JP2021155543A - Lubricant for chlorinated vinyl chloride resin composition - Google Patents

Abstract

To provide a lubricant for a chlorinated vinyl chloride resin composition that is blended in the chlorinated vinyl chloride resin composition to reduce the friction and adhesion between the resin composition and metal.MEANS FOR SOLVING THE PROBLEM: A lubricant for chlorinated vinyl chloride resin compositions has polypentaerythritol fatty acid ester satisfying the following conditions (A)-(C) as an active ingredient. Condition (A): the content of tripentaerythritol in the polypentaerythritol is 50 mass% or more, condition (B): the esterification ratio is 93% or more, and condition (C): the acid value is 30 mgKOH/g or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to a lubricant to be blended in a chlorinated vinyl chloride resin composition.

Since vinyl chloride resin is excellent in water resistance, flame retardancy, electrical insulation, etc., and is inexpensive, it has been conventionally used in a wide range of fields such as pipe-related products, electric wire coating materials, and building materials. On the other hand, ordinary vinyl chloride resin has a low heat resistant temperature and is not suitable for applications requiring heat resistance (heat resistant pipes, heat resistant industrial plates, heat resistant films, heat resistant sheets, etc.). Therefore, in such an application, a chlorinated vinyl chloride resin having an improved heat resistant temperature by increasing the degree of chlorination compared to the vinyl chloride resin is used.

In the molding process of vinyl chloride resin and chlorinated vinyl chloride resin, usually, various additives are mixed with the resin to prepare a resin composition, and then heat kneading is performed. However, these resins are decomposed at the molding temperature and the resin itself. Since the temperatures are close to each other, thermal decomposition is likely to occur during molding, and the influence of frictional heat generated by friction between resin molecules and friction between the resin and a metal surface such as a kneader cannot be ignored. Therefore, in order to suppress the generation of such frictional heat and to improve the metal peelability from the viewpoint of workability, various vinyl chloride resin compositions and chlorinated vinyl chloride resin compositions have been conventionally used. Contains lubricant.

As the lubricant for the vinyl chloride resin composition, for example, hydrocarbon-based lubricants such as paraffin wax and polyethylene wax, and ester wax-based lubricants such as pentaerythritol fatty acid ester and dipentaerythritol fatty acid ester are known and are different from each other. Since it has characteristics, it is used properly or used together according to the purpose.

As patented technologies related to lubricants, for example, a lubricant for plastic molding mainly composed of a reaction product of pentaerythritol and / or dipentaerythritol, a dibasic organic acid and a fatty acid (Patent Document 1), and an aliphatic polybase. A lubricant composition for polyvinyl chloride (Patent Document 2) and the like, which comprises acid / solid hydrocarbon and / or ester WAX = 5 to 35% by weight / 95 to 65% by weight, are known.

However, in the chlorinated vinyl chloride resin composition, even if the above-mentioned known lubricant for vinyl chloride resin composition is blended as it is, a sufficient effect may not be obtained in some cases. In particular, when a conventional ester wax-based lubricant (for example, dipentaerythritol fatty acid ester) is blended with the chlorinated vinyl chloride resin composition, the effect of reducing the friction and adhesiveness between the resin composition and the metal (metal peeling property or Not only is the effect of improving the metal slipperiness) insufficient, but the heat resistance of the resin composition also tends to decrease.

Therefore, there has been a demand for a new ester wax-based lubricant capable of sufficiently reducing friction and adhesiveness with a metal even in a chlorinated vinyl chloride resin composition.

Japanese Unexamined Patent Publication No. 53-006350 Japanese Unexamined Patent Publication No. 9-143325

An object of the present invention is to provide a lubricant for a chlorinated vinyl chloride resin composition, which can reduce friction and adhesiveness between the resin composition and a metal by blending with the chlorinated vinyl chloride resin composition. And.

As a result of intensive research to solve the above problems, the present inventor blends a polyvinyl chloride resin composition with a polypentaerythritol fatty acid ester made from polypentaerythritol containing a large amount of tripentaerythritol. As a result, it was found that the friction and adhesiveness between the resin composition and the metal were reduced, and further research was carried out based on this finding, and the present invention was completed.

