JPS6365111B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a lubricant-containing thermoplastic resin composition comprising reacting one or more of monohydric alcohols, monohydric carboxylic acids, or acid acids with an organic diisocyanate. Monohydric alcohols represented by the general formula R ₁ OH (in the formula R ₁ represents an alkyl group, alkenyl group, or aryl group having 10 to 26 carbon atoms), or monohydric alcohols represented by the general formula R ₂ COOH (in the formula R ₂ represents a carbon number 15 to 30 alkyl, aryl, or alkenyl groups) or the general formula R ₃ CONH ₂
(In the formula, R ₃ represents an alkyl group, an alkenyl group, or an aryl group having 6 to 22 carbon atoms.) A novel method consisting of reacting one or more acid amides with a specific organic diisocyanate. The present invention relates to a thermoplastic resin composition containing a lubricant. In general, thermoplastic resins are used for purposes such as (1) preventing the generation of frictional heat during mixing and kneading, (2) improving the fluidity of the resin during molding, and (3) preventing the resin from sticking to the walls of machines such as molds. Lubricants are used in For example, thermoplastic resins made of polar monomers such as vinyl chloride resins have strong intermolecular cohesive forces and poor fluidity during molding. For this reason, higher alcohol,
Attempts have been made to add various lubricants such as fatty acids. However, the addition of these lubricants may cause bleeding, bloom, extraction, migration, volatilization, strength reduction, etc. unless a lubricant with the same polarity and good compatibility as the resin to which the lubricant is added is chosen. Become. Thermoplastic polyurethane resin, which has been attracting attention as a thermoplastic elastomer in recent years, has excellent abrasion resistance, cold resistance, solvent resistance, and toughness. , sports shoe soles, hoses, tubes, films, seats, belts, wire sheathing,
It has applications in an extremely wide range of fields, including automobile parts. However, like vinyl chloride resin, it has drawbacks such as fluidity during molding, thermal stability, and adhesion to metal surfaces such as molds, barrels, screws, rolls, etc., so there are no lubricants that can improve these points. desired. For this reason, the present inventors used conventionally known lubricants,
For example, aliphatic hydrocarbons, fatty acids, aliphatic alcohols, acid amides, metal soaps, and aliphatic esters have been investigated singly or in various combinations, but in all cases, they have poor compatibility, resulting in problems such as bleeding, blooming, and reduced strength. A phenomenon has occurred. Therefore, the present inventors further conducted extensive research into lubricants that would improve the above-mentioned drawbacks, and found that a reaction product of one or more specific monohydric alcohols, monohydric carboxylic acids, or acid amides with diisocyanate was found to be the most prominent. The present inventors have discovered that this material has a lubricious effect, and have completed the present invention. That is _, the present invention provides: a thermoplastic _resin ();
Monohydric alcohols represented by (I-B) general formula R ₂ COOH (wherein R ₂ is a carbon number of 4 to 45
monovalent carboxylic acids represented by the general formula R ₃ CONH ₂ (representing an alkyl group, aryl group _, or alkenyl group);
(2) 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and (b) 4,4'-diphenylmethane diisocyanate, One or more types selected from 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, o-, m-, or p-xylylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, and hexamethylene diisocyanate. The present invention relates to a lubricant-containing thermoplastic resin composition containing a lubricant () obtained by reacting an organic diisocyanate of the present invention with an organic diisocyanate. The monohydric alcohols represented by the general formula R ₁ OH (wherein R ₁ represents an alkyl group, alkenyl group, or aryl group having 10 to 26 carbon atoms) of component (A) are:
For example, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachyl alcohol, behenyl alcohol,
Examples include carunarabil alcohol, ceryl alcohol, and the like, and the alcohol is selected from one type or a mixture of two or more of these. The monovalent carboxylic acid represented by the general formula R ₂ COOH (in the formula R ₂ represents an alkyl group, alkenyl group, or aryl group having 15 to 30 carbon atoms) of component (B) is, for example, palmitic acid, margarine, etc. Acid, stearic acid, n-menadecylenic acid, aragidic acid, n-henicosanoic acid, behenic acid, n-tricosanoic acid, lignoceric acid, cerotic acid, n-heptacosanoic acid, montanic acid, n-nonacosanoic acid, melisic acid, n-hentriacontanoic acid, Linderic acid,
tuzunic acid, fisetoleic acid, myristoleic acid,
Examples include zomaric acid, petroselic acid, oleic acid, elaidic acid, gadolenic acid, gondolic acid, erucic acid, branzic acid, linoleic acid, linolenic acid, moroctic acid, sardine acid, and nisic acid, one or two of these. Selected from a mixture of more than one species. Furthermore, the acid amide represented by the general formula R ₃ CONH ₂ (in the formula, R ₃ represents an alkyl group, alkenyl group, or aryl group having 6 to 22 carbon atoms) of component (A-C) is caprylic acid amide, caprylic acid amide, caprylic acid amide, caprylic acid amide, caprylic acid amide, etc. Acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, arachidic acid amide, behenic acid amide, palmitoleic acid amide, oleic acid amide, eicosenoic acid amide, erucic acid amide, elaidic acid amide, linoleic acid amide , linolenic acid amide, lysinoleic acid amide, etc., or a mixture of two or more thereof. Also, monohydric alcohol, monohydric carboxylic acid,
Two or more kinds of acid amides may be used in combination. Examples of the organic diisocyanate (b) used in the present invention include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5
