JPH0729975B2 - Metal soap and thermoplastic resin composition containing the same - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention is a metal soap produced by a so-called dry direct method, in which an aliphatic carboxylic acid and an oxide or hydroxide of a Group II metal of the periodic table are directly reacted with heating, and the amount of metal contained is theoretical The present invention relates to a metal soap in excess of the amount thereof, and further relates to a thermoplastic resin composition in which the workability and heat stability of the thermoplastic resin is remarkably improved by adding the metal molded product to the thermoplastic resin. Is.

[Prior art]

Conventionally, various metal soaps have been used together with a phenol-based antioxidant, an organic phosphoric acid-based antioxidant and the like in order to improve thermal stability, processability and the like when molding a thermoplastic resin. Typical metal soaps currently used are calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, lithium stearate and the like. However, even if these conventional metal soaps are used, the eye-dip phenomenon in the mold, the plate-out phenomenon to the mold wall or the machine wall, the clogging phenomenon on the screen, At present, it cannot be said that the problems such as the discharge (embossing) phenomenon of the additive generated on the surface of the molded product have been sufficiently solved.

[Problems to be Solved by the Invention]

Therefore, addition of various lubricants has been attempted as a means for solving these problems, but satisfactory results have not yet been obtained. Therefore, at present, when such trouble occurs,
The molding machine is temporarily stopped, the area is cleaned, and then restarted. To take such measures,
Since continuous molding for a long time cannot be performed, workability is deteriorated, and in some cases, the quality of a molded product is deteriorated. Therefore, it has been demanded to establish a measure to solve this early.

[Means for solving problems]

As a result of intensive studies to solve such problems, the present inventors have found that it is a Group II metal of the Periodic Table produced by the dry direct method, and the content of the metal is 0.1 to more than the reaction equivalent. 1.0
By developing a metal soap containing a molar excess (a kind of basic metal soap, hereinafter referred to as basic metal soap), and replacing this metal soap with a conventional metal soap and adding it to a thermoplastic resin, The present invention has been completed by eliminating the various problems described above, improving the workability and forming, and preventing the deterioration of product quality.

[Constitution of the invention]

The basic metal soap of the present invention comprises an aliphatic monocarboxylic acid (hereinafter referred to as a fatty acid) and an oxide or hydroxide of a Group II metal of the periodic table (hereinafter referred to as a metal inorganic compound) according to a known production method. Although it is obtained by heating and reacting by a dry direct method (also known as melting method), which is different from known metal soaps, the difference between known metal soaps is that fatty acid reacts with a reaction equivalent of a metal inorganic compound. On the other hand, the basic metal soap of the present invention is obtained by adding a metal inorganic compound in excess of a reaction equivalent to a fatty acid and completely reacting the reaction product to make it transparent. Metal content, melting point,
The acid number is naturally different. The excess metal content of the basic metal soap of the present invention is 0.1
~ 1.0 mol, preferably 0.1-0.8. Below 0.1 mol, there is not much difference in performance from conventional metal soap, and 1.
When it is 0 mol or more, the melt of the product is not transparent, and unreacted metal-inorganic compound remains, which is not preferable. The fatty acid used as the raw material of the basic metal soap of the present invention has 12 carbon atoms
One or more kinds of natural or synthetic saturated or unsaturated monocarboxylic acid having 30 to 30 may have a side chain, a hydroxyl group, a ketone group, an aldehyde group, an epoxy group or the like in the structure. As typical examples thereof, lauric acid, myristic acid, palmitic acid, stearic acid, araginic acid, heptadecyl acid, behenic acid, oleic acid, elaidic acid, ericic acid,
Examples thereof include linoleic acid, linoleic acid, ricinoleic acid, hydroxystearic acid, montanic acid, isostearic acid, and epoxystearic acid. Further, a part thereof may be replaced with a carboxylic acid or a dicarboxylic acid other than the aliphatic monocarboxylic acid. The metal constituting the basic metal soap of the present invention has a periodic table
One or more Group II metals, specifically IIa alkaline earth metals and IIb zinc group metals, preferably Mg, Ca, Zn
Is. The thermoplastic resin composition of the present invention is a composition obtained by adding the above basic metal soap to a thermoplastic resin, and exhibits molding processability that cannot be obtained by a conventional thermoplastic resin composition to which a metal soap is added. . That is, since the melting point of the metal soap of the present invention containing an excessive amount of metal is remarkably higher than that of the conventional metal soap, as shown in Examples below, in a thermoplastic resin for high-temperature molding,
It is possible to expect an improvement in the sliding effect and the releasing effect. In addition to the dry direct method basic metal soap of the present invention, a basic metal soap can be produced by a wet precipitation method,
When the basic metal soap produced by this wet precipitation method is heated and melted, the metal inorganic compound in the basic portion is separated, and precipitation occurs. In addition, when the basic metal soap produced by this wet precipitation method is added to the thermoplastic resin and molding is performed, not only the phenomenon of eye blemishes in the mold cannot be improved, but conversely, the phenomenon of clogging of the screen occurs. Occurs, which is a problem that promotes troubles, and is not comparable in performance to the basic metal soap of the present invention. The thermoplastic resin used in the present invention is a resin having thermoplasticity, and examples of the chlorine-containing resin include polyvinyl chloride, chlorinated polyvinyl chloride, chlorinated polyethylene, vinyl chloride / vinyl acetate copolymers and other resins. Examples of copolymers and polymer blends with resins and polyolefin resins include low-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene and resins, copolymers with α-olefin or other resins, and polymer blends. Copolymers and polymer blends with various polyamide resins and other resins. Copolymers and polymer blends with various polyester resins and other resins. Various ABS resin and other resin copolymers and polymer blends. Examples include various polyacetal resins, copolymers with other resins, polymer blends, and various engineering plastics. The amount of the basic metal soap used in the composition of the present invention is 0.01 to 5 parts by weight, preferably 0.03 to 3.0 parts by weight, based on 100 parts by weight of the thermoplastic resin. The thermoplastic resin composition of the present invention contains necessary additives other than the above basic metal soaps, such as plasticizers, fillers, stabilizers, antioxidants (phenol-based, organic phosphorus-based, etc.) and ultraviolet absorbers. (Bezotriazole type, benzophenone type, hindered amine type), pigment, lubricant, antistatic agent, antifogging agent, flame retardant, antibacterial agent, antifungal agent, foaming agent, epoxy compound, processing aid, etc. Good.