That is, the present invention comprises the following (1) and (2).
(1) A lubricant for a chlorinated vinyl chloride resin composition containing a polypentaerythritol fatty acid ester satisfying the following conditions (a) to (c) as an active ingredient.
Condition (a): Content of tripentaerythritol in polypentaerythritol is 50% by mass or more Condition (b): Esterification rate is 93% or more Condition (c): Acid value is 30 mgKOH / g or less (2) A chlorinated vinyl chloride resin composition containing the lubricant for the chlorinated vinyl chloride resin composition according to 1).

The lubricant for a chlorinated vinyl chloride resin composition according to the present invention can reduce friction and adhesiveness between the resin composition and a metal by blending it with the chlorinated vinyl chloride resin composition.
Even if the lubricant for a chlorinated vinyl chloride resin composition according to the present invention is blended with a chlorinated vinyl chloride resin composition, the heat resistance of the resin composition is less likely to be lowered as compared with a conventional ester wax-based lubricant.
The chlorinated vinyl chloride resin composition containing the lubricant for the chlorinated vinyl chloride resin composition according to the present invention has reduced friction and adhesiveness with a metal.

FIG. 1 is a graph recording changes in torque over time when the resin composition 1 containing the lubricant 1 of the example and the resin composition 10 containing the lubricant 10 of the comparative example were kneaded with a plastomill. be. FIG. 2 is a photograph of the state of the metal rotor of the plast mill (state of adhesion of the resin composition to the metal rotor) after kneading the resin composition 1 containing the lubricant 1 of the example with a plast mill. FIG. 3 is a photograph of the state of the metal rotor of the plast mill (state of adhesion of the resin composition to the metal rotor) after kneading the resin composition 10 containing the lubricant 10 of the comparative example with a plast mill. FIG. 4 is a photomicrograph of the surface of the resin composition molded product extruded from the measuring instrument when the MFR of the resin composition 1 containing the lubricant 1 of the example was measured. FIG. 5 is a photomicrograph of the surface of the resin composition molded product extruded from the measuring instrument when the MFR of the resin composition 10 containing the lubricant 10 of the comparative example was measured.

The lubricant for a chlorinated vinyl chloride resin composition according to the present invention (hereinafter, also referred to as “the lubricant of the present invention”) is a polypentaerythritol fatty acid ester, which is an ester of polypentaerythritol and a fatty acid obtained by polymerizing two or more pentaerythritol molecules. It is an active ingredient and is characterized in that the polypentaerythritol fatty acid ester satisfies the following conditions (a) to (c).

[Condition (a)]
The condition (a) of the polypentaerythritol fatty acid ester (hereinafter, also referred to as "polypentaerythritol fatty acid ester of the present invention") which is the active ingredient of the lubricant of the present invention occupies 100% by mass of the polypentaerythritol constituting the ester. The content of tripentaerythritol (that is, polypentaerythritol obtained by polymerizing three pentaerythritol molecules) is 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. That is.

As the polypentaerythritol having a tripentaerythritol content of 50% by mass or more, a commercially available mixture of tripentaerythritol can be used. Usually, a commercially available tripentaerythritol mixture contains pentaerythritol, dipentaerythritol, tetrapentaerythritol, etc. in addition to tripentaerythritol, but the content of tripentaerythritol in 100% by mass of the mixture is 50% by mass or more. If there is, it can be used as a raw material for the polypentaerythritol fatty acid ester of the present invention. The content of tripentaerythritol in the mixture can be analyzed by using gas chromatography or the like, and numerical values such as standard values and analytical values published by the manufacturer can be adopted.

Examples of the commercially available tripentaerythritol mixture include tripentaerythritol (trade name; tripentaerythritol content representative analytical value 81.3% by mass; manufactured by Yong'an Kako Co., Ltd.), which can be used in the present invention. can.

[Condition (b)]
The condition (b) of the polypentaerythritol fatty acid ester of the present invention is that the esterification rate of the ester is 93% or more, preferably 96% or more, and more preferably 98% or more.

The esterification rate (%) can be calculated by the following formula. The ester value and hydroxyl value in the following formula are [2.3-3-1996 ester value] and [2.3.3-1996 ester value] of "Standard Oil and Fat Analysis Test Method (I)" (edited by Japan Oil Chemists' Society). 6-1996 hydroxyl value] is measured.

