JPH04252217A - Graft copolymer having slipperiness-imparting effect and thermoplastic resin composition compounded therewith - Google Patents

Abstract

PURPOSE:To provide a graft copolymer to be compounded to a resin to impart the resin with lubricating effect such as moldreleasability, flowability, etc., in molding. CONSTITUTION:The objective graft copolymer having a reduced viscosity (etasp/c) of <2 (isolated polymer) and exhibiting lubrication effect can be produced by the graft-polymerization of (A) 80-10 pts.wt. of one or more monomers selected from a styrene monomer, a methacrylic acid ester and an acrylic acid ester in the presence of (B) 20-90 pts.wt. (in terms of solid) of a rubber (a) latex of a non-crosslinked ethylene-propylene-nonconjugated diene copolymer. A thermoplastic resin composition is produced by compounding 0.01-20 pts.wt. of the graft copolymer to 100 pts.wt. of a thermoplastic resin.

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a graft copolymer having the property of imparting lubricating effects such as mold releasability and fluidity during molding to a thermoplastic resin composition. Furthermore, a thermoplastic resin with good lubricity is obtained by blending the graft copolymer with a thermoplastic resin such as vinyl chloride resin, polycarbonate resin, polyester resin, ABS resin, styrene resin, methacrylic resin, polyethylene resin, etc. Regarding the composition.

BACKGROUND OF THE INVENTION Thermoplastic resins have the disadvantage of poor processability in various ways. In order to improve this processability, plasticizers, processing aids such as copolymers mainly composed of methyl methacrylate, and lubricants are added and blended, but what is the general solution? It wasn't possible. Therefore,
In order to solve these problems, we have improved the maintenance of transparency, processability such as drawdown, fluidity during molding, elongation at high temperatures,
A variety of research and development efforts are being carried out with the aim of improving the sustainability of lubricity, such as releasability from the roll surface during calendering. For example, regarding vinyl chloride resin compositions, Various formulations have been proposed as shown in Japanese Patent Publication No. 781, Japanese Patent Publication No. 52-3668, Japanese Patent Publication No. 50-37699, etc.

[Problems to be Solved by the Invention] However, in recent years, from the standpoint of improving productivity, improving quality, and saving energy, it has become necessary to improve the durability of lubricity during various processing before molding, and to maintain good lubricity during molding. There is a strong demand for a lubricant that can be used as a resin composition that can impart mold releasability and fluidity as well as gloss and transparency to molded products. It cannot be said that the vinyl chloride resin compositions described in the above-mentioned publications still fully satisfy market demands. An object of the present invention is to provide a lubricant that fully satisfies the above-mentioned needs, and furthermore, to provide a resin composition containing this lubricant.

