JPH10330561A - Lubricant for chlorine-containing resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lubricant being excellent in compatibility with chlorine- containing resin such as PVC and reduced in retardation of gelation even when used in combination with an organotin stabilizer by using a hydrolytically ring- opened maleinized polyethylene wax prepared by grafting maleic anhydride onto a polyethylene wax in a specified molecular weight range and hydrolytically opening the rings of the cyclic acid anhydride moieties. SOLUTION: The polyethylene wax used is one having a number-average molecular weight of 400-5,000, and maleic anhydride is grafted threreonto by a method such as thermal addition. The grafting ratio is desirably 2-10 wt.%. From the viewpoint of quality, it is desirable to obtain the hydrolytically ring- opened maleinized polyethylene wax by adding water to the maleic-anhydride- grafted wax in the state of a melt. The degree of hydrolytic opening of rings is desirably in the range of 40-100%. The hydrolytic ring opening gives a lubricant improved on external lubrication and suppressed in the defect of retarding a gelation time and improved in the persistence of post lubrication. This lubricant is particularly effective when used in combination with an organotin stabilizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lubricant used for molding a chlorine-containing resin such as polyvinyl chloride.

[0002]

2. Description of the Related Art Chlorine-containing resins such as polyvinyl chloride (hereinafter abbreviated as "PVC") are plastics which have poor fluidity and are difficult to mold. Therefore, molding is carried out near the decomposition temperature of PVC. General. As a result, hydrogen chloride generated by decomposition corrodes metal parts such as barrels and screws of extruders and injection molding machines, calender rolls, and resin adheres to metal surfaces, causing poor peeling and seizure, resulting in workability. , The workability may be significantly deteriorated. In order to avoid such problems, the frictional resistance (torque) between metal and a stabilizer that has the effect of trapping hydrogen chloride
It has been widely and generally practiced to incorporate a lubricant to lower the viscosity.

[0003] The purpose of addition of the stabilizer is not uniform depending on the case of mainly trapping hydrogen chloride and the physical properties such as compatibility, lubricity, resistance to sulfide contamination and transparency. In recent years, the integration of lubricants, stabilizers, other plasticizers, pigments, fillers, reinforcing agents, etc. has been actively performed for process automation and labor saving, depending on product characteristics and molding machines. A variety of complex stabilizers have been proposed.

As a stabilizer for chlorine-containing resins such as PVC,
Conventionally, lead-based stabilizers such as lead stearate and tribasic lead sulfate have been mainly used because of their excellent thermal stability and electrical insulation, good lubricity and excellent workability. However, in recent years, dewatering of PVC pipes and fittings for water supply has been progressing due to toxicity problems, and secondary aggregation is likely to occur, it does not dissolve in resins and plasticizers, there is an initial coloration, and transparent products can not be obtained. Therefore, the organic tin-based stabilizer or the calcium zinc-based stabilizer has been gradually shifted. Organotin-based stabilizers are characterized by excellent heat resistance and weather resistance, can produce transparent products, have excellent compatibility with resins, and have a large effect of promoting gelation of PVC. It is the most promising stabilizer in the movement.

However, when compared with other stabilizers, this organotin-based stabilizer acts to reduce friction between polymers in the resin melt and improve internal fluidity such as improving fluidity. The effect of lowering the frictional resistance of the steel, that is, the so-called external lubrication, is poor, and it is necessary to reinforce the external lubrication by adding a lubricant at a high level. Therefore, as the lubricant used in combination with the organotin-based stabilizer, a lubricant having good compatibility with the stabilizer and the resin and having a large external lubricating effect is required. However, a lubricant having high external lubrication generally lowers the maximum gelling torque, but also has a strong effect of delaying gelation, and acts in a direction to reduce the gelation accelerating effect characteristic of the organotin-based stabilizer, which is not preferable. Therefore, a lubricant having a contradictory property that the external lubricity is strong and the maximum gelling torque is lowered, but the internal lubricity delay effect of gelation is weak is strongly desired as an ideal.