[Condition (c)]
The condition (c) of the polypentaerythritol fatty acid ester of the present invention is that the acid value of the ester is 30 mgKOH / g or less, preferably 20 mgKOH / g or less, more preferably 10 mgKOH / g or less, still more preferably 5 mgKOH / g or less. That is. When the acid value of the polypentaerythritol fatty acid ester is low, it tends to exhibit an excellent effect of improving metal peelability when blended in the chlorinated vinyl chloride resin composition.

The acid value is measured according to [2.3.1-1996 acid value] of "Reference Oil and Fat Analysis Test Method (I)" (edited by the Japan Oil Chemists' Society).

The fatty acid constituting the polypentaerythritol fatty acid ester of the present invention is not particularly limited, and for example, a linear or branched saturated fatty acid or unsaturated fatty acid having 8 to 28 carbon atoms, or a hydroxy group to these fatty acids Examples thereof include fatty acids having the above functional groups. Specifically, for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, araquinic acid, aicosapentaenoic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, elaidic acid, erucic acid, Examples thereof include elaidic acid, linoleic acid, linoleic acid, elaidic acid, hydroxystearic acid, isostearic acid and the like. Among these, palmitic acid is obtained because a polyvinyl chloride resin composition having an excellent slipperiness improving effect and a polypentaerythritol fatty acid ester which is hard to volatilize during heat kneading or molding of the chlorinated vinyl chloride resin composition can be obtained. , Stearic acid or behenic acid is preferable, and stearic acid or behenic acid is more preferable. These fatty acids may be naturally occurring fatty acids or chemically synthesized fatty acids. In addition, only one of these fatty acids may be used alone, or two or more of these fatty acids may be used in combination.

The method for producing the polypentaerythritol fatty acid ester of the present invention is not particularly limited, and the polypentaerythritol and the fatty acid may be esterified by a known method. Specifically, the following method can be exemplified.
For example, polypentaerythritol and fatty acid are charged in an arbitrary molar ratio in a normal reaction vessel equipped with a stirrer, a jacket for heating, a nitrogen introduction tube, a water content metering tube, an air cooling tube, etc., and zinc oxide, calcium hydroxide, etc. are used as catalysts. By adding alkali or Lewis acid such as tin, stirring and mixing, and heating at a predetermined temperature using a temperature controller while removing the water generated by the esterification reaction from the system in a nitrogen gas atmosphere. Examples thereof include a method for obtaining an esterified reaction product.

The mixing ratio of polypentaerythritol and fatty acid during the esterification reaction is such that the molar ratio of polypentaerythritol: fatty acid is 1: 2n to 2 (n + 1), where n is the average degree of polymerization of polypentaerythritol. Is preferable, and is more preferably 1: 2 (n + 0.5) to 2 (n + 1). The reaction temperature conditions are usually in the range of 180 to 250 ° C, preferably in the range of 220 to 240 ° C. The reaction pressure conditions are preferably reduced pressure or normal pressure, and the reaction time at that time is 5 to 12 hours.

The end point of the esterification reaction is determined with reference to a time point when the acid value of the esterified reaction product falls within the range satisfying the condition (b).

In addition to the polypentaerythritol fatty acid ester of the present invention, the lubricant of the present invention may contain any other component as long as the effect of the present invention is not impaired. It may contain an ingredient used as a lubricant for physical use. That is, the lubricant of the present invention can be prepared as a composite lubricant in which the polypentaerythritol fatty acid ester of the present invention and a known lubricant for a chlorinated vinyl chloride resin composition are mixed and unified. Known lubricants for chlorinated vinyl chloride resin compositions include, for example, esters of polypentaerythritol with dibasic acid or fatty acids and dibasic acid, polyhydric alcohols other than polypentaerythritol (glycerin, propylene glycol, etc.) and fatty acids. Ester wax-based lubricants such as esters with and / or dibasic acids, esters with monovalent alcohols (palmityl alcohol, stearyl alcohol, etc.) and fatty acids and / or dibasic acids; paraffin wax, microcrystallin wax, slack wax ( Petroleum wax), carnauba wax, rice wax, castor wax, candelilla wax (vegetable wax), montan wax (mineral wax), polyethylene wax, fishertroph wax, polypropylene wax (synthetic wax), polyethylene oxide wax (processed) (Modified wax) and other hydrocarbon-based lubricants; fatty acids such as stealic acid and stearyl alcohol or higher aliphatic alcohol-based lubricants; metal soap-based lubricants such as zinc stearate and calcium stearate; fatty acid amide-based lubricants and the like.