[Means for Solving the Problems] As a result of intensive studies to obtain a lubricant that satisfies the above-mentioned requirements, the present inventors have developed a non-crosslinked ethylene-propylene-nonconjugated diene copolymer rubber that contains styrene and methacrylic acid. Graft copolymerization obtained by polymerizing at least one monomer selected from the group consisting of esters and acrylic esters, in which the free polymer when extracted with acetone has a reduced viscosity η within a specific range.
It was discovered that a graft copolymer having sp/c has an excellent lubricity effect, and the present invention was achieved. That is,
The invention of claim 1 is a non-crosslinked ethylene-propylene-nonconjugated diene copolymer rubber (a) latex 20-90
80 to 10 parts by weight of at least one monomer (b) selected from the group consisting of styrene monomers, methacrylic esters, and acrylic esters in the presence of 80 to 10 parts by weight (as solid content) Total amount of a) + (b) 100 parts by weight]
A graft copolymer obtained by polymerizing the free polymer, which has a reduced viscosity ηsp/c of 2 when extracted with acetone.
It is a graft copolymer having a lubricity effect of less than 0.1 g (measured at 25° C. after dissolving 0.1 g of the polymer in 100 ml of chloroform). Further, the invention of claim 2 provides that the thermoplastic resin 1
0.00 parts by weight and 0.01 to 20 parts by weight of the graft copolymer having a lubricating effect according to claim 1. The ethylene-propylene-nonconjugated diene copolymer rubber used in the present invention includes ethylene, propylene, and a third component such as dicyclopentadiene, ethylidene norbornene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl -Ethylene-propylene-nonconjugated diene terpolymer (hereinafter abbreviated as EPDM) consisting of one or more nonconjugated dienes such as -1,5-hexadiene, 1,4-cycloheptadiene, and 1,5-cyclooctadiene It is. As this non-conjugated diene component, it is particularly preferable to use one or more of dicyclopentadiene and ethylidene norbornene. The molar ratio of ethylene and propylene in EPDM is 5:1
to 1:3, and EPDM
The proportion of unsaturated groups therein is preferably in the range of 4 to 50 in terms of iodine value. There are no particular restrictions on the manufacturing method of EPDM latex, but EPD
Generally, M is finely dispersed and stabilized in water by applying mechanical shearing force to form latex. The particle size of the EPDM latex is preferably 2 μm or less. 2μm
If the graft copolymer is graft-polymerized with this and is blended with other thermoplastic resins and molded, it will affect the transparency and gloss of the molded product, making it difficult to obtain an excellent product. I can't. EPDM used in the present invention needs to be non-crosslinked. If this EPDM is crosslinked, the mold releasability and fluidity during molding will be poor, and no lubricity effect will be obtained, which is not preferable. Further, in the present invention, the content of the non-crosslinked ethylene-propylene-nonconjugated diene copolymer rubber (a) in the graft copolymer is preferably 20 to 90 parts by weight (as solid content), preferably 30 to 80 parts by weight. It is. If the content is less than 20 parts by weight, the lubricating effect that is the objective of the present invention cannot be obtained, and if the content exceeds 90 parts by weight,
The surface gloss of a molded article made of a resin composition containing this compound is poor, which is not preferable. The graft copolymer in the present invention is produced by an emulsion polymerization method. In preparing the graft copolymers of the present invention, the graft copolymers are prepared from a group consisting of styrene, methacrylic esters and acrylic esters in the presence of 20 to 90 parts by weight (as solids) of a latex of EPDM(a). At least one selected monomer (b
) 80 to 10 parts by weight [total amount of (a) + (b) 100 parts by weight] in the presence of a radical polymerization initiator, monomer (b)
Polymerization is carried out by adding the entire amount to the latex at once, in portions, or continuously. Polymerization initiators include thermal decomposition type initiators such as potassium persulfate and ammonium persulfate;
Alternatively, a redox initiator such as a sugar-containing pyrophosphate formulation, which is a combination of cumene hydroperoxide, iron compound, sodium pyrophosphate, and dextrose, can be used. tert instead of cumene hydroperoxide
-Butyl hydroperoxide, diisopropylbenzene hydroperoxide, etc. can also be used. It is also possible to use sodium salt of ethylenediaminetetraacetic acid (EDTA-2Na) instead of sodium birophosphate. It is also possible to use sodium formaldehyde sulfoxylate instead of dextrose. During graft polymerization, it is preferable to add an additional emulsifier to stabilize the polymerization. As the emulsifier, any anionic emulsifier that can be used in normal emulsion polymerization can be used without any particular restriction, but fatty acid soaps, rosin acid soaps, etc. are common. The monomer (b) used in the production of the graft copolymer of the present invention should be Examples include styrene, α-methylstyrene, etc., which have poor compatibility with vinyl chloride resin, and monomers with a low glass transition temperature Tg are preferred as methacrylic esters and acrylic esters. Furthermore, if the monomer used in the graft copolymer has a low molecular weight and the reduced viscosity ηsp/c is in the range of less than 2, preferably 1.8 or less, the lubricity effect can be obtained. When the reduced viscosity is 2 or more, mold release properties and fluidity tend to be poor during molding. The reduced viscosity can be adjusted as appropriate by adjusting the chain transfer agent, catalyst, and polymerization temperature used during polymerization. The reduced viscosity η sp/c defined in the present invention is measured by dissolving 0.1 g of the above graft copolymer in 100 ml of chloroform and measuring at 25° C. using an Ostwald viscometer. The above graft copolymer can be mixed with vinyl chloride resin, polycarbonate resin, polyester resin, AB
By blending 0.01 to 20 parts by weight per 100 parts by weight of S resin, styrene resin, methacrylic resin, or polyethylene resin, it has a slippery effect, that is, excellent fluidity and mold release properties during molding, and improves the shape of the molded product. A resin composition with excellent gloss can be obtained. The amount of graft polymer blended is 20
If it exceeds parts by weight, the lubricity effect will be too great. That is, the fluidity during molding is too high, resulting in poor shape, gloss, etc. of the resulting molded product. If the amount is less than 0.01 part by weight, mold releasability and fluidity during molding will be low, extensive heat generation will occur, and discoloration of the molded product will occur, which is undesirable. The graft copolymer of the present invention may be added to a thermoplastic resin by mixing according to a conventional method. In addition, such resin compositions may contain stabilizers such as organotin compounds, lead-based, barium-based, zinc-based metal soaps, and other epoxy compounds; stearic acid, ester wax, paraffin wax, and stearyl. , lubricants such as alcohol; plasticizers such as phthalate esters, phosphate esters, fatty acid esters, and epoxy systems; colorants such as carbon black and titanium oxide; fillers such as calcium carbonate and asbestos; Inorganic foaming agents such as ammonia carbonate and sodium bicarbonate; organic foaming agents such as nitro, sulfohydrazide and azo foams may also be blended.