[0006] Commonly used lubricants for molding chlorine-containing resins such as PVC include hydrocarbons such as liquid paraffin, natural paraffin, synthetic paraffin, microwax, polyolefin wax, chlorinated hydrocarbons and fluorocarbons, and higher fatty acids. , Fatty acids such as oxyfatty acids, fatty acid amides such as fatty acid amides and alkylenebisfatty acid amides, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters, fatty acid ester systems such as fatty acid glycol esters, fatty acid alcohols, polyhydric alcohols, There are alcohols such as polyglycols, metal soaps which are non-alkali metal salts such as calcium, magnesium and barium fatty acids, and mixtures thereof.
Usually, 3 to 6 types of lubricants are compounded according to the processing system, type of molding machine, molding conditions and other combinations of compounding agents, but polyethylene wax having high lubricity and being inexpensive is widely used. This polyethylene wax has a different lubricating effect depending on the molecular structure, molecular weight and crystallinity, but generally has a strong external lubricating effect and can provide lubrication with a small amount of addition. The system stabilizer is blended as an essential component. However, in the organotin-based stabilizer compounding system, the polyethylene wax has a poor compatibility with the resin and the stabilizer, so that when used in a large amount, a problem that the transparency of the molded article is deteriorated is caused. Since a phenomenon in which polyethylene wax adheres to a metal surface from a resin (hereinafter, referred to as a “plate-out phenomenon”) is likely to occur, workability and workability are reduced. Therefore, in the organotin-based stabilizer compounding, the polyethylene wax is limited to a small amount.

[0007] As a specific means for improving the compatibility problem with chlorine-containing resins such as PVC, attempts have been made to introduce a polar group such as an acid group or an ester bond into polyethylene wax. For example, a material obtained by introducing a carboxyl group into a metal salt by air oxidation of polyethylene wax is used to form a metal salt. With respect to the proposal that the lubricant is excellent in lubricity (late lubricity) (Japanese Patent Publication No. 52-23662), it is necessary to increase the acid value in order to obtain a sufficient compatibility aimed at by the present invention. In addition to the increase, the high acid value product has excellent compatibility but has a disadvantage that the lubricating effect is low. Also disclosed are techniques for graft-polymerizing or further esterifying maleic anhydride (JP-A-54-30287, JP-A-56-287).
-26915, JP-B 52-22986, JP-B 52-
22987), but this is only a disclosure of the manufacturing method, and there is no description of a specific effect relating to the lubricating effect aimed at by the present invention. In addition, esterification is costly and impractical. JP-A-53-102353 discloses a composition in which a lubricant is blended with an organotin-based stabilizer, which comprises a granulated composition of a liquid organotin stabilizer and a mixture of an organotin-based stabilizer and a modified polyethylene wax. The compatibility was evaluated, and there is no description about compatibility or lubricity with the resin intended by the present inventors, and there is a fundamental difference. Among these modified polyethylene waxes, polyethylene waxes having a relatively low acid value in which a carboxyl group has been introduced by air oxidation are widely used in practice. However, when compared with unmodified polyethylene wax, although it is superior in terms of compatibility and lubricating effect, when the amount added is large, there is still a problem of plate-out phenomenon and transparency inhibition, and fatty acid polyhydric alcohol esterified products Used together with an ester wax such as a partially esterified saturated fatty acid.

[0008]

Therefore, the present invention has an excellent maximum gelling torque which is excellent in compatibility with a chlorine-containing resin and has an external lubricity when used in combination with an organotin stabilizer as a lubricating effect. Despite its low internal lubricity, the effect of retarding gelation is weak, and the late lubricity is persistent,
An object of the present invention is to provide a lubricant for chlorine-containing resin.

[0009]

Means for Solving the Problems In order to solve the above problems, the present inventors have focused on the compatibility and lubricity of various modified polyethylene waxes and resins, and as a result of intensive studies, as a result, the specific modified polyethylene We have found that wax is effective. That is, the specific polyethylene wax is obtained by further hydrolyzing a maleated polyethylene wax of an acid-modified cyclic acid anhydride obtained by graft-polymerizing maleic anhydride to a polyethylene wax having a number average molecular weight of 400 to 5,000. Hydrolyzed ring-opened maleated polyethylene wax. In particular, the graft ratio of maleic anhydride is 2 to 10% by weight, and the rate of ring opening is 40 to 100.
%, The compatibility with the resin is good, the effect of lowering the maximum gelling torque in the initial lubricity is great, and the time until the maximum gelling torque is reached (gelation time) is not greatly delayed. A lubricant can be provided. As the chlorine-containing resin, polyvinyl chloride (PVC) is particularly desirable.

The raw material polyethylene wax used in the present invention uses a titanium compound and an organoaluminum compound which are highly activated by a magnesium compound, and is used in an inert hydrocarbon solvent at a temperature of from 120 to 300 ° C. at a temperature of 120 to 300 ° C. Obtained by polymerization or copolymerization of α-olefins in the presence of hydrogen, obtained by pyrolyzing high-molecular-weight polyethylene at about 350 ° C. and then hydrogenating, and obtaining ethylene by a medium-low pressure method under a Ziegler catalyst. And those obtained by purifying a solvent-soluble component of polyethylene obtained.