The properties of the lubricant of the present invention are not particularly limited, and may be solid, liquid, paste, etc., but may be solid at room temperature (25 ° C.) from the viewpoint of handleability and the like. preferable. More specific properties of the lubricant of the present invention in the form of a solid include, for example, a block, a pellet, a flake, a powder, and the like, and a powder is preferable.

When the lubricant of the present invention is in the form of powder, the average particle size thereof is preferably 50 to 2000 μm, more preferably 100 to 1000 μm. When the average particle size is within the above range, the influence on the gelation behavior when processing the chlorinated vinyl chloride resin composition is reduced.

By blending the lubricant of the present invention with a chlorinated vinyl chloride resin composition, the resin composition and a metal (for example, a metal rotor of a kneader, a mouthpiece or screw of an extrusion molding machine, or a gold of an injection molding machine) can be used. Friction and stickiness between the mold and the like can be reduced. This is expected to have effects such as suppression of frictional heat generation during kneading, improvement of metal peelability, and improvement of extrusion efficiency during extrusion molding.

The chlorinated vinyl chloride resin composition to which the lubricant of the present invention is used may be a composition containing only the chlorinated vinyl chloride resin and the lubricant of the present invention, and is arbitrary as long as the effect of the present invention is not impaired. It may be a composition containing the additive of.

The chlorinated vinyl chloride resin is a homopolymer of a chlorinated vinyl chloride monomer, a copolymer with another monomer copolymerizable with the chlorinated vinyl chloride monomer, or a polymer thereof. There is an alloyed version of and. Examples of other monomers copolymerizable with chlorinated vinyl chloride include olefins such as ethylene and propylene, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers such as butyl vinyl ether and cetyl vinyl ether, and acrylic acid. Examples thereof include acrylic acid esters such as acid esters and methacrylic acid esters, unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride, and anhydrides thereof.

The additive is not particularly limited as long as it is usually used for a chlorinated vinyl chloride resin composition and does not inhibit the effect of the present invention. For example, a stabilizer (organic tin-based stabilizer) is used. , Metal soap-based stabilizers, lead-based stabilizers, etc.), Inorganic fillers (calcium carbonate, clay, silica, carbon black, calcium silicate, diatomaceous earth, chalk, etc.), plasticizers (phthalic acid-based plasticizers, adipic acid-based Plasticizers, etc.), colorants (inorganic pigments, organic pigments, lake pigments, etc.), antistatic agents (glycerin fatty acid esters, diglycerin fatty acid esters, anionic surfactants, etc.), foaming agents (azo foaming agents, nitroso-based Foaming agent), polymer-based modifier (acrylic modifier, MBS modifier, CPE modifier, etc.), antioxidant (phenolic antioxidant, phosphorus-based antioxidant, etc.), UV absorber (Benzophenone-based UV absorbers, hindered amine-based UV absorbers, etc.), other stabilizing aids (stearoylbenzoylmethane, dipentaerythritol, hydrotalcite, zeolite, etc.) and the like can be mentioned.

Further, the lubricant of the present invention may be used in combination with other lubricants conventionally used in the chlorinated vinyl chloride resin composition, if necessary. Examples of the lubricant for the chlorinated vinyl chloride resin composition other than the lubricant of the present invention include an ester of polypentaerythritol and a dibasic acid or a fatty acid and a dibasic acid, and a polyhydric alcohol other than polypentaerythritol (glycerin, propylene glycol). Etc.) and esters of fatty acids and / or dibasic acids, ester wax-based lubricants such as esters of monovalent alcohols (palmityl alcohol, stearyl alcohol, etc.) and fatty acids and / or dibasic acids; paraffin wax, microcrystallin wax , Slack wax (petroleum wax), carnauba wax, rice wax, candelilla wax (vegetable wax), montan wax (mineral wax), polyethylene wax, Fishertropch wax, polypropylene wax (synthetic wax), polyethylene oxide wax (synthetic wax) Hydrocarbon-based lubricants such as processed / modified wax); fatty acids such as stealic acid and stearyl alcohol or higher aliphatic alcohol-based lubricants; metal soap-based lubricants such as zinc stearate and calcium stearate; fatty acid amide-based lubricants and the like. The lubricant of the present invention does not exclude the combined use with a lubricant containing a polypentaerythritol fatty acid ester other than the polypentaerythritol fatty acid ester of the present invention as an active ingredient, but in that case, the chlorinated vinyl chloride resin composition It is preferable that the conditions (a) to (c) of the present invention are satisfied as a whole of the polypentaerythritol fatty acid ester blended in the product.

