JPS58183736A - Thermoplastic resin composition containing lubricant - Google Patents

Abstract

PURPOSE:To prepare a resin composition containing a lubricant having remarkable lubricating effect, by compounding a base resin with a lubricant comprising the reaction product of a specific monohydric alcohol, a monobasic carboxylic acid or acid amide and a diisocyanate. CONSTITUTION:The objective composition is composed of a thermoplastic resin and a lubricant obtained by reacting ( I ) one or more compounds selected from (A) a monohydric alcohol of formula R1OH (R1 is 4-32C alkyl, aryl or alkenyl), (B) a monobasic carboxylic acid of formula R2COOH (R2 is 4-45C alkyl, aryl or alkenyl), and (C) an acid amide of formula R3CONH2 (R3 is 1-45C alkyl, aryl or alkenyl) with (II) an organic diisocyanate. For example, the reaction product of stearyl alcohol with 4,4'-diphenylmethane diisocyanate (MDI) or the reaction product of stearic acid with MDI is used as the lubricant.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides -monoalcohols, -monocarbo/acids,
・Is 1′ of acid amides! The present invention relates to a lubricant-containing thermoplastic resin composition obtained by reacting M or two or more kinds with an organic diisocyanate, and furthermore, it has the general formula R, OH (wherein R is an alkyl group having 4 to 32 carbon atoms). ,
alkenyl group, aryl group), or monohydric carboxylic acids represented by the general formula R, C00H (in the formula, R1 & 1 degree represents an alkyl group, aryl group, or alkenyl group with a prime number of 4 to 45) Or Niyabu NiR,
C0NH=(in the formula, R is an alkyl group having a vertical prime number of 1 to 45,
The present invention relates to a novel thermoplastic resin composition containing a lubricant, which is prepared by reacting one or more acid amides represented by an alkenyl group or an aryl group with a diisocyanate.

In general, thermoplastic resins are used for the following purposes: 11) Preventing the generation of frictional heat during mixing and kneading, (2) Improving the fluidity of the resin in molded parts, and (3) Preventing the resin from sticking to the walls of molds, etc. A lubricant is used.

For example, thermoplastic resins such as vinyl chloride resins, which are made of polyester monomers, have a strong intermolecular #orientation, which results in poor fluidity during molding. For this reason, male buttons for various lubricants such as ^-class alcohols and fatty acids are classified. However, the addition of these lubricants can cause problems such as bleeding, blooming, extraction, migration, and decreased volatile strength unless a lubricant with the same polarity as the resin to which it is added and a lubricant with good compatibility is selected. becomes. In recent years, thermoplastic polyurethane resin has attracted attention as a thermoplastic elastomer2 due to its excellent abrasion resistance, abrasion resistance, solvent resistance, and toughness, making it suitable for extrusion molding, injection molding, calendar processing, blow molding, etc. Depending on the various implantation processing methods, it has applications in an extremely wide range of fields such as sports shoe paper hoses, tubes, films, sheets, belts, electric wire coatings, and automobile parts.However, like vinyl chloride resin, during molding Since it has drawbacks such as fluidity, thermal stability, and adhesion to metal surfaces 11 of molds, pallets, screws, rolls, etc., a lubricant that can improve these points is desired.

For this reason, the present inventors used conventionally known lubricants, such as aliphatic hydrocarbons, fatty acids, aliphatic alcohols, acid amides,
Metal soaps and aliphatic esters were investigated individually or in combination, but even in the case of a difference between 1 and 2, AjJ phenomena such as rapid compatibility, bleeding, bloom, and a decrease in IMi degree occurred.

Therefore, as a result of intensive research into lubricants to improve the above-mentioned drawbacks, we found that a specific monohydric alcohol, -
18 or 2ai1 of carboxylic acids or acid amides
A reaction product of the above and a diisocyanate has been found to have a slippery effect over the wheel, and the present invention has been completed.