[Examples] The present invention will be explained in more detail with reference to Examples and Comparative Examples below. In Examples and Comparative Examples, all "parts" indicate parts by weight. Also, the reduced viscosity ηsp/c of each polymer
is the reduced viscosity η of the free polymer obtained by extracting the graft copolymer resin obtained by polymerization with acetone using the specified emulsifier, polymerization initiator, polymerization temperature, and chain transfer agent as variables.
sp/c was measured and set as ηsp/c. Each evaluation was performed using the following method. (Mold releasability) Kneading temperature 205℃ using 6 inch roll
A sample of 100 g is kneaded at 200° C. with a roll spacing of 1 mm, and the time required for the sheet to adhere to the roll surface and not peel off is measured. The longer this time, the better the durability of slipperiness. (Fluidity) The amount of extrusion was measured using a 25φmm single screw extruder. The larger the extrusion amount and the lower the pressure, the better the fluidity and the greater the slipperiness (judged by the amount over 3 minutes).Extrusion conditions C1 C2 C3
D Rotation speed 40 rpm 160℃ 170℃ 1
80°C 180°C Example 1 In a reaction vessel equipped with a stirrer and a reflux condenser, 280 parts of ion-exchanged water, 1 part of potassium oleate, 4 parts of cumene hydroperoxide, and 50 parts of EPDM latex (average particle size 0.07 μm) were added. (as a solid content), and after purging the inside of the container with nitrogen, ethylenediaminetetraacetic acid sodium salt (EDTA-2Na) 0.0001
After charging 0.0003 parts of ferrous sulfate and 2 parts of sodium formaldehyde sulfoxylate, 50 parts of styrene and 0.5 parts of n-octyl mercaptan were charged, and the reaction vessel was heated to 70°C. The polymerization was completed by heating and stirring for an hour. After cooling the obtained polymer latex, it was coagulated with sulfuric acid, filtered and washed, and dried to obtain a polymer powder having a reduced viscosity ηsp/c of 0.8. Examples 2 to 5 and Comparative Examples 1 to 3 The polymer powder prepared in Example 1 was mixed with 100 parts of polyvinyl chloride resin (average degree of polymerization 700) and 1 part of butyltin mercapto.
．． 5 parts of epoxy auxiliary agent, 1.0 part of dibutyltin maleate, and 0.5 part of dibutyltin maleate were mixed in a Henschel mixer in the amounts shown in Table 1 to obtain a vinyl chloride resin composition. The test results are shown in Table 1. Comparative Example 1 was prepared by adding a stabilizer etc. to vinyl chloride resin and was used as a blank.

[Table 1] Examples 6 and 7 and Comparative Examples 4 and 5 Each polymer powder was obtained by polymerizing the composition shown in Table 2 under the same conditions as in Example 1. 3 parts of each polymer, 100 parts of polyvinyl chloride resin (average degree of polymerization 700), 1.5 parts of butyltin mercapto
part, 1.0 part of epoxy auxiliary agent, 0.0 part of dibutyltin maleate.
5 parts in a Henschel mixer to obtain a vinyl chloride resin composition. Table 2 shows the test results for these vinyl chloride resin compositions.