The blending amount of the lubricant of the present invention into the chlorinated vinyl chloride resin composition is the structure and properties of the chlorinated vinyl chloride resin itself which is the main component of the resin composition, and any additive blended other than the lubricant of the present invention. Although it varies depending on the type, blending amount, desired degree of slipperiness, etc., for example, it is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the chlorinated vinyl chloride resin. , More preferably 0.1 to 3.0 parts by mass.

The method of blending the lubricant of the present invention into the chlorinated vinyl chloride resin composition is not particularly limited, and is obtained by premixing the chlorinated vinyl chloride resin and an arbitrary additive using, for example, a raker or the like. Examples thereof include a method of kneading the mixture and the lubricant of the present invention while heating the mixture to 95 to 140 ° C. with a known mixer having a heating function (for example, a Henschel mixer or the like). After heat kneading, it is preferable to quickly cool to less than 55 ° C. in order to prevent decomposition due to residual heat. The chlorinated vinyl chloride resin composition containing the lubricant of the present invention thus obtained is also one form of the present invention.

The chlorinated vinyl chloride resin composition containing the lubricant of the present invention can be further subjected to various molding means such as extrusion molding, injection molding, compression molding, sheet molding, blow molding, and vacuum molding to obtain an arbitrary shape. It can be used as a molded product. After molding, it is preferable to quickly cool to less than 55 ° C. in order to prevent deformation and decomposition due to residual heat. The obtained molded products are pipe-related products such as water and sewage pipes and fittings, electric wire covering materials, agricultural materials such as houses and tunnels, miscellaneous goods / daily necessities such as clothing, toys, packaging materials, containers, rain gutters, and window frames. , Can be used for building materials such as wallpaper.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

≪Manufacturing of lubricant≫
(1) Raw materials 1) Polypentaerythritol 1-1) Polypentaerythritol A (Product name: Tripentaerythritol; manufactured by Eiyasu Kako Co., Ltd.)
1-2) Polypentaerythritol B (trade name: dipentaerythritol; manufactured by Perstop)
2) Fatty acid 2-1) Stearic acid (trade name: stearic acid; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
2-2) Behenic acid (trade name: behenic acid 85; manufactured by Miyoshi Oil & Fat Co., Ltd.)

Table 1 summarizes the contents of monopentaerythritol, dipentaerythritol and tripentaerythritol (representative analytical values published by the manufacturer) for the raw materials polypentaerythritol A and B, respectively. Since polypentaerythritol contains by-products and the like other than the components in Table 1, the total of the values in the table is not necessarily 100% by mass.

(2) Method for producing lubricant [Production Example 1]
51.8 g of polypentaerythritol A and 298.2 g of stearic acid were added to a four-necked flask equipped with a temperature controller, a nitrogen introduction tube, a stirrer and a cooling tube, and these were retained in a nitrogen stream at 240 ° C. The reaction was carried out under normal pressure and reduced pressure conditions while removing. When the acid value of the reaction product became 5 mgKOH / g or less, the reaction was stopped to obtain 320 g of polypentaerythritol fatty acid ester. The esterification rate of the ester was about 98%. This was designated as lubricant 1.

[Manufacturing Example 2]
To a four-necked flask equipped with a temperature controller, a nitrogen introduction tube, a stirrer and a cooling tube, 43.4 g of polypentaerythritol A and 306.6 g of behenic acid were added, respectively, and the reaction water was retained at 245 ° C. under a nitrogen stream. The reaction was carried out under normal pressure and reduced pressure conditions while removing. When the acid value of the reaction product became 5 mgKOH / g or less, the reaction was stopped to obtain 328 g of polypentaerythritol fatty acid ester. The esterification rate of the ester was about 98%. This was designated as lubricant 2.

[Manufacturing Example 3]
52.9 g of polypentaerythritol A and 297.1 g of stearic acid were added to a four-necked flask equipped with a temperature controller, a nitrogen introduction tube, a stirrer and a cooling tube, and these were retained in a nitrogen stream at 240 ° C. The reaction was carried out under normal pressure and reduced pressure conditions while removing. When the acid value of the reaction product became 5 mgKOH / g or less, the reaction was stopped to obtain 322 g of polypentaerythritol fatty acid ester. The esterification rate of the ester was about 96%. This was designated as lubricant 3.

