JP2000319516A - Auxiliary for processing resin and thermoplastic resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an auxiliary which is used for processing resins, can impart persistent lubricity to the resins, and can prevent the deterioration of the resins, and to provide a thermoplastic resin composition using the auxiliary. SOLUTION: This auxiliary for processing resins comprises a copolymer composition which comprises 40 to 90 wt.% of a methacrylic acid (1 to 18C) alkyl ester-based units and 10 to 60 wt.% of an acrylic acid (1 to 18C) alkyl ester-based units and has a weight-average mol.wt. of 100,000 to 500,000, and contains 10 to 50 wt.% of a component having a weight-average mol.wt. of <=50,000. A thermoplastic resin composition uses the auxiliary.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin processing aid and a thermoplastic resin composition using the same, and more particularly, to a resin processing aid which imparts excellent lubricity and prevents resin deterioration. The present invention relates to an agent and a thermoplastic resin composition using the same.

[0002]

2. Description of the Related Art Thermoplastic resins such as ABS resin, styrene resin, and polyvinyl chloride resin have chemical resistance, impact resistance,
Because of its excellent properties such as weather resistance, it is widely used as a general-purpose resin material having high utility value. In particular, polyvinyl chloride resin is inexpensive and advantageous in cost, so that it is more versatile. These thermoplastic resins are blended with a processing aid such as a copolymer containing high-molecular-weight methyl methacrylate as a main component to adjust the melt viscosity of the thermoplastic resin and improve the moldability. In particular, polyvinyl chloride resin has a low thermal decomposition temperature and cannot be set at a high molding processing temperature. Therefore, a method of adjusting the melt viscosity by adding a processing aid and improving the molding processability is widely used. I have. However, since the high molecular weight methyl methacrylate copolymer has adhesiveness to the metal surface and has a high melt viscosity, when a resin containing such a copolymer is calendered, the calender roll surface In addition, there were problems such as adhesion of the resin sheet and deterioration of the releasability. In addition, when the extrusion is continuously performed for a long time, the resin may deteriorate and stay in the resin, or the deteriorated resin may adhere to the exit of the die, or the like. To solve these problems, polyvinyl chloride resin compositions are disclosed in Japanese Patent Publication No. 6-62826 and Japanese Patent Publication No. 2-50.
No. 137, the ABS resin composition is disclosed in
Japanese Patent Application Laid-Open No. Hei 10-87928 and the like have widely studied processing aids to be added to thermoplastic resins for styrenic resin compositions such as JP-208798-A. It has been improved to some extent. Also, the use of lower molecular weight processing aids has been attempted.

[0003]

However, when a processing aid having a low molecular weight is used, a decrease in lubricity continuity,
There were new problems, such as bloom on the surface of the molded product and plate out to the mold during molding. In recent years, in order to improve the productivity of thermoplastic resins, there has been a strong demand for high-speed molding and continuous operation for a long period of time. And when extruding for a long time,
There has been a strong demand for the development of a processing aid capable of improving the lubricity and long-run property for preventing the resin from deteriorating due to stagnation and adherence of the degraded resin to the die outlet.

The present invention has been made in view of the above circumstances, and provides a thermoplastic resin with more excellent lubricity lasting property, thereby improving the releasability of a calender roll. A processing aid for resins that can prevent adhesion of degraded resin to the outlet, does not cause bloom on the surface of molded products, and does not cause plate-out to a mold during molding, and a thermoplastic resin composition using the same. The task is to provide

[0005]