[0011] The polyethylene wax generally has a number average molecular weight of several hundreds to several thousands, and its chemical formula is as follows.

[0012]

Embedded image

The polyethylene wax used in the present invention preferably has a number average molecular weight of 400 to 5,000 as measured by high performance liquid chromatography (GPC). 4
If it is less than 00, it is unfavorable because it volatilizes during molding to lower the late lubricity and the molded product exudes wax over time. When the molecular weight exceeds 5,000, the compatibility with the resin decreases, and as the molecular weight increases, the melt viscosity increases, the transition to the interface during kneading and molding becomes slow, and not only the gelling torque is high but also the The stability of lubricity is poor, and sufficient compatibility and initial lubricity intended in the present invention cannot be obtained. As a method for measuring the number average molecular weight of the polyethylene wax used in the present invention, a high performance liquid chromatograph (GPC) was used, and the number average molecular weight in terms of polystyrene was adopted. Further, as to the polyethylene wax as a raw material used in the present invention, if there are many unsaturated bonds in the molecule, a coupling reaction between polyethylene waxes and a single reaction of maleic anhydride are likely to occur. The lubricant obtained by such a side reaction not only increases the viscosity and decreases the compatibility with the resin and the lubricating effect, but also reduces the product value by being colored brown and the hue of the molded article. The adverse effect of worsening occurs. Specifically, the number of unsaturated bonds is preferably 1.5 or less per 1000 carbon atoms, more preferably 1 or less. However, the number of unsaturated bonds is not particularly limited as long as the graft polymerization is achieved by a special production method without a side reaction.

Various production methods have been disclosed for graft polymerization of maleic anhydride onto polyethylene wax. For example, those using an organic peroxide such as dicumyl peroxide, di-tert-butyl peroxide or benzoyl peroxide as an initiator (JP-A-48-29878, JP-A-56-26915),
There are those which add heat while refluxing maleic anhydride at a high temperature of 300 ° C. (JP-A-54-30287) and those which generate hydroperoxide by air oxidation (JP-B-48-41710). Either a system-based or solvent-free synthesis method may be used. The method of recovering the solvent, unreacted maleic anhydride, decomposed organic peroxide, decomposed product of polyethylene wax, and the like includes distillation under reduced pressure and purification with a solvent, and any method may be used. Is economically preferred. As described above, the method of graft polymerization of maleic anhydride onto polyethylene wax is not particularly limited, but a production method involving a coupling reaction between polyethylene waxes, a crosslinking reaction with maleic anhydride, and a peroxide crosslinking reaction is not preferred.

The graft ratio is an important factor that affects the compatibility and lubricity with the resin, as in the case of the raw material polyethylene wax. When the graft ratio is increased, the polarity is increased and the compatibility with the resin is improved, but conversely, the localization at the resin interface is insufficient, and the external lubricity tends to decrease. Further, the graft ratio disclosed in the present invention is more preferably 2 to 10% by weight. The graft ratio is arbitrarily set according to the molecular weight of the raw material polyethylene wax in consideration of the balance between compatibility and initial lubricity. When the graft ratio is less than 2% by weight, the compatibility with the resin is slightly lowered to cause a plate-out phenomenon, and the dynamic thermal stability is lowered, so that the processability is remarkably deteriorated. In particular, when used in combination with an organic tin-based stabilizer, transparency is impaired, and a small amount of the compound must be added. When the graft ratio exceeds 10% by weight, the compatibility with the chlorine-containing resin is improved, but the external lubrication is slightly weak, the kneading torque value is increased, and the processability is lowered. Load is undesirably applied. When used in combination with an organic tin-based stabilizer, the maximum gelling torque is too high, resulting in poor processability and accelerated decomposition. The method of measuring the graft ratio disclosed in the present invention measures the weight of unreacted maleic anhydride and maleic anhydride homopolymer in an extract obtained by acetone-extracting a maleic anhydride-grafted polyethylene wax with a Soxhlet extractor, The weight of the reacted maleic anhydride was calculated, and the graft ratio was calculated from the following equation (1).