[Manufacturing Example 4]
54.1 g of polypentaerythritol A and 295.9 g of stearic acid were added to a four-necked flask equipped with a temperature controller, a nitrogen introduction tube, a stirrer and a cooling tube, and these were retained in a nitrogen stream at 240 ° C. The reaction was carried out under normal pressure and reduced pressure conditions while removing. When the acid value of the reaction product became 5 mgKOH / g or less, the reaction was stopped to obtain 324 g of polypentaerythritol fatty acid ester. The esterification rate of the ester was about 93%. This was designated as lubricant 4.

[Manufacturing Example 5]
47.6 g of polypentaerythritol A and 302.4 g of stearic acid were added to a four-necked flask equipped with a temperature controller, a nitrogen introduction tube, a stirrer and a cooling tube, and these were retained in a nitrogen stream at 240 ° C. The reaction was carried out under normal pressure and reduced pressure conditions while removing. When the acid value of the reaction product reached about 20 mgKOH / g, the reaction was stopped to obtain 325 g of polypentaerythritol fatty acid ester. The esterification rate of the ester was about 98%. This was designated as lubricant 5.

[Manufacturing Example 6]
In a four-necked flask equipped with a temperature controller, nitrogen introduction tube, stirrer and cooling tube, 37.95 g of polypentaerythritol A and 12.65 g of polypentaerythritol B (mass ratio of polypentaerythritol A: B = 75:25), 299.4 g of stearic acid was added, and these were reacted under normal pressure and reduced pressure conditions while distilling off the reaction water at 240 ° C. under a nitrogen stream. When the acid value of the reaction product became 5 mgKOH / g or less, the reaction was stopped to obtain 326 g of polypentaerythritol fatty acid ester. The esterification rate of the ester was about 98%. This was designated as lubricant 6.

[Manufacturing Example 7]
24.75 g of polypentaerythritol A and 24.75 g of polypentaerythritol B (mass ratio of polypentaerythritol A: B = 50:50), in a four-necked flask equipped with a temperature controller, a nitrogen introduction tube, a stirrer and a cooling tube. 300.5 g of stearic acid was added, and these were reacted under normal pressure and reduced pressure conditions while distilling off the reaction water at 240 ° C. under a nitrogen stream. When the acid value of the reaction product became 5 mgKOH / g or less, the reaction was stopped to obtain 323 g of polypentaerythritol fatty acid ester. The esterification rate of the ester was about 98%. This was designated as lubricant 7.

[Manufacturing Example 8]
61.3 g of polypentaerythritol A and 288.7 g of stearic acid were added to a four-necked flask equipped with a temperature controller, a nitrogen introduction tube, a stirrer and a cooling tube, and these were retained in a nitrogen stream at 240 ° C. The reaction was carried out under normal pressure and reduced pressure conditions while removing. When the acid value of the reaction product became 5 mgKOH / g or less, the reaction was stopped to obtain 324 g of polypentaerythritol fatty acid ester. The esterification rate of the ester was about 80%. This was designated as lubricant 8.

[Manufacturing Example 9]
To a four-necked flask equipped with a temperature controller, a nitrogen introduction tube, a stirrer and a cooling tube, 40.5 g of polypentaerythritol A and 309.5 g of stearic acid were added, and the reaction water was retained at 240 ° C. under a nitrogen stream. The reaction was carried out under normal pressure and reduced pressure conditions while removing. When the acid value of the reaction product reached about 50 mgKOH / g, the reaction was stopped to obtain 322 g of polypentaerythritol fatty acid ester. The esterification rate of the ester was about 98%. This was designated as lubricant 9.

[Manufacturing Example 10]
47.4 g of polypentaerythritol B and 302.6 g of stearic acid were added to a four-necked flask equipped with a temperature controller, a nitrogen introduction tube, a stirrer and a cooling tube, and these were retained in a nitrogen stream at 240 ° C. The reaction was carried out under normal pressure and reduced pressure conditions while removing. When the acid value of the reaction product became 5 mgKOH / g or less, the reaction was stopped to obtain 325 g of polypentaerythritol fatty acid ester. The esterification rate of the ester was about 98%. This was designated as lubricant 10.