【Example】

Hereinafter, the present invention will be described more specifically with reference to examples. Example 1 100 g of stearic acid (NV = 200) was heated to 130 ° C., 16.76 g of zinc oxide was gradually added with stirring, and then the temperature was changed to 150 ° C.
When the solution is heated for 20 minutes and is melted by stirring, it is transparent and has a zinc content of 11.86% by weight, a melting point of 130 ° C., 0.15 MgO · Mg (C ₁₇ H
_{As a} zinc oxide represented by ₃₅ COO) ₂ , a 0.15 molar excess of basic zinc stearate was obtained. For reference, it was obtained by carrying out an equivalent reaction with zinc oxide corresponding to the NV of this stearic acid.
The zinc content of the normal salt (normal salt) zinc stearate represented by Mg (C ₁₇ H ₃₅ COO) ₂ is 10.47% by weight and the melting point is 1.
It was 23 ° C. Example 2 After heating 100 g of 12-hydroxystearic acid (NV = 179) to 120 ° C., 10.06 g of magnesium oxide was gradually added to the mixture while stirring, and after the total amount was added, the temperature was raised to 165 ° C. and stirring was continued for 20 minutes. To complete the reaction, magnesium content 5.8% by weight, melting point 228 ° C, transparent when melted, 0.4MgO ・ Mg (C
_{As a} magnesium oxide represented by ₆ H ₁₃ .CH (OH) .C ₁₀ H ₂₀ .COO) ₂ , 0.44 mol excess of basic 12-hydroxystearate was obtained. For reference, Mg (C ₆ H ₆₎ obtained by reacting an equivalent amount of magnesium oxide corresponding to the NV of 12-hydroxystearic acid was used.
_The magnesium salt of magnesium 12-hydroxystearate as a normal salt (normal salt) represented by ₁₃ · CH (OH · C ₁₀ H ₂₀ · COO) ₂ was 3.7% by weight, and the melting point was 143 ° C. Example 3 100 g of lauric acid (NV = 280) was heated to 125 ° C., 21.10 g of calcium hydroxide was gradually added with stirring, and the temperature was changed to 175.
Up to ℃ and continue stirring for 20 minutes to complete the reaction,
As a calcium oxide represented by 0.115CaO · Ca (C ₁₁ H ₂₃ COO) ₂ , which had a calcium content of 10.03% by weight and a melting point of 171 ° C. and was transparent, 0.115 mol excess of basic calcium calcium laurate was obtained. For reference, this lauric acid NV
Ca obtained by the equivalent reaction with calcium hydroxide corresponding to
The normal salt (normal salt) represented by (C ₁₁ H ₂₃ COO) ₂ has a calcium content of 9.13% by weight of calcium laurate.
The melting point was 155 ° C. Example 4 After heating 100 g of behenic acid (NV = 167.26) to 130 ° C., 11.45 g of magnesium oxide was gradually added thereto with stirring to cause reaction, and the temperature was gradually raised to 175 ° C. Stir until the melt becomes transparent to complete the reaction and
6.34% by weight, melting point 210 ℃, 0.8MgO ・ Mg (C ₂₁ H ₄₃ COO) ₂
As a magnesium oxide represented by the formula, 0.8 molar excess of basic magnesium behenate was obtained. For reference, the magnesium content of magnesium behenate of the normal salt (normal salt) represented by Mg (C ₂₁ H ₄₃ COO) ₂ obtained by reacting with an equivalent amount of magnesium oxide corresponding to the NV of behenic acid is 3.
The content was 15% by weight and the melting point was 119 ° C. Example 5 The following composition was kneaded with a 6-inch test roll adjusted to 160 ° C. for 5 minutes to prepare a 0.3 mm-thick sheet. A part of this sheet was placed in a gear oven adjusted to 170 ° C, the thermal stability was compared, and the remaining sheet was pressed with a hot press adjusted to 170 ° C for 5 minutes to form a 1 mm thick sheet. And the phenomenon of ejection (embossing) on the surface after immersion in a constant temperature water bath adjusted to 70 ° C for 24 hours.
The results were evaluated by the scores shown in Table-1 and shown in Table-2. <Compound> PVC (= 1000) 100 parts by weight DOP (plasticizer) 40〃 Epoxidized soybean oil 2〃 Organic phosphite 0.5〃 Zinc stearate 0.4〃 Metal soap (Table-2) 0.6〃 Example 6 The following composition was kneaded with a test roll adjusted to 180 ° C. for 7 minutes to prepare a 0.5 mm-thick sheet. This sheet was hot-pressed at 240 ° C and hot-pressed at each temperature shown in Table-3.
The sheet was formed into a sheet having a thickness of 1 mm, and the degree of coloring of the sheet was measured using a photovolt reflectance meter manufactured by Toyo Seiki, and the whiteness is shown in Table-3. The larger this value, the better the thermal stability.) <Compound> Polypropylene (MFR = 0.3) 100 parts by weight Fine powder talc 43 〃 Titanium oxide 2 〃 Irganox 1010 0.05 〃 Metal soap (Table-3) 0.2 〃 Example 7 A single screw extruder having the following composition of 26φ mm and L / D = 16.5 (cylinder temperature: C ₁ = 150 ° C., C ₂ = 210 ° C., die temperature: 230 ° C.,
Rotation speed: 40 rpm, screen: 200 mesh, mold size: 3
(0 mm x 1 mm) was continuously extruded for 12 hours, and the amount of adhesion of the resin to the mold and the amount of clogging to the screen were measured, and the motor load of the extruder was recorded. The results are shown in Table-4. <Compound> Polypropylene (MFR = 0.3) 100 parts by weight Fine powder talc 43 〃 Titanium oxide 2 〃 Irganox 1010 0.1 〃 Ultranox 626 0.05 〃 Metal soap (Table-4) 0.3 〃 Example 8 The following composition was kneaded with a 6-inch test roll adjusted to 160 ° C. for 8 minutes to prepare a 1.2 mm-thick sheet. The peelability from the test roll at this time was observed and shown in Table-5. This sheet was heat-pressed for 2 minutes, 5 minutes, and 10 minutes with a heat press adjusted to 240 ° C to prepare each sheet with a thickness of 1 mm, and the whiteness of this heat-discolored sheet was measured by Toyo Seiki Photobolt reflection. Measure with a rate measuring machine and display the results.
5 shows. <Compound> ABS resin (Diapet 3001MH) 100 parts by weight Brominated flame retardant (DB-101) 12〃 Antimony trioxide 5〃 Metal soap (Table-5) 0.5〃