[0016]

(Equation 1)

The hydrolyzed ring-opened maleated polyethylene wax of the present invention can be obtained by hydrolyzing the cyclic anhydride by adding water in a state where the wax grafted with maleic anhydride is further melted under heat. This method of ring opening is disclosed in JP-A-52-108491, and is a known fact. As another synthesis method, hydrolyzed ring-opened maleated polyethylene wax is obtained in one step by graft polymerization of maleic acid, but maleic acid has low grafting efficiency due to low polymerizability, removal of unreacted substances, It requires labor for purification. Cyclic anhydrides have the property of easily hydrolyzing and ring-opening by absorbing water in the atmosphere, and it is possible to obtain hydrolyzed ring-opened maleated polyethylene wax over time, but it is difficult to control the rate of hydrolyzing and opening of wax. There is a disadvantage that the rate of ring opening between the surface and the inside of the block varies. From the above, in order to obtain a ring-opened product, a method of forcibly adding water to open the ring is preferred in terms of efficiency and quality. The hydrolytic ring opening ratio of the lubricant for chlorine-containing resin of the present invention is more preferably set to 40 to 100%. When it is less than 40%, the gelation time is slightly slow, the moldability and the molding speed are reduced, and the purpose of the present invention is to obtain a lubricant having a strong external lubricity and a fast internal lubrication gelation time. Can not. If the rate of ring opening is 40% or more,
There is no large difference in the gelation time, and there is no large change in the quality even when the ring opening ratio changes due to the influence of moisture in the air. In the present invention, the method of measuring the rate of hydrolytic ring opening was determined from the absorbance of an anhydride cyclic group at 1790 cm-1 and the absorbance of a carboxyl group at 1710 cm-1 in the infrared absorption spectrum according to the following formula for convenience. In the infrared absorption spectrum, when the intensity of light incident on the sample is I0 and the intensity of light passing therethrough is I in the infrared absorption spectrum, A =
The lengths of I0 and I were measured and measured from the chart paper of the infrared absorption spectrum at an amount defined by log (I0 / I).

[0018]

(Equation 2)

The addition of a lubricant generally improves the external lubrication, lowers the maximum gelling torque, and tends to delay the gelation time. A very important finding was found that the internal lubricating gelation time can be shortened by hydrolyzing the maleic acid group. It was also confirmed that the continuity of late lubrication was improved. In other words, the one subjected to the hydrolytic ring-opening treatment has the same maximum gelation torque as the compatibility with the resin and the initial lubricity as compared to the untreated one,
It was confirmed that the gelation time was short. As a result, it is apparent to those skilled in the art that the processing speed can be increased, and that a great effect can be obtained, such as easy balance of external lubrication and internal lubrication and easy adjustment of processing. In particular, in the compounding system of the organotin-based stabilizer, the amount of the lubricant added is large, and the effect of the lubricant for chlorine-containing resin of the present invention is remarkably exhibited.

The hydrolyzed ring-opened maleated polyethylene wax in the present invention may be used in combination with other lubricants such as polyethylene wax, ester wax, and oxidized wax.
It is preferable to add 0.5 to 5.0 parts by weight based on 100 parts by weight of VC. When the amount is less than 0.5 part by weight, compatibility with a chlorine-containing resin such as PVC, which is the object of the present invention, and sufficient lubricity cannot be obtained, and the addition of more than 5.0 parts by weight is economical. Is not preferred. The lubricant for chlorine-containing resin of the present invention may be used in the form of a composite stabilizer mixed with a stabilizer, a plasticizer, a pigment, a filler, a reinforcing agent, and the like.

The hydrolyzed ring-opened maleated polyethylene wax of the present invention is particularly effective when used in combination with an organotin-based stabilizer, but can be sufficiently incorporated into other lead-based stabilizers and calcium zinc-based stabilizers. The effect is recognized and there is no problem.

The chlorine-containing resin for blending the ring-opened maleated polyethylene wax obtained by the method of the present invention includes polyvinyl chloride (PVC), polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polychloroprene, and the like. Ethylene-vinyl chloride copolymer and the like can be mentioned. Among them, the chlorinated resin having a remarkable effect is hard PVC. There are no particular restrictions on the polymerization system, degree of polymerization, molecular weight distribution, particle size distribution, chlorine content, etc. of the rigid PVC.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.

Various measurement methods are described below. The method for measuring the molecular weight is a fully automatic high-temperature high-performance liquid chromatograph ACL / GPC150C type manufactured by Waters, and the separation column is GMH-HT 60 cm × 1, GMH-HT manufactured by Tosoh Corporation.
L60 cm × 1, using o-dichlorobenzene for the moving layer, creating a calibration curve using standard polystyrene of known molecular weight, converting to a calibration curve for polyethylene using the viscosity equation, and then calculating the number average molecular weight from the differential molecular weight curve Was calculated.

The acid value was measured by a potassium hydroxide neutralization method according to JIS-K-5902. In the method, 1 g of the modified polyethylene wax was dissolved in 25 ml of toluene, and toluene: 2-propanol: water = 100:
50 ml of a solvent adjusted at 99: 1 (volume ratio) was added,
Neutralization titration was performed with 0.1N potassium hydroxide in ethanol using phenolphthalein as an indicator.