-naphthylene diisocyanate, o-, m-, or p-xylylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, etc., and one type or a mixture of two or more of these may be used. Further, a portion of the diisocyanate used in the present invention can be replaced with a small amount of trifunctional or higher functional polyisocyanate for mixed use. An example of the lubricant of the present invention is given by a formula using 4,4'-diphenylmethane diisocyanate (hereinafter referred to as MDI): (A) Monohydric alcohol MDI (I-B) Monovalent carboxylic acid + MDI (I-B′) Unsaturated carboxylic acid + MDI (I-C) Monovalent acid amide + MDI etc., but are not limited to these. The method for producing a lubricant of the present invention includes monohydric alcohol,
One or two monohydric carboxylic acids or acid amides
It is synthesized by heating and melting 1 mole of seeds or more to a temperature above the melting point and adding 0.5 mole of organic diisocyanate. Further, in order to exhibit the desired performance of the lubricant of the present invention, it is added in an amount of 0.1 to 5.0 parts by weight, more preferably 0.2 to 3.0 parts by weight, per 100 parts by weight of the resin. be. If the amount is less than 0.1 part by weight, the lubricating effect will hardly be observed;
If the amount exceeds 5.0 parts by weight, adverse effects such as a bleeding phenomenon and a decrease in strength will occur in the resulting resin composition. The lubricant according to the present invention may be added to a synthetic resin by mixing and adding it to pellets, flake powder, or a resin compound during the resin manufacturing process or resin processing. Furthermore, as necessary, lubricants such as aliphatic hydrocarbons, higher fatty acids, aliphatic alcohols, fatty acid amides, metal soaps, fatty acid esters, pigments, dyes, flame retardants, fillers, antistatic agents, plasticizers, and antioxidants are added. It is also possible to use additives, weathering stabilizers, etc. In the present invention, examples of the thermoplastic resin with which the lubricant is mixed include thermoplastic polyurethane resin, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, and polyvinyl fluoride. Vinylidene chloride, brominated polypropylene, vinyl chloride
Vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-acronitrile copolymer, polyethylene, polypropylene, polystyrene, polyvinyl acetate, acrylic Examples include resins, acrylonitrile-butadiene-styrene copolymers, linear polyesters, polyacetals, polyamides, polycarbonates, etc. alone or in blends, but they are particularly preferably used as lubricants for thermoplastic polyurethane resins or vinyl chloride resins. The vinyl chloride resins mentioned here include, for example, Kanevinyl (Jongbuchi Chemical Products), Nipporizto (Chitsuso Products), Denka Vinyl (Denki Kagaku Kogyo Products), Zeon PVC (Nippon Zeon Products), Vinica (Mitsubishi Monsanto Kasei Products), Vinicron. (Mitsui Toatsu Chemical Products), Aron PVC (Toagosei Chemical Products), Sumiritz (Ouyu Chemical Products), etc. Further, the thermoplastic polyurethane resin is obtained by reacting a polymer diol component with a diisocyanate, and a chain extender can also be used in combination. Examples of the polymer diol component include polyester diol, polyether diol, polylactone diol, polyolefin diol, and the like. The number average molecular weight of polymer diol is 300~
6000 is preferred. Dicarboxylic acids and diols are used to make polyester diols, and examples of dicarboxylic acids include glutaric acid, adipic acid, succinic acid, suberic acid, sebacic acid, methyladipic acid, pimelic acid, phthalic acid, and terephthalic acid. acid,
Examples of diols include isophthalic acid, maleic acid, fumaric acid, and the like. Examples of diols include ethylene glycol, 1,4-butanediol, 1,6 hexanediol, propylene glycol, diethylene glycol, and neopentyl glycol. Polyether diols include polyethylene glycol, polypropylene glycol,
Examples include polytetramethylene glycol.
Examples of polylactone diols include polyε-caprolactone diols. Examples of the polyolefin diol include polybutadiene diol. Examples of the chain extender include diamines such as ethylene diamine and propylene diamine in addition to the diols exemplified as components of polyester diol. Examples of diisocyanates include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2-6-tolylene diisocyanate, 1-5-naphthylene diisocyanate, o
-, m- or p-xylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, etc., or a mixture of two or more thereof can be selected. EXAMPLES Below, in order to explain the present invention more specifically, Examples will be given and described in detail, but the present invention is not limited thereto. Synthesis example 1 Stearyl alcohol (trade name Calcol 80,
(manufactured by Kao Soap Co., Ltd.) 54g in a flask equipped with a stirrer.
Melts at a temperature of 80°C. Next, 4,4'-diphenylmethane diisocyanate (trade name Millionate)
25 g of MT (manufactured by Nippon Polyurethane Kogyo Co., Ltd.) was gradually added. The temperature of the reaction mixture rises to 130°C due to the exotherm, but stirring is continued for about 2 hours. After 2 hours, the reactants were poured into a vat, cooled and crushed, and a lubricant was added.
I got 1. Synthesis Example 2 A lubricant-2 was obtained in the same manner as in Synthesis Example 1 except that 17.4 g of 2,4-tolylene diisocyanate was used in place of 4,4'-diphenylmethane diisocyanate. Synthesis Example 3 Lubricant-3 was prepared in the same manner as in Synthesis Example 1 except that 56.9 g of stearic acid (Lunatsuku S-30, manufactured by Kao Soap Co., Ltd.) was used instead of stearyl alcohol.
I got it. Examples 1 to 4 Molar ratio of polybutylene adipate diol with a number average molecular weight of 2000 and 1,4-butanediol 1:2
A polyurethane resin obtained by reacting a mixture of and 4,4'-diphenylmethane diisocyanate.
To 100 parts by weight, lubricant-1 and lubricant-2 obtained in Synthesis Examples 1 and 2 were added in the amounts shown in Table 1, and the mixture was heated in a 30 mm single-screw extruder at a temperature of 160° to 180°C. (L/D: 18, compression ratio 3.0) A spiral flow test was carried out on the mixture pelletized using a 3.0 oz injection molding machine under constant molding temperature conditions and mold temperature to examine fluidity. The results are shown in Table-1. The lubricant of the present invention showed excellent fluidity. Comparative Examples 1 to 2 The cases in which no lubricant was added and the cases in which stearyl alcohol was used as a lubricant were investigated under the same conditions as in Examples 1 to 4. The test results are shown in Table-1.