The object of the present invention is to provide an alkyl methacrylate ester unit having from 1 to 18 carbon atoms in an amount of from 40 to 90% by weight and an ester group having from 1 to 18 carbon atoms.
A copolymer composition having a weight average molecular weight of 100,000 to 500,000 containing 10 to 60% by weight of an alkyl acrylate ester unit of 18 and a component having a weight average molecular weight of 50,000 or less being 10 to 50% by weight. The problem is solved by a processing aid for resins characterized by containing. The component having a weight average molecular weight of 50,000 or less is composed of 30 to 70% by weight of an alkyl methacrylate unit having 1 to 4 carbon atoms and an alkyl acrylate unit having 2 to 4 carbon atoms of an ester group. Preferably, it comprises 30 to 70% by weight. Further, such a problem is, with respect to 100 parts by weight of the thermoplastic resin,
The problem is solved by a thermoplastic resin composition containing 0.01 to 20 parts by weight of a resin processing aid.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
As the alkyl methacrylate having 1 to 18 carbon atoms in the ester group constituting the copolymer composition of the present invention,
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid-2-
There are no particular restrictions on ethylhexyl and the like, and these can be used alone or in combination of two or more. Of these, alkyl methacrylates having 1 to 4 carbon atoms in the ester group such as methyl methacrylate and n-butyl methacrylate are preferred. Furthermore, it is particularly preferable to use a combination of methyl methacrylate and n-butyl methacrylate because the resulting copolymer composition becomes a resin processing aid having excellent compatibility with a thermoplastic resin. Examples of the alkyl acrylate having 1 to 18 carbon atoms in the ester group include ethyl acrylate,
Propyl acrylate, butyl acrylate, acrylic acid-
Examples thereof include 2-ethylhexyl, and there is no particular limitation. These can be used alone or in combination of two or more. In these, the carbon number of the ester group is 2
To 4 are preferred, but the resulting copolymer composition is controlled in compatibility with a thermoplastic resin and serves as a resin processing aid capable of imparting more lubricity to acrylic acid-n- It is particularly preferred to use butyl.

[0007] The proportion of the alkyl methacrylate having 1 to 18 carbon atoms in the ester group constituting the copolymer composition is 40 to 90% by weight, preferably 50 to 80% by weight. The copolymer composition obtained as this ratio is higher,
It is easy to disperse uniformly in the thermoplastic resin, becomes a processing aid for the resin with excellent compatibility, and the smaller this ratio is, the more the obtained copolymer composition is a resin processing agent capable of imparting lubricity to the thermoplastic resin. Auxiliary. Accordingly, by adjusting the proportion of the alkyl methacrylate ester unit having 1 to 18 carbon atoms in the ester group within the above range, the compatibility and lubricity imparting property of the resin processing aid can be adjusted. . Further, when the amount of the alkyl methacrylate ester unit having 1 to 18 carbon atoms in the ester group exceeds 90% by weight, the lubricity-imparting property is reduced. It may be difficult to recover this as a powder from the latex.

The proportion of the alkyl acrylate unit having 1 to 18 carbon atoms in the ester group constituting the copolymer composition is 10 to 60% by weight, preferably 20 to 50% by weight.
It is. The copolymer composition obtained as the ratio increases becomes a resin processing aid capable of imparting lubricity to the thermoplastic resin. In addition, the smaller the ratio is, the more the obtained copolymer composition becomes a resin processing aid which suppresses bloom on the surface of a molded article and plate-out to a mold during molding. Therefore, the lubricity imparting property of the resin processing aid can be adjusted by adjusting the ratio of the acrylic acid alkyl ester-based unit having 1 to 18 carbon atoms in the ester group within the above range. Further, when the carbon number of the ester group is 1
When the acrylic acid alkyl ester-based unit of (A) to (C) exceeds 60% by weight, the glass transition temperature becomes low. Therefore, the copolymer composition is coagulated and recovered from the latex obtained when the copolymer composition is produced by emulsion polymerization. It can be difficult. If it is less than 10% by weight, the lubricity-imparting property may decrease.

The units constituting the copolymer composition are copolymerizable with an alkyl methacrylate having an ester group of 1 to 18 carbon atoms and an alkyl acrylate having an ester group of 1 to 18 carbon atoms. Vinyl monomer units can be introduced in the range of 0 to 20% by weight. Examples of such a vinyl monomer include (meth) acrylic esters having an aromatic functional group such as benzyl (meth) acrylate and phenyl (meth) acrylate; styrene, α-methylstyrene, and vinyltoluene. And vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate; and acid anhydrides such as maleic anhydride.