The penetration was measured in accordance with JIS-K-2235. The needle was dropped from the sample at a constant height at 25 ° C., and the hardness of the wax was evaluated by measuring the degree of penetration of the needle.

The viscosity was measured at 140 ° C. with a BL viscometer manufactured by Tokyo Keiki Co., Ltd.

The method for measuring the graft ratio is described in paragraph 0015.
The weight of the reacted maleic anhydride was calculated from the weight of the unreacted maleic anhydride and maleic anhydride homopolymer in the extract obtained by extracting the maleic anhydride-grafted polyethylene wax with acetone using a Soxhlet extractor as described in Then, the graft ratio was calculated from the calculation formula of Equation 1.

The method of measuring the rate of ring opening is described in paragraph 001.
As described in 7, the infrared absorption spectrum was measured using a Shimadzu Fourier Transform Infrared Spectrophotometer FTIR-8100M manufactured by Shimadzu Corporation, and an anhydride cyclic group at 1790 cm-1 and a carboxyl group at 1710 cm-1 were measured. Was obtained from the absorbance of the above formula for convenience.

The lubricating effect was measured by using a Labo Plastomill of Model 75C100 manufactured by Toyo Seiki Seisaku-Sho, Ltd., and the maximum gelling torque and gelling time were measured. This device is well known to those skilled in the art, but a blend of PVC, stabilizers, lubricants and other compounding agents is placed in a heated mixer block and sheared by two rotors having different rotation speeds. It is to graph the torque curve of the screw at the time of dispersion and kneading. The workability is determined from the torque curve, and the selection of the stabilizer and the lubricant and the molding conditions are determined. FIG. 1 shows a sample obtained by blending a lead-based stabilizer and a commercially available lubricant with hard PVC, and is made of Toyo Seiki Seisakusho Co., Ltd. 75
Examples of data measured on a Labo Plastomill of type C100 are provided.

Method for Preparing Maleated Polyethylene Wax and Hydrolyzed Ring Opened Product Synthesis Example 1 A flask equipped with a stirrer, thermometer, nitrogen inlet tube and cooling tube was charged with a number average molecular weight of 750 and an unsaturated bond having 1000 carbon atoms.
Melt viscosity of 15 cps with 0.8 pieces per piece, penetration 3
And 100 parts by weight of Neowax CL manufactured by Yashara Chemical Co., Ltd. was heated and melted at 150 ° C. under a nitrogen stream. Next, 5.0 parts by weight of maleic anhydride and 1.0 part by weight of benzoyl peroxide were sequentially added, and the mixture was stirred for 2 hours. After the completion of the reaction, the mixture was stirred for 1
By maintaining for a long time, volatile components such as unreacted maleic anhydride and peroxide decomposition products are removed, and the number average molecular weight is 78.
A maleated polyethylene wax having 0, an acid value of 42, a melt viscosity of 24 cps, a penetration of 1, and a graft ratio of 4.7% by weight was obtained. Then, at 130 ° C. in a nitrogen stream, water was added dropwise over 30 minutes to hydrate the equivalent of the anhydride group of the anhydride of the maleated polyethylene wax over 30 minutes, and the reaction was stirred for 15 minutes. The obtained hydrolyzed ring-opened maleated polyethylene wax had a number average molecular weight of 780, an acid value of 53, a melt viscosity of 29 cps, a penetration of 1, and a hydrolytic ring opening rate of 61%. Tables 1 and 2 show the properties of the synthesized wax.

Synthesis Example 2 Synthesis Example 1 was repeated except that the amount of water required to hydrate 0.5 times the acid anhydride equivalent of the anhydride of the maleated polyethylene wax obtained in Synthesis Example 1 was used. The same operation was performed to obtain a graft ratio of 4.7% by weight, a number average molecular weight of 780, an acid value of 48, a melt viscosity of 27 cps, and a penetration of 1,
A ring-opened maleated polyethylene wax having a ring-opening ratio of 40% was obtained. Tables 1 and 2 show the properties of the synthesized wax.

Synthesis Example 3 The same operation as in Synthesis Example 1 was carried out except that water was used in an amount required to hydrate three times the acid anhydride equivalent of the maleated polyethylene wax obtained in Synthesis Example 1. Graft ratio: 4.7% by weight; number average molecular weight: 780; acid value: 65; melt viscosity: 33 cps; penetration: 1;
9% of a hydrolyzed ring-opened maleated polyethylene wax was obtained. Tables 1 and 2 show the properties of the synthesized wax.