[Table 2] Examples 8 to 10 and Comparative Examples 6 and 7 The compositions shown in Table 3 were polymerized under the same conditions as in Example 1 to obtain each polymer powder. 3 parts of each polymer, 100 parts of polyvinyl chloride resin (average degree of polymerization 700), 1.5 parts of butyltin mercapto
part, 1.0 part of epoxy auxiliary agent, 0.0 part of dibutyltin maleate.
5 parts in a Henschel mixer to obtain a vinyl chloride resin composition. Table 3 shows the test results for these vinyl chloride resin compositions.

[Table 3] Examples 11 to 17 and Comparative Examples 8 to 14 100 parts of each of the following thermoplastic resins were blended with 3 parts of the polymer obtained in Example 1, and 3 parts of the polymer obtained in Example 1 were mixed in a Henschel mixer. did. The obtained mixture was passed through a single screw extruder (
25φm/m), the extrusion amount (g/10 minutes) was measured for each resin at different temperatures as shown below, and a fluidity test was conducted. Moreover, the pressure (Kg-m) during extrusion was measured. The larger the extrusion amount and the lower the pressure, the greater the slipperiness. (1) ABS resin (Diapet ABS#3001; trade name, manufactured by Mitsubishi Rayon Co., Ltd.) Molding temperature: C1 = 180°C, C2 = 200°C, C3 = 2
00℃, head = 200℃, die = 200℃ (2) Styrene resin (Styrene NF-20; trade name,
(manufactured by Idemitsu Petrochemical Co., Ltd.) Molding temperature: C1 = 160°C, C2 = 180°C, C3 = 2
00°C, head = 200°C, die = 210°C (3) Polycarbonate resin (Novarex 7022:
Product name, manufactured by Mitsubishi Chemical Industries, Ltd.) Molding temperature: C1 = 230°C, C2 = 260°C, C3 = 2
70°C, head = 270°C, die = 280°C (4) Polyethylene resin (Hyzex 7000F; trade name, manufactured by Mitsui Petrochemical Industries, Ltd.) Molding temperature: C1 = 150°C, C2 = 165°C, C3 = 1
75°C, head = 175°C, die = 175°C (5) Polyester resin (Dianite PA-200:
Product name, manufactured by Mitsubishi Rayon Co., Ltd.) Molding temperature: C1 = 280°C, C2 = 280°C, C3 = 2
80°C, head = 260°C, die = 260°C (6) Polyphenylene ether resin (Noryl 731J
(manufactured by GE Plastics Co., Ltd.) Molding temperature: C1 = 200°C, C2 = 260°C, C3 = 2
60℃, head = 260℃, die = 260℃ (7) Vinyl chloride resin (Zeon PVC polymerization degree 700
) Molding temperature: C1=160°C, C2=170°C, C3=
180℃, head = 175℃, die = 180℃

[Table 4] As shown in Tables 1 to 4 above, by blending the polymer of the present invention with various thermoplastic resins, mold releasability and fluidity during molding are improved compared to conventional ones, and , the shape and gloss of the molded product are improved.

[Effects of the Invention] By blending the graft copolymer of the present invention with various thermoplastic resins such as vinyl chloride resin, it is possible to improve the fluidity and mold releasability of the thermoplastic resin during molding. It is also possible to improve the gloss and transparency of the molded product. Moreover, it has the effect of improving productivity.

Claims (2)

[Claims] Claim 1: 80 to 10 parts by weight of a styrenic monomer in the presence of 20 to 90 parts by weight (as solid content) of a non-crosslinked ethylene-propylene-nonconjugated diene copolymer rubber (a) latex. , a graft copolymer obtained by polymerizing at least one monomer (b) selected from the group consisting of methacrylic esters and acrylic esters [total amount of (a) + (b) 100 parts by weight] and the reduced viscosity ηsp/c of the free polymer when extracted with acetone is less than 2 (
Dissolve 0.1 g of polymer in 100 ml of chloroform and add 2
A graft copolymer having a lubricating effect, characterized in that: 2. 0.01 to 20 parts by weight of the graft copolymer having a lubricating effect according to claim 1 to 100 parts by weight of the thermoplastic resin.
A thermoplastic resin composition comprising parts by weight.