That is, the present invention provides: a thermoplastic resin; (1) a monohydric alcohol represented by the general formula R, OH (in the formula, R represents an alkyl group, an aryl group, or an alkenyl group of the vertical wood @ 4 to 62); (B) General formula R1C00H (in the formula, R8 has 4 to 45 carbon atoms)
represents an alkyl group, an aryl group, or an alkenyl group), (C) a general formula R, C0NH1 (wherein R1 has 1 to 4 carbon atoms);
A lubricant formed by reacting one or more acid amides represented by an alkyl group, aryl group, or alkenyl group (5) with (9) an organic diisocyanate. The present invention relates to a plastic resin composition containing heat.

(A+acid component is represented by the general formula Ill, OH (in the formula, R1 represents an alkyl group, alkenyl group, or aryl group having 4 to 32 carbon atoms).-*Alcohols include, for example, caprylyl alcohol, nonyl alcohol , 2-uryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachyl alcohol, behenyl alcohol, carunarabil alcohol, seryl alcohol, mericyl alcohol, among which 1al
or a mixture of two or more, preferably one having 10 to 20 carbon atoms.

General formula of component (B) R, C00) I (wherein R1 is RIA
Monovalent carboxylic acids represented by the number 4 to 450 (representing an alkyl group, an alkenyl group, or an aryl group) include, for example, capric acid, n-undecyle/#, lauric acid, n-)ridecylenic acid, myristic acid, and n-penmedecylene. San, palmitic acid, margaric acid, stearic acid, n-menadecylenic acid, aragidic acid, n-henicosanoic acid, behenic acid, n-) licosanoic acid, lignosanoic acid, serotin [
% n-hebutacanoic acid, montanic acid, n-nonacosanoic acid, melisic acid, n-hentriacontanoic acid, n-todoriacontanoic acid, n-tetratriacontanoic acid, cellograstenic acid, linderic acid, tuzunic acid, fisetlein acid, myristoleic acid, cy-1 phosphoric acid, petroselic acid,
Oleics, elaidic acid, gadolenic acid, gondola,
Erucic acid, branzic acid, linoleic acid, linoleic acid, molofnic acid, sardine acid, and nisic acid are mentioned.F5 Among these, selected from 1al or a mixture of 2 or more tanks, preferably one having 15 to 60 carbon atoms. .

Furthermore, the acid amide represented by the general formula R, C0NH, (wherein R8 represents an alkyl group, alkenyl group, or aryl group having 1 to 45 carbon atoms) of component (C) is caproic acid amide, caprylic acid amide, caprylic acid amide, Capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, araxic acid amide, behenic acid amide, palmitoleic acid amide, oleic acid amide, eicosenoic acid amide, erucic acid amide, elaidic acid amide, linoleic acid It is selected from one type or a mixture of two or more of amide, linoleic acid amide, ricinoleic acid amide, etc., and preferably one having 6 to 22 carbon atoms. or,
2g or more of -monoalcohol, -valent carboxylic acid, and acid amide may be used in combination (・.

Examples of organic diisocyanates (D) used in the present invention include 4,4'-diphenylmethane diisocyanate, 2.6-)lylene diisocyanate, 1,5-naphthylene diisocyanate, Examples include 0-1m-1 or p-xylylene/diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, and one or a mixture of two or more of these is used. In addition, part of the diisocyanate used in the present invention can be fit (
Alternatively, they can be used in combination. The examples of the above-mentioned compounds are for illustrative purposes only and are not limited to these.

An example of the erasure of the present invention is given in an aqueous system using 4,4'-diphenylmethane diisocyanate (hereinafter referred to as MDI). Examples include, but are not limited to, acids, ten MDI (Dl-a set of acid amides+MDI), and the like.

The method for producing the lubricant of the present invention involves heating and melting 1 mole of monohydric alcohol, monocarboxylic acid, or acid amide to a temperature above the - point, adding 15 moles of an organic diisocyanate, Synthesis down.