Synthesis Example 4 The same operation as in Synthesis Example 1 was carried out except that the amount of water required to hydrate 0.4 times the acid anhydride equivalent of the maleated polyethylene wax obtained in Synthesis Example 1 was used. The graft ratio was 4.7% by weight and the number average molecular weight was 78.
A hydrolyzed maleic polyethylene wax having an acid value of 0, an acid value of 44, a melt viscosity of 24 cps, a penetration of 1 and a hydrolytic ring opening rate of 39% was obtained. Tables 1 and 2 show the properties of the synthesized wax.

Synthesis Example 5 The procedure of Synthesis Example 1 was repeated except that maleic anhydride was changed to 2.3 parts by weight and benzoyl peroxide to 0.5 part by weight. 0
Weight%, number average molecular weight 765, acid value 18, melt viscosity 23
A hydrolyzed ring-opened maleated polyethylene wax having cps, a penetration of 1 and a hydrolytic ring-opening rate of 60% was obtained. Tables 1 and 2 show the properties of the synthesized wax.

Synthesis Example 6 In Synthesis Example 1, 10.5 parts by weight of maleic anhydride was added.
Except that benzoyl peroxide was changed to 2.1 parts by weight, all operations were performed in the same manner as in Synthesis Example 1, and the graft ratio was 1
A hydrolyzed maleated polyethylene wax having 0.0% by weight, a number average molecular weight of 815, an acid value of 76, a melt viscosity of 34 cps, a penetration of 1 and a hydrolyzing rate of 63% was obtained. Tables 1 and 2 show the properties of the synthesized wax.

Synthesis Example 7 The procedure of Synthesis Example 1 was repeated except that maleic anhydride was changed to 2.0 parts by weight and benzoyl peroxide was changed to 0.4 parts by weight. 9
Weight%, number average molecular weight 760, acid value 12, melt viscosity 22
A hydrolyzed ring-opened maleated polyethylene wax having a cps of 1 and a penetration of 58% was obtained. Tables 1 and 2 show the properties of the synthesized wax.

Synthesis Example 8 In Synthesis Example 1, 11.0 parts by weight of maleic anhydride was added.
Except that benzoyl peroxide was changed to 2.2 parts by weight, all operations were performed in the same manner as in Synthesis Example 1 to obtain a graft ratio of 1
A hydrolyzed ring-opened maleated polyethylene wax having 0.1% by weight, a number average molecular weight of 820, an acid value of 79, a melt viscosity of 46 cps, a penetration of 1 and a hydrolyzing rate of 57% was obtained. Tables 1 and 2 show the properties of the synthesized wax.

Synthesis Example 9 In Synthesis Example 1, number-average molecular weight 400, unsaturated bond obtained by purifying a solvent-soluble component of polyethylene obtained by a medium-low pressure method using ethylene instead of Neowax CL in the presence of a Ziegler catalyst. Was performed in the same manner as in Synthesis Example 1 except that a linear polyethylene wax having a melt viscosity of 8 cps and a penetration of 13 having 0.9 carbon atoms per 1000 carbon atoms was used, and the graft ratio was 4.6% by weight. A ring-opened maleated polyethylene wax having an average molecular weight of 460, an acid value of 53, a melt viscosity of 10 cps, a penetration of 9, and a ring-opening rate of 64% was obtained. Tables 1 and 2 show the properties of the synthesized wax.

Synthesis Example 10 In Synthesis Example 1, ethylene and propylene were mixed at 180 ° C. in the presence of hydrogen in a hexane solvent using titanium tetrachloride and triethylaluminum supported on anhydrous magnesium chloride instead of neowax CL. After polymerization, the volatile matter was separated to obtain a number average molecular weight of 5,000, a linear polyethylene wax having a melt viscosity of 3,970 cps having an unsaturated bond of 0.4 per 1,000 carbon atoms and a penetration of 3 was used. Are performed in the same manner as in Synthesis Example 1,
A hydrolyzed ring-opened maleated polyethylene wax having a graft ratio of 4.9% by weight, a number average molecular weight of 5010, an acid value of 54, a melt viscosity of 4130 cps, a penetration of 1 and a hydrolyzing rate of 62% was obtained. Tables 1 and 2 show the properties of the synthesized wax.

Synthesis Example 11 In Synthesis Example 1, number-average molecular weight 395, unsaturated bond obtained by purifying a solvent-soluble component of polyethylene obtained by a medium-to-low pressure method using ethylene instead of Neowax CL under a Ziegler catalyst. Was carried out in the same manner as in Synthesis Example 1 except that a linear polyethylene wax having a melt viscosity of 5 cps and a penetration of 15 having 1.0 carbon atoms per 1000 carbon atoms was used, and the graft ratio was 4.5% by weight. Average molecular weight 455, acid value 52, melt viscosity 8cps, penetration 1
1. A ring-opened maleated polyethylene wax having a ring-opening rate of 61% was obtained. Tables 1 and 2 show the properties of the synthesized wax.