[0010] A copolymer containing 40 to 90% by weight of an alkyl methacrylate unit having 1 to 18 carbon atoms of an ester group and 10 to 60% by weight of an alkyl acrylate unit having 1 to 18 carbon atoms of an ester group. The weight average molecular weight of the polymer composition is 100,000 to 500,000, preferably 100,000 to 3
100,000. Here, the weight average molecular weight is a polystyrene equivalent weight average molecular weight (hereinafter, referred to as weight average molecular weight) measured by gel permeation chromatography (hereinafter, referred to as GPC). The smaller the weight average molecular weight of the copolymer composition is, the more preferable it is because the copolymer composition is uniformly dispersed in the thermoplastic resin and melted, and also becomes a resin processing aid capable of imparting more lubricity. Also, a larger weight average molecular weight is preferable because it becomes a processing aid for resin that is less likely to cause bloom on the surface of the molded product or plate out to a mold during molding. Therefore, by adjusting the weight average molecular weight of the copolymer composition within the above range, the lubricity imparting property of the resin processing aid can be adjusted. If the weight average molecular weight exceeds 500,000, the lubricity imparting property decreases. If it is less than 100,000, the glass transition temperature becomes low, so that it may be difficult to coagulate and collect the latex obtained when the copolymer composition is produced by emulsion polymerization.

Further, the copolymer composition contains 10 to 50% by weight, preferably 20 to 50% by weight, of a component having a weight average molecular weight of 50,000 or less as measured by GPC. The low molecular weight component having a weight average molecular weight of 50,000 or less is to impart excellent lubricity to the thermoplastic resin,
When such a low molecular weight component is less than 10% by weight, the lubricating effect of the resin processing aid is not sufficient. On the other hand, if the low-molecular weight component exceeds 50% by weight, the resulting resin processing aid tends to cause bloom on the surface of the molded product or plate-out to the mold at the time of molding, and the glass transition temperature is low. In some cases, it becomes difficult to coagulate and recover the latex obtained when the copolymer composition is produced by emulsion polymerization, because of the lowering.

As the component having a weight average molecular weight of 50,000 or less, a component having a low glass transition point and having a certain degree of compatibility with a thermoplastic resin is preferably used. By including such a low molecular weight component, the effect of imparting lubricity of the resulting resin processing aid can be further enhanced. The components having a weight average molecular weight of 50,000 or less have an ester group having 1 to 1 carbon atoms.
It is preferable that the methacrylic acid-based unit is a combination of a methacrylic acid alkyl ester-based unit having 4 to 4 carbon atoms and an acrylate alkyl ester-based unit having 2 to 4 carbon atoms. 30 to 70% by weight of an alkyl ester unit and 30 to 70% by weight of an alkyl acrylate unit having 2 to 4 carbon atoms in the ester group
Preferably it consists of% by weight. Above all, it is preferable to use a unit composed of n-butyl methacrylate unit and n-butyl acrylate unit because the effect of imparting lubricity by controlling the compatibility with the thermoplastic resin is large.

The method of the polymerization reaction for producing the copolymer composition can be a known method, and is not particularly limited, but is preferably polymerized by an emulsion polymerization method. Further, the copolymer composition has a weight average molecular weight of 100,000 to 500,000, and preferably is a copolymer composition containing 10 to 50% by weight of a component having a specific composition and a weight average molecular weight of 50,000 or less. So, a method of forming a multiphase structure composed of a high molecular weight component and a low molecular weight component by sequential multi-stage polymerization, or obtaining a high molecular weight component and a low molecular weight component by an emulsion polymerization method, etc., and then blending both components It is manufactured by a method or the like. Although there is no particular limitation on such a production method, it is preferable that the production is carried out by sequential multi-stage polymerization since a resin processing aid having a more excellent lubricity-imparting effect can be obtained.

When the copolymer composition is produced by the emulsion polymerization method, known emulsifiers can be used, and examples thereof include fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, and alkyl phosphates. Anionic surfactants such as ester salts and dialkyl sulfosuccinates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan acid fatty esters, and glycerin fatty acid esters; and alkylamine salts Isocationic surfactants and the like. In addition, these emulsifiers alone,
Alternatively, two or more kinds can be used in combination.
When the pH of the polymerization reaction system becomes alkaline depending on the type of the emulsifier to be used, a suitable pH adjuster can be used to prevent the hydrolysis of the alkyl (meth) acrylate. pH adjusters include boric acid-potassium chloride-potassium hydroxide, potassium dihydrogen phosphate-disodium hydrogen phosphate, boric acid-potassium chloride-potassium carbonate, citric acid-potassium hydrogen citrate, potassium dihydrogen phosphate Borax, disodium hydrogen phosphate-citric acid, etc. can be used. As the polymerization initiator, a water-soluble or oil-soluble single type or a redox type can be used. Inorganic initiators such as, for example, persulfates; t
Organic peroxides such as -butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, and lauroyl peroxide; and azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile. These initiators may be used alone, but can also be used as a redox initiator in combination with sulfites, bisulfites, thiosulfates, sodium formaldehyde sulfoxylate, etc., and particularly with organic peroxides When used as a redox initiator in combination with sodium formaldehyde sulfoxylate, etc., the polarity of the terminal group of the obtained copolymer is suppressed as much as possible, the adhesiveness between the thermoplastic resin and the metal surface is reduced, and It is preferable because the lubricating effect of the processing aid is more excellent.

