc.), ultraviolet absorbers (bezotriazole-based, benzophenone-based, hindered amine-based), pigments, lubricants, antistatic agents, antifogging agents. , flame retardants, antibacterial agents, antifungal agents, foaming agents, epoxy compounds,
Processing aids and the like may be added as appropriate.

【Example】

The present invention will be explained in more detail below by giving examples. Example 1 100g of stearic acid (NV-200) was heated to 130°C, 16.76g of zinc oxide was gradually added while stirring, the temperature was lowered to 150°C, and stirring was continued for 20 minutes to melt. A clear basic zinc stearate with a zinc content of 11.86% by weight and a melting point of 130° C. with an excess of 0.15 mol ZnO was obtained. For reference, the zinc content of zinc stearate reacted equivalently with zinc oxide corresponding to the NV of stearic acid is 1
The content was 0.47% by weight, and the melting point was 123°C. 19 = Example 2 12-hydroxystearic acid (NV-179) 100
After heating 120°C of magnesium oxide to 120°C, 0.6g of magnesium oxide I2O was gradually added with stirring, and after the entire addition was completed, the temperature was raised to 165°C, stirring was continued for 20 minutes to complete the reaction, and the magnesium content was 5. A basic magnesium 12-hydroxystearate of 8% by weight, melting point 22.8 DEG C., transparent when melted, with an excess of 0.44 mol MgO was obtained. For reference, the NV of this 12-hydroxystearic acid
Magnesium 12-hydroxystearate, which was equivalently reacted with magnesium oxide corresponding to the above, had a magnesium content of 3.7% by weight and a melting point of 123°C. Example 3 Lauric acid (NV=280) 100g7il-125°C
21.10g of calcium hydroxide while stirring.
was gradually added, the temperature was increased to 175°C, stirring was continued for 20 minutes to complete the reaction, and the calcium content was 10.
03 double lance shape, melting point 171°C, transparent when melted, 0.
,,IL Basic calcium laurate with 5 mol CaO excess was obtained. For reference, calcium laurate, which was equivalently reacted with calcium hydroxide corresponding to the NV of lauric acid, had a calcium content of 9.13% by weight, a melting point of I, and 55°C. Example 4 After heating 100 g of behenic acid (NV-167,26) to 130°C, 45 g of magnesium oxide 11y was gradually added with stirring to react, and the temperature was gradually increased to 175°C.
shall be. The reaction was completed by stirring until the melt became transparent, and the magnesium content was 6.34% by weight and the melting point was 210°C.
A basic magnesium behenate with a 0.8 mol MgO excess was obtained. For reference 1. Magnesium behenate, which was equivalently reacted with magnesium oxide corresponding to the NV of behenic acid, had a magnesium content of 3.15% by weight and a melting point of 119°C. Example 5 The following formulation was kneaded for 5 minutes using a 6-inch test roll adjusted to 160°C to form a sheet with a thickness of 0.3 mm. A portion of this sheet was placed in a gear oven adjusted to 170°C to compare thermal stability, and the remaining sheet was pressed for 5 minutes in a heat press adjusted to 170°C to form a 1mm x 1' sheet. The transparency of the sheet and the ejection (embossment) phenomenon on the surface after being immersed in a constant temperature water bath adjusted to 70° C. for 24 hours were observed. The results were evaluated using the scores shown in Table-1 and shown in Table-2.・ <Formulation> PvC (P・1000) 100 Part by weight DOI) (plasticizer) 40 Epoxidized soybean oil 2 Organic phosphate ester 0.5 Zinc stearate
0.4 〃Metal soap (Table-2)
0.6 7 Table-1 (Rating) Table-2 (Results of Example-5) Example 6 The following formulation was kneaded for 7 minutes using a test roll adjusted to 180°C to create a 0.5 mm thick sheet. . This sheet was heat-pressed at each temperature shown in Table 3 using a heat press adjusted to 240°C to form a sheet with a thickness of In+n+, and the degree of coloration of the sheet was measured using a photovolt reflectance meter manufactured by Toyo Seiki. , is listed in Table 3 as my own seat. (The higher this value is, the better the thermal stability is.) <Formulation> Polypropylene (MPR=0.3) 100
Part by weight Finely powdered talc 43 Titanium oxide 2 Irganox 1010 0.05 // Metal soap (Table 3)
' 0.2 - 15 Example 7 The following formulation was heated in a 26φmm XL/D-16.5 single-screw extruder (cylinder temperature: C, = 150°C, C9 = 210°C
, die temperature: 230°C, rotation speed: 40 rpm 1 screen: 200 mesh, mold size = 30 mmX l
Continuous extrusion was carried out for 12 hours at 1 mm), and the amount of L1 tar attached to the mold and the amount of clogging and ill on the screen were visually measured, and the motor load of the extruder was recorded. The results are shown in Table-4. Blend> Polypropylene L/N (MFR=0.3) 100
Part by weight Finely powdered talc 43
Titanium oxide 2 Irganox 1010 0.1 Ultranox 626 0.05 Metal soap (Table 4)
0.3 〃Example 8 The following formulation was heated to 160℃? The mixture was kneaded for 8 minutes using a 6-inch test roll adjusted in this manner to form a sheet with a thickness of 1.2 mm. The peelability from the test roll at this time was observed and is shown in Table 5. This sheet was heat-pressed in a heat press adjusted to 240°C for 2 minutes, 5 minutes, and 10 minutes to prepare sheets with a thickness of 1 mm. The results are shown in Table 5. Blend> ABS resin (Diapet 3001MT () 100 parts by weight

Claims (1)

[Claims] 1. Obtained by directly heating and reacting an aliphatic carboxylic acid with an oxide or hydroxide of a Group II metal in the periodic table, and having a metal content in excess of the theoretically calculated amount. A metal soap from Group II of the periodic table, characterized by: 2. The metal soap according to claim 1, wherein the excess metal content is in the range of 0.1 to 1.0 mol. 3. The metal soap according to claim 1, wherein the metal constituting the metal soap is one or more metals selected from Mg, Ca, Sr, or Zn. 4. The carboxylic acid constituting the metal soap has 12 to 3 carbon atoms.
1 of the carboxylic acids selected from 0 aliphatic monocarboxylic acids
The metal soap according to claim 1, which is more than 100% of the metal soap. 5. A thermoplastic resin composition in which 0.01 to 5 parts by weight of one or more metal soaps described in any of claims 1 to 4 are added to 100 parts by weight of the thermoplastic resin. . 6. The thermoplastic resin composition according to claim 5, wherein the thermoplastic resin is a chlorine-containing resin. 7. The thermoplastic resin composition according to claim 5, wherein the thermoplastic resin is a polyolefin resin. 8. The thermoplastic resin composition according to claim 5, wherein the thermoplastic resin is an ABS resin.