In addition, in order for the lubricant of the present invention to exhibit the desired performance, it is necessary to add [1.1 parts by weight to 5.0 parts by weight] per 100 parts by weight of the resin.
It is added in parts by weight, more preferably in 1211M-50 parts. If α is less than 1 part by weight, the lubricating effect will hardly be obtained, and if it is more than 5.0 parts by weight, the resulting resin composition will have bleeding agglomerates, Ii! Bad tax phenomena such as ii & decline will arise.

The lubricant according to the present invention may be added to the synthetic resin by mixing and adding it to pellets, flake powder, or resin compound during the #M resin production process or during resin processing.

Furthermore, if necessary, fatty acid hydrogen, higher fatty acids, aliphatic alcohols, fatty acid amides, metal soaps, *fatty acid ester lubricants, dyes, flame release agents, fillers, antistatic agents, plasticizers , antioxidants, weathering stabilizers, etc. can also be used in combination.

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 1m, chlorinated polyethylene, chlorinated polypropylene, Polyvinylidene fluoride, 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 li&, acrylonitrile-butadiene-styrene copolymer, linear polyester,
Examples include polyacetal, polyamide, polycarbonate, etc. alone or in blends, and they are preferably used as lubricants for thermoplastic polyurethane resins or vinyl chloride resins.

Here, 105-polyvinyl resins include, for example, Kanevinyl (Kanebuchi Chemical Products), Nitsuborit (Chisso Products), Denka Vinyl (Denki Kagaku Kogyo Products), Zeon PVC (Nippon Zeon Products), Viniriki (Mitsubishi Monsanto Chemical Products) ), Vinicron (Mitsui Toatsu Chemicals), Aron PVC (Toagosei Chemicals), and Sumilit (Sumitomo Chemicals) Hiro.

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, and polyolefin diol. The number average molecular weight of the polymer diol is 3
00-6, ooo is preferred.

Dicarboxylic acids and diols are used for making polyester diols, but dicarboxylic acids and diols include, for example, geltaric acid, adipic acid, succinic acid, speric acid, sebacic acid, methyladipic acid, pimelic acid, and phthalic acid. , terephthalic acid, isophthalic acid, maleic acid, and fumar In. Examples of the diol include ethylene glycol, 1,4-ptasidiol, 1,6-hexanediol, propidine glycol, diethylene glycol, and neopentyl glycol. etc. Polyether diols include polyethylene glycol,
Examples include polypropylene glycol and polytetramethylene glycol. As a polylactone,
Poly-1-caprolactone diol is mentioned. Examples of the polyolefin diol include polybutadiene diol.

As a chain extension agent, it is used as a component of polyester diol.
In addition to the exemplified diols, diamines such as ethylene diamine and propylene diamine may be mentioned.

As the diisocyanate, 4. 4'-diphenylmethane diisocyanate, 2.4-) lylene diisocyanate, 2-6-) lylene diisocyanate), 1-5-naphthylene diisocyanate, 0-, m- or p-xylylene diisocyanate, tetramethylene diisocyanate, penta It can be selected from one or a mixture of two or more of methylene diiso7anate, hexamesol diisocyanate, and the like.

In order to specifically explain the present invention to the person skilled in the art, the present invention will be described in detail by way of examples, but the present invention will not be understood in any way by these examples.
It is not limited.

Synthesis Example-1 54g of stearyl alcohol (cotton product name Calcol 80, manufactured by Kao Soap Co., Ltd.) was heated to 80'C in a flask equipped with a stirrer.
It forms a melt layer at a temperature of . Next, 25Ii of 4,4'-diphenylmethane diisocyanate (product name: Millionate MT1, manufactured by Nippon Polyurethane Industries, Ltd.) was gradually added. Although the temperature of the reaction mixture rises to 130° C. due to exothermic heat, stirring is continued for about 2 hours. After 2 hours, pour #1L of the reactant into the vat,
After cooling, it was crushed to obtain lubricant-1.