(3) Formulation of Lubricants Table 2 summarizes the content of tripentaerythritol in the polypentaerythritol used as a raw material, the esterification rate of the ester, and the acid value of the lubricants 1 to 10. Of these, lubricants 1 to 6 are examples that satisfy all the conditions (a) to (c) of the polypentaerythritol fatty acid ester of the present invention, and lubricants 7 to 10 are comparative examples thereof.

<< Preparation of chlorinated vinyl chloride resin composition >>
(1) Raw materials 1) Chlorinated vinyl chloride resin (trade name: Sekisui PVC HA-58K; manufactured by Sekisui Chemical Co., Ltd.)
2) MBS modifier (trade name: Kaneka B-564; manufactured by Kaneka Corporation)
3) CPE modifier (trade name: CPE-135A; manufactured by Novista)
4) Organic tin stabilizer (trade name: TVS # 8831; manufactured by Nitto Kasei Kogyo Co., Ltd.)
5) Acrylic modifier (trade name: Kaneka PA-30; manufactured by Kaneka Corporation)
6) Pigment (trade name: CR-80; titanium oxide; manufactured by Ishihara Sangyo Co., Ltd.)
7) Lubricants (any of the lubricants 1 to 10)

(2) Formulation of chlorinated vinyl chloride resin composition Table 3 shows the composition of the chlorinated vinyl chloride resin composition prepared by using the above raw materials. The production was carried out using 50 times the amount of this raw material.

(3) Method for producing chlorinated vinyl chloride resin composition 50 times the amount of the raw materials shown in Table 3 is put into a super mixer (model: SMV-20Ba; manufactured by Kawata Co., Ltd.) and heated until the resin temperature reaches 105 ° C. After stirring and mixing while stirring, the mixture was cooled to 55 ° C. while mixing with a ribbon blender (model: KRM-40J; manufactured by Seiwa Kogyo Co., Ltd.) to obtain chlorinated vinyl chloride resin compositions 1-10.

≪Evaluation test of chlorinated vinyl chloride resin composition≫
[Kneading test with plast mill]
(1) Test Method The chlorinated vinyl chloride resin compositions 1 to 10 were kneaded with a lab plast mill (model: 4C150-01; manufactured by Toyo Seiki Seisakusho Co., Ltd.) under the following conditions.
<Conditions>
Jacket temperature: 190 ° C
Rotor speed: 50 rpm
Filling amount: 70g
Preheating time: 2 minutes

(2) Evaluation of initial slipperiness When the change over time in the torque (Nm) of the plast mill during the kneading test was recorded, the torque that temporarily increased immediately after the start of kneading was about 20 seconds later. It became the lowest value at, and the torque tended to increase gradually as the kneading proceeded from there (see FIG. 1). At this time, the lower the minimum value of the torque, the higher the slipperiness (initial slipperiness) between the resin composition and the metal rotor of the plast mill at the initial stage of kneading, and the smaller the friction. Therefore, it is presumed that in the resin composition having high initial slipperiness, the generation of frictional heat during kneading was also suppressed. Therefore, the initial slipperiness of each resin composition was evaluated based on the minimum value of the torque. The evaluation is symbolized according to the following criteria and the results are shown in Table 4.
[Criteria for symbolization]
⊚: Minimum value less than 50 N ・ m 〇: Minimum value 50 N ・ m or more, less than 55 N ・ m Δ: Minimum value 55 N ・ m or more, less than 60 N ・ m ×: Minimum value 60 N ・ m or more

(3) Evaluation of metal peelability After the kneading test was completed, the amount of the resin composition adhering to the metal rotor of the plast mill was visually observed, and the metal peelability of each resin composition was evaluated based on this (FIG. 2). And 3). The evaluation is symbolized according to the following criteria and the results are shown in Table 4.
[Criteria for symbolization]
◎: Very small amount of adhesion 〇: Small amount of adhesion △: Slightly large amount of adhesion ×: Large amount of adhesion

[MFR measurement test]
(1) Test Method 200 g of each of the chlorinated vinyl chloride resin compositions 1 to 10 was kneaded with an open roll (manufactured by Osaka Roll Machine Manufacturing Co., Ltd.) at 200 ° C. for 5 minutes to prepare 1 mm thick resin sheets 1 to 10. .. This was cut into a sample, and MFR was measured under the following conditions with an MFR (melt flow rate) measuring device (trade name: Melt Indexer; model: FB01; manufactured by Toyo Seiki Seisakusho Co., Ltd.).
<Conditions>
Jacket temperature: 210 ° C
Load: 21.6 kg
Filling amount: 2g
Preheating time: 4 minutes