After the completion of the polymerization reaction, the copolymer is recovered by a known method. For example, when polymerized by an emulsion polymerization method, after cooling the copolymer latex, an acid such as sulfuric acid, hydrochloric acid, phosphoric acid, or a salt such as aluminum chloride, calcium chloride, magnesium sulfate, aluminum sulfate, calcium acetate, or the like. The copolymer can be coagulated and precipitated by acid coagulation or salting-out with the above electrolyte, and then filtered, washed, dried and the like to obtain copolymer particles. Further, a method of collecting the obtained polymer latex by a method such as spray drying or freeze drying can also be used.

The obtained copolymer composition is blended with a thermoplastic resin as a resin processing aid. There is no particular limitation on the thermoplastic resin, for example, polyvinyl chloride resin, polyolefin resin, polyurethane resin, polyvinylidene fluoride resin, ABS resin, AES resin, ASA resin, styrene resin, modified PPE resin, polycarbonate resin, Commercially available resins such as acrylic resins, polyester resins, polyacetal resins, polyamide resins, polysulfone resins, polyphenylene sulfide resins, polyarylate resins, polyetherimide resins, polyetherketone resins, and polyimide resins can be used.
The mixing ratio of the resin processing aid to the thermoplastic resin is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the thermoplastic resin. If the amount is less than 0.01 part by weight, the lubricating effect may be small. If the amount exceeds 20 parts by weight, the properties such as heat resistance and mechanical strength of the thermoplastic resin may be impaired, and the performance of the obtained thermoplastic resin composition may be reduced.

The method of blending the resin processing aid with the thermoplastic resin is not particularly limited, and a known mixing method and a melt-kneading method can be used. For example, a predetermined amount of a thermoplastic resin and a processing aid for a resin are mixed with a Henschel mixer, a Banbury mixer, a V-type mixer, a ribbon blender or the like to obtain a compound, which is then subjected to a single screw extruder, a twin screw extruder, or the like. And a thermoplastic resin composition can be obtained. In this case, if necessary, various additives such as known processing aids, stabilizers, fillers, flame retardants, foaming agents, impact modifiers, antistatic agents, coloring agents, plasticizers, lubricants, etc. Can be added.

The thermoplastic resin composition thus obtained can be applied to a known molding method such as calender molding, extrusion molding, injection molding and blow molding to obtain various molded products. In addition, the effect of imparting lubricity is particularly large in extrusion molding. The method of using the product obtained by molding the obtained thermoplastic resin composition is not limited at all, and can be widely used, for example, for building materials, vehicles, and electric appliances.

[0019]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to only these examples. In the Examples and Comparative Examples, “parts” means “parts by weight” unless otherwise specified. The measurement and evaluation of various physical properties in the following Examples and Comparative Examples were measured and evaluated by the following methods. (1) Weight average molecular weight distribution measurement (GPC measurement) The dried sample was added to tetrahydrofuran (THF) for 40 minutes.
After dissolving at 1 ° C. for 1 hour, the mixture was allowed to stand at room temperature overnight, and GPC (HLC-8020) manufactured by Tosoh Corporation, a GPC column (TSK-GEL GMHXL × 2) manufactured by Tosoh Corporation
Was measured under the following conditions. In addition, the calibration curve of GPC was created using the company's monodisperse polystyrene. -Sample concentration: 0.1 g / dl-Injection amount: 0.1 ml-Column temperature: 40 ° C (2) Evaluation of roll releasability 100 g of sample under the following conditions using a 6 inch 2 roll
Was kneaded, and the time until the sheet adhered to the roll surface and did not peel off was measured. The longer this time, the better the lubricity sustained at high temperatures.・ Roll temperature: 205 ° C. × 200 ° C. ・ Roll interval: 1 mm (3) Evaluation of long run property The sample was continuously extruded for 8 hours using a 25 mmφ single screw extruder. The amount was visually evaluated according to the following criteria. ：: Almost no deposits Δ: Slight deposits are found X: Considerable deposits are seen