SYNTHESIS EXAMPLE 12 The same procedure as in Synthesis Example 1 except that Neowax CL was replaced by a hydrogenated product of a high-molecular-weight polyethylene pyrolyzed wax having a number-average molecular weight of 5005 and a melting point having 0.7 unsaturated bonds per 1,000 carbon atoms. Viscosity 4280 cps, penetration 5
Except for using the linear polyethylene wax, the same operation as in Synthesis Example 1 was carried out, and the graft ratio was 4.8% by weight.
Number average molecular weight 5015, acid value 56, melt viscosity 4450c
A hydrolyzed ring-opened maleated polyethylene wax having a ps of 2, a penetration of 2, and a hydrolytic ring-opening rate of 68% was obtained. Tables 1 and 2 show the properties of the synthesized wax.

Synthesis Example 13 In Synthesis Example 1, number-average molecular weight 360, unsaturated bond obtained by purifying a solvent-soluble component of polyethylene obtained by medium-to-low pressure method using ethylene instead of neowax CL in the presence of Ziegler catalyst Is a linear polyethylene wax having a melt viscosity of 5 cps and a penetration of 18 having 1.0 carbon atoms per 1000 carbon atoms, maleic anhydride of 15.0 parts by weight, dicumyl peroxide of 3.0 parts by weight, and maleation. The acid anhydride group equivalent of 0.
All operations were performed in the same manner as in Synthesis Example 1 except that an amount of water required for hydration of 2 times was used. The graft ratio was 14.8% by weight, the number average molecular weight was 420, the acid value was 68, and the melt viscosity was 14 cp.
Thus, a ring-opened maleated polyethylene wax having a s, a penetration of 13, and a ring-opening rate of 11% was obtained. Tables 1 and 2 show the properties of the synthesized wax.

Synthesis Example 14 In Synthesis Example 1, instead of Neowax CL, a hydrogenated product of a pyrolytic wax of high molecular weight polyethylene, having a number average molecular weight of 5,100 and a melt having 0.2 unsaturated bonds per 1,000 carbon atoms. Viscosity 4340 cps, penetration 4
1.0 parts by weight of maleic anhydride, 0.2 parts by weight of dicumyl peroxide and 0.1 times the equivalent of the anhydride group of the maleated polyethylene wax to the linear polyethylene wax of Was performed in the same manner as in Synthesis Example 1 except that water was used.
7% by weight, number average molecular weight 5110, acid value 9, melt viscosity 4
A hydrolyzed ring-opened maleated polyethylene wax having 360 cps, a penetration of 3 and a hydrolytic ring-opening rate of 8% was obtained. Tables 1 and 2 show the properties of the synthesized wax.

Example 1 A sample was blended in order to conduct a performance comparison test of the obtained ring-opened maleated polyethylene wax. Degree of polymerization 1050
100 parts by weight of PVC, dioctyltin laurate 3.5
Parts by weight and 1.5 parts by weight of the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 1 were mixed with a blender.
Performance tests for compatibility and lubricating effects were performed by the following methods. The results are shown in Tables 3 and 4.

The compatibility was evaluated as follows. First, the compounded sample is formed into a sheet by mixing at a temperature of 180 ° C. by preforming, and a pressed sheet is formed by pressing at the same temperature. Thereafter, using a press roll apparatus in which two rolls (8 inches in diameter) are horizontally arranged, a roll temperature of 190
° C, the roll interval was set to a value at which the sheet thickness became 0.3 mm, the roll rotation speed was set to 18 rpm for one side, and 13 rpm for the other side. Is evaluated visually to determine whether or not seizure has occurred, ：: particularly good, ：: good,
Δ: fairly good, x: poor.

The lubricating effect was evaluated as follows. 70 g of the blended sample was placed in a mixer block of a Labo Plastomill heated to a temperature of 185 ° C., and measured at a rotation speed of 60 rpm, and the initial lubricity at that time was evaluated by a maximum gelling torque and a gelation time. (1) Maximum gelling torque The torque increased with the progress of gelation, and the maximum torque value when gelation was almost completed was evaluated. (2) Gelation time The time required for the torque to increase with the progress of gelation and to reach the maximum torque when gelation was almost completed was evaluated.