(2) Evaluation of metal slipperiness The metal slipperiness of each resin composition was evaluated based on the MFR measured by the above test. The MFR is an index obtained by filling a cylindrical metal container with the resin composition and measuring the mass (g / 10 min) of the resin composition extruded from the opening at the bottom of the container for 10 minutes. Therefore, the larger the value of this MFR, the less the friction and adhesiveness of the resin composition with the metal container and the base of the opening thereof (that is, the higher the metal slipperiness), and the smoother the extruded. means. The evaluation is symbolized according to the following criteria and the results are shown in Table 4.
[Criteria for symbolization]
⊚: MFR 1.0 g / 10 min or more 〇: MFR 0.8 g / 10 min or more, less than 1.0 g / 10 min Δ: MFR 0.6 g / 10 min or more, less than 0.8 g / 10 min ×: MFR 0.6 g / 10 min or less

(3) Evaluation of surface properties In the above test, the surface of the rod-shaped resin composition molded product extruded from the MFR measuring instrument was observed with a microscope, and the surface properties (whether or not there was gloss or roughness) were evaluated (see FIGS. 4 and 5). ). The glossy and smooth the surface of the molded product means that the friction and adhesiveness between the resin composition and the mouthpiece of the opening of the MFR measuring instrument were reduced. The evaluation is symbolized according to the following criteria and the results are shown in Table 4.
[Criteria for symbolization]
◎: The surface is glossy and extremely smooth 〇: The surface is glossy and generally smooth △: The surface is not glossy and rough ×: The surface is not glossy and the roughness is remarkable be

[Measurement test of Vicat softening point]
(1) Test method The resin sheets 1 to 10 produced in the MFR measurement test are compression-molded at 180 ° C. for 5 minutes with a press molding machine (model: AYSR-5; manufactured by Shinto Metal Industry Co., Ltd.) to test a thickness of 5 mm. I got a piece. Using the test piece, the Bikat softening point (JIS K7206) was measured with an HDT (deflection temperature under load) measuring device (trade name: HDT TESTER; model: S-3; manufactured by Toyo Seiki Seisakusho Co., Ltd.) under the following conditions.
<Conditions>
Load: 50N
Temperature rise rate: 50 ° C / h

(2) Evaluation of heat resistance The heat resistance of each resin composition was evaluated based on the Vicat softening point measured by the above test. For the evaluation, the average value of the Vicat softening points measured three times for each resin composition was obtained and symbolized according to the following criteria. The results are shown in Table 4.
[Criteria for symbolization]
⊚: Average 115.5 ° C or higher 〇: Average 114.5 ° C or higher and less than 115.5 ° C Δ: Average 113.0 ° C or higher and lower than 114.5 ° C ×: Average less than 113.0 ° C

As is clear from the results in Table 4, the resin compositions 1 to 6 containing the lubricants 1 to 6 according to the examples of the present invention have any of initial slipperiness, metal peelability, metal slipperiness, and surface property. The evaluation was "◎" or "○". That is, the friction and adhesiveness of these resin compositions with the metal were sufficiently reduced. Further, since these resin compositions are also evaluated for heat resistance as "◎" or "○", the lubricant of the present invention lowers the heat resistance of the resin composition such as the conventional ester wax-based lubricant. No disadvantages were seen. On the other hand, the resin compositions 7 to 10 containing the lubricants 7 to 10 of the comparative example are evaluated as "Δ" or "x" in at least one or more items, and have friction and adhesiveness with a metal. The reduction effect of was inferior. In particular, in the resin composition 10 containing the lubricant 10, the heat resistance was also significantly reduced.

Claims (2)

A lubricant for a chlorinated vinyl chloride resin composition containing a polypentaerythritol fatty acid ester satisfying the following conditions (a) to (c) as an active ingredient.
Condition (a): Content of tripentaerythritol in polypentaerythritol is 50% by mass or more Condition (b): Esterification rate is 93% or more Condition (c): Acid value is 30 mgKOH / g or less A chlorinated vinyl chloride resin composition containing the lubricant for the chlorinated vinyl chloride resin composition according to claim 1.

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