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C07F 3/02 Z 7457-4H 3/04 7457-4H 3/06 7457-4H C08K 5/09 KAR (72) Tsunenosuke Hiramatsu 1-6-3 Nihombashi Muromachi, Chuo-ku, Tokyo (56) References JP-A-55-136244 (JP, A) JP-A-1-71836 (JP, A)

Claims (6)

[Claims] 1. An aliphatic monocarboxylic acid having 12 to 30 carbon atoms.
A metal soap obtained by heating and reacting one or more of them with an oxide or hydroxide of a Group II metal of the periodic table by a dry direct method, the metal content of which is higher than the corresponding equivalent weight.
Represented by the rational formula [1] containing 0.1 to 1.0 molar excess,
A metal soap characterized by being a viscous material which is transparent when melted by heat. Rational Formula [1] αMO · M (OOCR) ₂ [wherein α is an integer of 0.1 to 1.0, M is a divalent metal of Group II of the periodic table, and R is the number of carbon atoms. It represents 11 to 29 saturated or unsaturated alkyl groups. ] 2. The metal soap according to claim 1, wherein the metal is one or more metals selected from Mg, Ca, Sr or Zn. 3. To 100 parts by weight of a thermoplastic resin, 0.01 to 5 parts by weight of one or more kinds of the metal soaps described in any one of claims 1 and 2 are added. Thermoplastic resin composition. 4. The thermoplastic resin composition according to claim 3, wherein the thermoplastic resin is a chlorine-containing resin. 5. The thermoplastic resin composition according to claim 3, wherein the thermoplastic resin is a polyolefin resin. 6. The thermoplastic resin composition according to claim 3, wherein the thermoplastic resin is an ABS resin.