Example 2 Example 1 was repeated except that the ring-opened maleated polyethylene wax obtained in Synthesis Example 2 was used.
The same operation was performed. Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 3 The procedure of Example 1 was repeated, except that the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 3 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 4 The procedure of Example 1 was repeated, except that the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 5 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 5 The procedure of Example 1 was repeated, except that the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 6 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 6 The procedure of Example 1 was repeated, except that the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 9 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 7 The procedure of Example 1 was repeated except that the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 10 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 8 The procedure of Example 1 was repeated, except that the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 4 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 9 The procedure of Example 1 was repeated, except that the maleated polyethylene wax before ring-opening obtained in Synthesis Example 1 was used.
All operations were performed in the same manner as in Example 1. Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 10 The procedure of Example 1 was repeated, except that the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 7 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 11 The procedure of Example 1 was repeated, except that the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 8 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 12 The procedure of Example 1 was repeated except that the amount of the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 1 was changed to 0.3 part by weight. . Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 13 In Example 1, the composition of the sample was changed to PVC1 having a polymerization degree of 1020.
00 parts by weight, 1.5 parts by weight of tribasic lead sulfate, 0.5 parts by weight of tribasic lead stearate, 0.5 parts by weight of lead stearate, 0.5 parts by weight of calcium stearate, obtained in Synthesis Example 2. Hydrolyzed ring-opened maleated polyethylene wax
All operations were performed in the same manner as in Example 1 except that the amount was changed to 5 parts by weight. Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 14 The procedure of Example 13 was repeated, except that the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 3 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 15 In Example 1, the composition of the sample was changed to PVC1 having a polymerization degree of 1050.
The same operation as in Example 1 was carried out except that 00 parts by weight, 3 parts by weight of a calcium-zinc composite stabilizer, and 0.8 part by weight of the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 2 were used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 16 The procedure of Example 15 was repeated, except that the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 3 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 17 The procedure of Example 13 was repeated, except that the maleated polyethylene wax before ring-opening obtained in Synthesis Example 1 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Example 18 The procedure of Example 15 was repeated, except that the maleated polyethylene wax before the ring opening obtained in Synthesis Example 1 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Comparative Example 1 The procedure of Example 1 was repeated, except that the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 11 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Comparative Example 2 The procedure of Example 1 was repeated, except that the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 12 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Comparative Example 3 The procedure of Example 1 was repeated, except that the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 13 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Comparative Example 4 The procedure of Example 1 was repeated, except that the hydrolyzed ring-opened maleated polyethylene wax obtained in Synthesis Example 14 was used. Tables 3 and 4 show the performance comparison test results of the blended samples.

Comparative Example 5 This example shows that a metal salt of an oxidized polyethylene wax was not effective, not a hydrolyzed ring-opened maleated polyethylene wax. All operations were performed in the same manner as in Example 1, except that polyethylene wax having a sodium salt formed after air oxidation was used instead of the hydrolyzed ring-opened maleated polyethylene wax. Tables 3 and 4 show the performance comparison test results of the blended samples.

Comparative Example 6 This example shows that a synthetic paraffin, Fischer-Tropsch wax, which was not a hydrolyzed ring-opened maleated polyethylene wax, had no effect. All operations were performed in the same manner as in Example 1 except that FT100 manufactured by Shell Malaysia was used instead of the hydrolyzed ring-opened maleated polyethylene wax. Tables 3 and 4 show the performance comparison test results of the blended samples.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

[0074]

[Table 4]

[0075]

According to the present invention, when the chlorine-containing resin is molded, the compatibility with the chlorine-containing resin is good, the gelation torque in the initial lubrication is low, and the time to reach the maximum gelation torque is short. A lubricant could be found.

[Brief description of the drawings]

FIG. 1 is a diagram of data obtained by measuring a sample in which a lead-based stabilizer and a commercially available lubricant are blended with hard PVC, using a Labo Plastomill Model 75C100 manufactured by Toyo Seiki Seisaku-sho, Ltd.

[Explanation of symbols]

 A Maximum gelation torque B Gelation time C Initial lubricity D Late lubricity

Claims (4)

[Claims] An essential component is a hydrolyzed maleated polyethylene wax obtained by graft-polymerizing maleic anhydride onto a polyethylene wax having a number average molecular weight of 400 to 5,000 and hydrolyzing this cyclic acid anhydride. Lubricant for chlorine-based resin. 2. The lubricant for a chlorine-containing resin according to claim 1, wherein the graft ratio of maleic anhydride is 2 to 10% by weight. 3. The lubricant for a chlorine-containing resin according to claim 1, wherein the ring-opening ratio is in the range of 40 to 100%. 4. The lubricant for a chlorine-containing resin according to claim 1, wherein the chlorine-containing resin is polyvinyl chloride.