[Table] Examples 5 to 7 Epoxidized soybean oil 5.0 parts per 100 parts of polyvinyl chloride resin (Zeon 103EP, Nippon Zeon Co., Ltd. product)
1 part, 2.0 parts of Ca-Zn stabilizer, and 1 part each of lubricants -1, -2, and -3 obtained in Synthesis Examples 1, 2, and 3,
The mixture was kneaded at 170°C using an 8-inch mixing roll, and the peelability (lubricity) and gelation time on the roll were examined. The results are shown in Table-2. It was found from Table 2 that the lubricant of the present invention had excellent lubricity. Comparative Examples 3 to 4 The cases in which no lubricant was added and the cases in which stearyl alcohol was used as a lubricant were investigated under the same conditions as in Examples 5 to 7. Table 2 shows the test results.

【table】

[Table] Examples 8 to 10 100 weight polyurethane resins obtained by reacting a mixture of polyε-caprolactone diol with a number average molecular weight of 2000 and ethylene glycol in a molar ratio of 2:1 with 4,4'-diphenylmethane diisocyanate % of the lubricant obtained in Synthesis Examples 1 and 3.
1. Add lubricant-3 in the amounts shown in Table 3, knead on an 8-inch mixing roll at 180°C, check the peelability (lubricity) on the roll, and inject 3.0 oz of the roll blend. We investigated the occurrence of defective phenomena such as "bleed" and "bloom" on the surface of a 2 mm thick sheet produced by a molding machine, as well as its general physical properties. The results are shown in Table-3. By using the lubricant of the present invention, an excellent resin composition with no deterioration in physical properties, ie, good compatibility, and no defective phenomena was obtained. Comparative Examples 5 and 6 The cases in which no lubricant was added and the cases in which stearyl alcohol was used as a lubricant were investigated under the same conditions as in Examples 8 to 10. Table 3 shows the test results.

[Table] Example 11 In order to examine the fluidity improving effect of the lubricant according to the present invention on various resins, lubricant-1 of Synthesis Example 1 was added to 100 parts by weight of each resin in Table-4 as shown in Table-4. The mixture was mixed into pellets using an extruder, and the fluidity was measured using a melt indexer at a temperature of 200° C. and a load of 5 kg. The results are shown in Table-4. The resin containing the lubricant of the present invention exhibited excellent lubricity.

[Table] Example 12 Similarly to Synthesis Example 1, Table-5 A lubricant was synthesized by reacting 1 mole of the organic diisocyanate (b) shown in , and 100% of the polyurethane resin was prepared in the same manner as in Examples 1 to 4.
1 part by weight of the lubricant was added to each part by weight, and a spiral flow test was conducted to examine fluidity. The results are shown in Table-5.

【table】

【table】

Claims (1)

[Claims] 1 Thermoplastic resin () and (A-A) general formula R ₁ OH (wherein R ₁ represents an alkyl group, aryl group, or alkenyl group having 10 to 26 carbon atoms)
Monohydric alcohols represented by (I-B) general formula R ₂ COOH (in the formula, R ₂ has a carbon number of 15 to 30
(representing an alkyl group, aryl group, or alkenyl group), and (i-C) with the general formula R ₃ CONH ₂ (wherein R ₃ is a carbon number of 6 to 22
(2) 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,
6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, o-, m-, or p
- A lubricant-containing thermoplastic resin composition formed by reacting a lubricant () with one or more organic diisocyanates selected from xylylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, and hexamethylene diisocyanate. thing.