Reference Example 1 Production of Copolymer Composition (b-1) A polymerization reaction was carried out in two steps as follows to produce a copolymer composition (b-1). 280 ion-exchanged water in the reaction vessel
Parts, 1.5 parts of dipotassium alkenyl succinate was charged,
After replacing the inside of the vessel with nitrogen, the reaction vessel was cooled to 65 ° C. with stirring.
After the temperature was raised to t-butyl hydroperoxide 1
Parts, 0.0003 parts of ethylenediaminediacetic acid, 0.0001 parts of ferrous sulfate and 0.5 parts of sodium formaldehyde sulfoxylate. Next, 30 parts of n-butyl methacrylate and 35 parts of n-butyl acrylate
And a mixture consisting of 0.3 parts of n-octylmercaptan and 0.3 part of n-octylmercaptan were added dropwise over 1 hour, and the mixture was further stirred for 2 hours to carry out the first stage polymerization reaction. Then, 35 parts of methyl methacrylate, 0.02 part of t-butyl hydroperoxide, and 0.00 part of n-octyl mercaptan
A mixture of 6 parts was added dropwise over 1 hour, followed by 2 more parts.
Stirring was continued for an hour to complete the polymerization. After cooling the obtained latex to room temperature, it is coagulated with an aqueous solution of sulfuric acid, filtered, washed,
After drying, a copolymer composition (b-1) was obtained. Table 1 shows the weight average molecular weight of the obtained copolymer composition (b-1) and the content of components having a weight average molecular weight of 50,000 or less.

Reference Example 2 Production of Copolymer Composition (b-2) A polymerization reaction was carried out in three steps as follows to produce a copolymer composition (b-2). 280 parts of ion-exchanged water, 1.5 parts of dipotassium alkenyl succinate, 0.03 parts of t-butyl hydroperoxide, 0.007 parts of n-octyl mercaptan were placed in a reaction vessel equipped with a stirrer and a reflux condenser.
And 30 parts of methyl methacrylate were charged, and the inside of the vessel was replaced with nitrogen. Then, the temperature of the reaction vessel was raised to 65 ° C. with stirring,
0.0003 parts of ethylenediamine diacetic acid, 0.0001 parts of ferrous sulfate and 0.5 parts of sodium formaldehyde sulfoxylate were added, and stirring was continued for 4 hours to complete the first-stage polymerization reaction. Subsequently, 0.75 part of t-butyl hydroperoxide was added while maintaining the polymerization system at 65 ° C. under a nitrogen atmosphere, and then 20 parts of n-butyl methacrylate and 30 parts of n-butyl acrylate. And a mixture consisting of 0.25 parts of n-octylmercaptan was added dropwise over 1 hour, and the mixture was further stirred for 2 hours to carry out a second stage polymerization reaction. Thereafter, 20 parts of methyl methacrylate, 0.02 part of t-butyl hydroperoxide, and 0.0 part of n-octyl mercaptan 0.0
One part of the mixture was added dropwise over 1 hour, followed by 2 more parts.
Stirring was continued for an hour to complete the polymerization. The obtained latex was post-treated in the same manner as in Reference Example 1 to obtain a copolymer composition (b-
2) was obtained. Table 1 shows the weight average molecular weight of the obtained copolymer composition (b-2) and the content of components having a weight average molecular weight of 50,000 or less.