Synthesis Example 2 A lubricant 2 was obtained in the same manner as in Synthesis Example 1 except that 114 g of 2,4-toluene diisocyanate was used in place of 4,4'-diphenylmethane diisocyanate.

Synthesis Example-3 In place of stearyl alcohol in Synthesis Example-1, stearin aII (Lunatsuku 8-30, manufactured by Kako Soap Co., Ltd.) 5
Lubricant-3 was obtained in the same manner except that 49.9 was used.

! J Examples 1 to 4 100 parts by weight of a polyurethane resin obtained by reacting a mixture of polybutylene adipate diol with a number average molecular weight of 2000 and 1.4-butanediol in a molar ratio of 1:2 with 4.4'-diphenylmethane diisocyanate. Synthesis example-1 for
The lubricant-1 and lubricant-2 obtained in ,-2 were added in the amounts shown in Table-1, and the mixture was heated at a temperature fK of 160° to 180°C for 30
The mixture was pelletized using a single-screw extruder (14/b: 18, Compression Kako 〇), and a spiral flow test was conducted using a 50-ounce injection molding machine under constant molding temperature conditions and mold temperature. We considered gender. 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. Table 1 shows the test results.

Examples 5 to 7 5.0 parts of epoxidized soybean oil per 100 parts of polyvinyl chloride resin (Zeon 105EP, product of Nippon Zeon Co., Ltd.), C
a - 2.0 parts of Zn-based stabilizer, Synthesis Examples -1, -2, -5
Add 1 part each of lubricants -1, -2, and -6 obtained in 17
Kneading was performed at 0°C using an 8-inch mixing roll, and peelability (lubricity) on the roll was determined.

The gelation time was investigated. The results are shown in the 2nd percentile.

It was found from Table 1-2 that the lubricant of the present invention had excellent lubricity.

Comparative Examples 3 to 4 Under the same conditions as Examples 5 to 7, cases in which no lubricant was added and cases in which stearyl alcohol was used as a lubricant were investigated. Table 2 shows the test results.

Examples 8 to 10 A mixture of polyε-caprolactone diol having a number average molecular weight of 2000 and ethylene glycol in a molar ratio of 2:1;
To 100 parts by weight of the polyurethane resin obtained by reacting 4'-diphenylmethane diisocyanate, lubricant-1 and lubricant-3 obtained in Synthesis Examples-1 and -3 were added in amounts as shown in Table-3. Add it and knead it on an 8-inch mixing roll at 180°C to make it releasable (slippery) on the roll.
The presence or absence of defects such as ``bleed'' and ``bloom'' occurring on the surface of a 2-way sheet formed by a 50-ounce injection molding machine using a roll compound was examined, as well as the physical properties of the film. 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 Example 5.6 When no lubricant was added and stearyl alcohol was used as a lubricant under the same conditions as Examples 8 to 10 (・
I considered it. Table 5 shows the test results.

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 in the amounts shown in Table-4 for 100 parts by weight of each resin in Table-4. Each was added, mixed into pellets using each extruder, and fluidized using a melt indexer at a temperature of 200°C and a load of 5.
Measured with klil. The results are shown in Table-4. The resin containing the lubricant of the present invention exhibited excellent lubricity.

Table 4 (Dix Styrene CR-, 5000) Note 3) Polypropylene: Mitsubishi Yuka number (Mitsubishi Noprene MW-6) Note 4) Polyethylene: Mitsubishi Yuka number (Yukalon YH50)

Claims (1)

[Scope of Claims] A thermoplastic resin; 8) General formula R1C00H (R1 in the formula is station height ridge 4 to 45
(C) General formula R, C0NH, where R1 has 1 to 45 carbon atoms;
one or more acid amides represented by the alkyl group, aryl group, alkenyl group) and CD
) A lubricant-containing thermoplastic resin composition comprising a lubricant obtained by reacting with an organic diisocyanate.