Reference Example 3 Production of Copolymer Composition (b-3) A copolymer and a polymer were blended as follows to produce a copolymer composition (b-3). A reaction vessel equipped with a stirrer and a reflux condenser was charged with 280 parts of ion-exchanged water and 1.5 parts of dipotassium alkenyl succinate. After the inside of the vessel was replaced with nitrogen, the temperature of the reaction vessel was raised to 65 ° C. with stirring, and then t. −
1.5 parts of butyl hydroperoxide, 0.0003 parts of ethylenediamine diacetate, 0.0001 part of ferrous sulfate and 0.5 part of sodium formaldehyde sulfoxylate are added, and then 40 parts of n-butyl methacrylate, A mixture consisting of 60 parts of n-butyl acrylate and 0.5 part of n-octylmercaptan was added dropwise over 1 hour, and stirring was continued for another 2 hours to complete the polymerization to obtain a latex (x1). Meanwhile, 280 parts of ion-exchanged water and 1.5 parts of dipotassium alkenyl succinate were charged into another reaction vessel equipped with a stirrer and a reflux condenser, and the inside of the vessel was replaced with nitrogen. Then, the temperature of the reaction vessel was raised to 65 ° C. with stirring. After that, 0.1 part of t-butyl hydroperoxide,
0.0003 parts of ethylenediaminediacetic acid, 0.0001 part of ferrous sulfate and 0.5 part of sodium formaldehyde sulfoxylate are added, followed by 100 parts of methyl methacrylate and 0.1 part of n-octylmercaptan.
A mixture consisting of 02 parts was added dropwise over 1 hour, and the mixture was further stirred for 2 hours to terminate the polymerization, and a latex (x2)
I got The two latexes thus obtained were mixed with x1:
The blend was blended at a weight ratio of x2 = 1: 1, and the obtained latex was post-treated in the same manner as in Reference Example 1 to obtain a copolymer composition (b-3). Obtained copolymer composition (b-3)
Table 1 shows the weight average molecular weight and the content of components having a weight average molecular weight of 50,000 or less.

Reference Example 4 Production of Copolymer Composition (b-4) As monomers used in the first stage polymerization reaction, 30 parts of n-butyl methacrylate and 35 parts of n-butyl acrylate were used. Was replaced with 30 parts of styrene and 35 parts of n-butyl acrylate in the same manner as in Reference Example 1 to obtain a copolymer composition (b-4). The obtained copolymer composition (b
Table 1 shows the weight average molecular weight of -4) and the content of the component having a weight average molecular weight of 50,000 or less.

Reference Example 5 Production of Copolymer Composition (b-5) As monomers used in the first stage polymerization reaction, 30 parts of n-butyl methacrylate and 35 parts of n-butyl acrylate were used. Instead of methyl methacrylate 40 parts, acrylic acid-
A copolymer composition (b-5) was obtained in the same manner as in Reference Example 1, except that 5 parts of n-butyl and 20 parts of styrene were used. Table 1 shows the weight average molecular weight of the obtained copolymer composition (b-5) and the content of components having a weight average molecular weight of 50,000 or less.

Reference Example 6 Production of Copolymer Composition (b-6) The n-butyl hydroperoxide used in the second stage polymerization reaction was changed to 0.1 part instead of 0.75 part, A copolymer composition (b-6) was obtained in the same manner as in Reference Example 2, except that octyl mercaptan was changed to 0.02 parts instead of 0.25 parts. Obtained copolymer composition (b-6)
Table 1 shows the weight average molecular weight and the content of components having a weight average molecular weight of 50,000 or less.

[0026]

[Table 1]

Examples 1 to 5 and Comparative Examples 1 to 3 Using the copolymer compositions obtained in the above Reference Examples 1 to 6 as a resin processing aid, polyvinyl chloride resin (average degree of polymerization 700) And a mixture shown in Table 2 using a Henschel mixer to obtain a polyvinyl chloride resin composition. At this time, 2.0 parts of dibutyltin mercaptide, 1.0 part of epoxidized soybean oil, and 0.5 part of dibutyltin malate were mixed together. Table 2 shows the results of evaluating the roll release properties of the obtained polyvinyl chloride resin composition.

Comparative Example 4 A polyvinyl chloride resin composition was obtained in the same manner as in Example 1 except that no resin processing aid was added. Table 2 shows the results of evaluating the roll release properties of the obtained polyvinyl chloride resin composition.

[0029]

[Table 2]

As is apparent from Table 2, 40 to 90% by weight of alkyl methacrylate units having 1 to 18 carbon atoms in the ester group and alkyl acrylate units having 1 to 18 carbon atoms in the ester group. The polyvinyl chloride resin composition blended with a copolymer composition having a specific molecular weight distribution of 10 to 60% by weight had good roll release properties and excellent sustained lubrication.

Examples 6 to 15 Reference Example 2 was used as a resin processing aid for 100 parts of each thermoplastic resin shown in Table 3.
2 parts of the copolymer composition (b-2) obtained in the above was mixed with a Henschel mixer to obtain a thermoplastic resin composition. Table 3 shows the long-run evaluation results of the obtained thermoplastic resin composition. The following resin was used as the thermoplastic resin. (1) Polyvinyl chloride resin: TK-800 (manufactured by Shin-Etsu Chemical Co., Ltd.) (2) ABS resin: Diapet SW-3 (manufactured by Mitsubishi Rayon Co., Ltd.) (3) Styrene resin: Stylon 492 (Asahi Kasei Corporation) (4) Polycarbonate resin: Lexan (Mitsubishi Chemical Corporation) (5) Acrylic resin: Acrypet MD (Mitsubishi Rayon Co., Ltd.) (6) Polyester resin: Diamondite A- 200
(Mitsubishi Rayon Co., Ltd.) (7) ASA resin: Diamond Rack (Mitsubishi Rayon Co., Ltd.)
(8) Polyamide resin: Amilan CM1061 (manufactured by Toray Industries, Inc.) (9) Modified polyolefin oxide resin: Noryl HB
(Nippon GE Plastics) (10) Polyacetal resin: DURACON AW01 (polyplastic)

Comparative Examples 6 to 15 Thermoplastic resin compositions were obtained in the same manner as in Examples 1 to 6, except that no resin processing aid was added to each thermoplastic resin. Table 3 shows the long-run evaluation results of the obtained thermoplastic resin composition.

[0033]

[Table 3]

As is apparent from Table 3, 40 to 90% by weight of alkyl methacrylate units having 1 to 18 carbon atoms of the ester group and alkyl acrylate units having 1 to 18 carbon atoms of the ester group. In a thermoplastic resin composition in which a copolymer composition having a specific molecular weight distribution of 10 to 60% by weight was blended as a processing aid for a resin, almost no deposits were observed in the long run property evaluation, and resin deterioration was observed. Had been suppressed.

[0035]

The resin processing aid of the present invention comprises 40 to 90% by weight of an alkyl methacrylate ester unit having 1 to 18 carbon atoms in the ester group and 1 to 1 carbon atom in the ester group.
8 is a copolymer composition having a weight average molecular weight of 100,000 to 500,000 containing 10 to 60% by weight of an acrylic acid alkyl ester-based unit, and a component having a weight average molecular weight of 50,000 or less being 10 to 50% by weight. Because it is a processing aid for resins characterized by containing, it gives the thermoplastic resin excellent lubricity persistence,
Also, it imparts lubricity and long-run properties to the thermoplastic resin by improving the releasability of the calender roll during calendering and preventing the resin from deteriorating due to stagnation during the extrusion process and preventing the adhesion of the degraded resin at the die exit. be able to. Also,
A component having a weight-average molecular weight of 50,000 or less is converted into an alkyl methacrylate-based unit 30 having an ester group of 1 to 4 carbon atoms.
-70% by weight and 30-70% by weight of an acrylic acid alkyl ester-based unit having 2 to 4 carbon atoms in the ester group, whereby an excellent resin processing aid capable of imparting more lubricity continuity. It can be. In addition, the thermoplastic resin composition of the present invention is one in which 0.01 to 20 parts by weight of the above-mentioned resin processing aid is blended with respect to 100 parts by weight of the thermoplastic resin, so that excellent lubricity lasting property is obtained. And has excellent calender roll releasability and also has long run properties. Therefore, it is a thermoplastic resin composition excellent in industrial productivity suitable for high-speed molding and continuous operation for a long time.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 33:10) F-term (reference) 4J002 AA011 BG042 BG052 GT00 4J100 AL03P AL03Q AL04P AL04Q CA04 CA05 CA06 DA01

Claims (3)

[Claims] 1. An alkyl methacrylate unit having 1 to 18 carbon atoms in an ester group having 40 to 90% by weight and an alkyl acrylate unit having 1 to 18 carbon atoms in an ester group having 10 to 60% by weight. Contains a weight average molecular weight of 1
A processing aid for a resin, which is a copolymer composition of 100,000 to 500,000 and contains 10 to 50% by weight of a component having a weight average molecular weight of 50,000 or less. 2. A component having a weight average molecular weight of 50,000 or less, 30 to 70% by weight of an alkyl methacrylate unit having 1 to 4 carbon atoms in an ester group, and an acryl having 2 to 4 carbon atoms in an ester group. Acid alkyl ester-based unit 30 to 70
The processing aid for resins according to claim 1, wherein the processing aid consists of% by weight. 3. The resin processing aid according to claim 1 or 2, based on 100 parts by weight of the thermoplastic resin.
A thermoplastic resin composition containing parts by weight.